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11858793 | DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The drawings and the description hereinafter contain, for the most part, elements of a certain nature. They can therefore not only be used to understand the present invention better, but also contribute the definition thereof, where applicable. The invention can apply to different types of lift columns, in particular including links according to AU 2010212303, US 2009/008615, FR 2 573 832, FR 2 345 626, FR 2 786 476 or FR 2 780 472 as well as FR 3 043 747 to which the reader is invited to refer to. The thrust chains in applications of great height tend to bow. Bowing is a lateral displacement of the substantially vertical thrust chain. The bowing according to the axis of the chain links can be limited by a tight adjustment of the elements of the chain. The bowing perpendicular to the axis of the chain links is critical due to the aptitude of the chain to be folded from one link to the other. In order to counteract the bowing, the Applicant has developed a thrust lifting device1shown in the figures. The lifting device1is able to transmit a thrust force allowing for the lifting of loads. In the embodiment shown inFIGS.1to3, the lifting device1comprises four articulated lift columns2, four rotary pinions3each driving one of said lift columns2, four opposite arms4, and a movable stabilizer5. The lift columns2support a plateau6, for example a plateau of a show room. The lifting device1rests on a base. Each lift column2is provided with at least one meshing part20, and with at least one arm21directed upward from the meshing part20. The lift column2is made up of links22with a link of rank1at the upper end of the upwardly directed arm21and running links of rank n, with n comprised between 2 and N the number of links22of the lift column2. The running links of rank n are part either of the meshing part20, or of the upwardly directed arm21, according to the position of the lift column2in lifting. For example, in the low position, the link of rank3is in the meshing part20and passes to the upwardly directed arm21rapidly after the beginning of the lifting; in the low position, the link of rank N−3 is in the opposite arm4and passes to the meshing part20then to the upwardly directed arm21near the end of the lifting. The pinion3is in constant meshing connection with said meshing part20. The meshing part20can be straight, for example aligned on the upwardly directed arm21, or, preferably, rounded hugging the shape of the pinion3. The pinion3is driven by an electric motorization, optionally with reducer, or hydraulic motorization. The arm4opposite the upwardly directed arm21is formed by resting links22. The resting links22are able to pass to the meshing part20then to the upwardly directed arm21by rotation of the pinion3in the direction of the lifting. The active links22i.e. subjected to compression, are able to pass to the meshing part20then to the opposite arm4by rotation of the pinion3in the direction of descent. The opposite arm4is housed in a magazine7. The magazine7is, more preferably, horizontal. The four magazines7can be disposed on two parallels, the end of a first magazine7opposite a first pinion3facing the end of a second magazine7opposite a second pinion3. Each magazine7can contain the resting links22on one row or, preferably, several rows with folding at the end of the row. The resting links22can form a flattened spiral. For a low maneuvering height, the resting links22can form a straight segment. The stabilizer5is movable along the upwardly directed arms21. The movable stabilizer5is able to stabilize the lift column2in position in the horizontal plane and in orientation. The stabilizer5has the form of a spaced frame50. The stabilizer5can be mechanically welded. Here, the stabilizer5comprises a rectangular frame50with two side members51and two cross-members52; two intermediate spacers53parallel to the cross-members52and equally spaced; and four diagonal legs54, one extending from an end cross-member52to an intermediate spacer53, the second extending from the opposite end cross-member52to the opposite intermediate spacer53and the third and fourth crossing in an X between the two intermediate spacers53. Two crossed Vs are formed. The frame50has a size low in height, defined by the height of the beams that form it, and a low mass. Each movable stabilizer5comprises one ring55per lift column2. The frame50rigidly connects the rings55. Each ring55comprises a sliding member56with respect to the corresponding lift column2and a stabilizer5finger57for driving the movable stabilizer5in motion. The stabilizer finger57is bearing on the corresponding lift column2in the position ofFIG.1, which is with maximum lift. The stabilizer finger57is inactive in the position ofFIG.3, in the low position. In the position ofFIG.2, a mid-stroke, the stabilizer finger57makes contact on the corresponding lift column2while the stabilizer5is still in the low position. In the position ofFIGS.2and3, the movable stabilizer5rests on the frames also supporting the pinions3. Thus, during the first portion of the rising stroke, the movable stabilizer5remains in the low position, and during the second portion of the rising stroke, the movable stabilizer5rises at the same speed as the plateau6. In the embodiment shown, the stabilizer5is at rest on the first half of the stroke of the lift column2and is supported in the vicinity of the link of rank N/2±1 on the second half of said stroke. The finger57has the shape of an inverted T with an asymmetric bar. The foot58of the T is fastened to the ring55, here by screws. The large portion59of the bar of the T passes under the ring55while being able to directly transmit a compression force, thus relieving the screws. The large portion59of the bar of the T is protruding between the link22cheeks26along a direction perpendicular to the axes of the bars24while remaining distant from the bars24. The large portion59of the bar of the T interferes with a tappet23according to the respective positions of said large portion and of said tappet23along the axis of the bars24. InFIG.7, the large portion59of the bar of the T substantially occupies the space between the inside cheeks of links22in such a way as to substantially intercept any tappet23during mounting. InFIG.8, the large portion59of the bar of the T substantially occupies half the space between the inside cheeks of links22in such a way as to intercept a corresponding tappet23and to allow to pass a non-interfering tappet23, for another stabilizer, such as the tappet23ofFIG.7, during mounting. The small portion60of the bar of the T is protruding a few millimeters, cf.FIG.5. The small portion60of the bar of the T is protruding from the thickness of a ring55collar62in such a way as to directly transmit to the lower end of the collar62a compression force. The sliding member56can comprise pads61made from a material with a low friction coefficient. The sliding member56forms a sheath or guide of links22, in contact with two links22. The height of the sliding member56greater than the height of a link22makes it possible to provide for the position of two links22in X and in Y and according to the angles (X{circumflex over ( )}Z) and (Y{circumflex over ( )}Z). In other terms, the position in the horizontal plane and the vertical orientation of two links22. Said two links22cooperating with the sliding member56are of rank N/2±1 in the case of a stabilizer, of ranks N/3±1 and 2N/3±1 in the case of two stabilizers, etc. The ring55surrounds the upwardly directed arm21of the lift column2on the four sides. The ring55comprises a folded collar62opposite the upwardly directed arm21. The collar62is horizontal. The collar62is provided with fastening holes for the frame50. The ring55extends, cf.FIG.5, over a height greater than the height of two links22. More precisely, the ring55extends from the middle bar24of a link of rank n to the lower bar24of the link of rank n+2. The lift column2is formed from links22articulated on bars24provided with rollers25, cf.FIGS.4to6. The rollers25are provided to come into contact with the pinion3. The links22comprise cheeks26disposed symmetrically with respect to a central plane. The cheeks26are identical to one another. The cheeks26are of a substantially constant thickness perpendicularly to the main plane thereof. Here, the cheeks26have the form of flats with a generally rectangular shape, with rounded corners towards the pivot axis. The cheeks26are formed from simple flats superimposed in thickness. Alternatively, the cheeks26are formed from flats with an offset in thickness formed at the press or from machined parts. Holes and notches are arranged in the flats for the mounting of bars. The cheeks26are disposed in two rows of outside cheeks and two rows of inside cheeks in contact. The cheeks26bear against one another by their edge perpendicular to the axis of the column2. The cheeks26are provided with two holes on the side of the pivot axis and one hole and two notches opposite the pivot axis. Two notches of two superimposed cheeks form the equivalent of a hole and allow a bar24to pass. The bars24are disposed staggered viewed from the side, cf.FIG.5. The outside cheeks are offset by a cheek half-height in relation to the inside cheeks. The rollers25can be disposed on ends of the bars24beyond the links22. The sliding member56forms a link roller guide, preferably in contact with at least three rollers25. The freedom of rotation of rollers25is taken advantage of, not only to cooperate with the corresponding pinion3, but also with the corresponding sliding member56. The sliding member56is disposed between two rows of rollers25or on either side of a row of rollers25, cf.FIG.9. The sliding member56forms a link cheek guide, cf.FIG.10. The sliding member56is in contact with two links22over a portion of the height of each one of the two links22. Alternatively, the sliding member56is in contact with a column pad guide, the pads being fastened to the links22or to the link bars24. In the embodiment ofFIG.11, the movable stabilizer5comprises a damper63, cf.FIG.11, by lift column2. The damper63is disposed between the stabilizer finger57on the one hand and the sliding member56. The finger57is slidably mounted according to the axis Z with respect to the sliding member56. The sliding of the finger57is produced along a rail68. The rail68is fastened to the ring55. The rail68is mounted along the axis Z. The rail68is disposed in the size in height of the ring55. The damper63is disposed parallel to the finger57. The damper63is connected to the finger57by a bracket64fastened to the finger57in an upper zone of the sliding member56. The bracket64covers the damper63and is fastened to an upper end of the damper63. A lower end of the damper63is fastened to the sliding member56. The bracket64and the finger57are slidably mounted. A spring70is disposed between the bracket64and the finger57, for example in blind holes arranged in the bracket64and the finger57. In the driving position of the stabilizer5, the spring70is compressed. In the low position of the stabilizer5, the finger57is distant from the tappet23and the spring70is relaxed. When the tappet23encounters the finger57, by the upper surface30thereof, the finger57can be displaced with respect to the sliding member56with dampening of said displacement by the damper63. In the case of several movable stabilizers, one damper63is provided per lift column2and per movable stabilizer5. The damper63reduces the acceleration of the stabilizer5when the stabilizer finger57comes into contact with the lift column2. The forces and the mechanical vibrations in the lift column2and in the pinion3, and the noise are reduced. In the absence of such a damper, the finger57is permanently fastened to the ring55. Each movable stabilizer5comprises at least one active damper in the vicinity of the low position. The low position damper reduces the acceleration of the stabilizer5at the arrival of the stabilizer in the low position. The mechanical vibrations and the noise are reduced. As shown, the damper63is also during the arrival of the stabilizer5in the low position. To this effect, seeFIG.18, the frame50is provided with a lower damper71directed downwards. The damper71is provided to cooperate with a corresponding surface of a stationary portion of the device1. Said surface can be horizontal. Said surface can be formed from an upwardly directed arm. The damper71can be connected to a plate72fastened, for example screwed, to the frame50. The damper71can be made up of a block of elastomer material. When the tappet23drives the finger57to lift the stabilizer5, the damper71is separated from the stationary surface. During the descent of the stabilizer5, the damper71stamps the stationary surface. The tappet23moves away from the finger57. The mass of the stabilizer5rests on the damper71. The column2is not concerned with the mass of the stabilizer5. The downward docking of the stabilizer5is dampened. Each lift column2comprises one tappet23per movable stabilizer5. The tappet23is able to support said movable stabilizer5, in particular by bearing on a stabilizer finger57. The tappet23is integral with the upwardly directed arm21of the lift column2. The tappet23is fastened to at least one axis of links. As shown inFIGS.4to8, the tappet23is supported by two link bars24that belong to the same row. The row of bars24is next to the pivot axis of the links. Each tappet23is fastened to links22of an equal rank for the same movable stabilizer5in the case of at least two lift columns2. The tappet23has a general parallelepiped rectangular shape with a main dimension in the direction of the height, a secondary dimension in the direction of the axes of the bars24, and a third dimension in the direction perpendicular to the axes of the bars24. Chamfers are arranged on the horizontal edges facing the other row of bars24, distal from the pivot axis of the links, in this case. The tappet23has an upper surface30disposed parallel to the plane XY. The upper surface30has a clear edge, i.e. with a low connection fillet radius, with a surface of the tappet23flush with the edges of links22. The upper surface30forms a support for the stabilizer5in a position other than the low position. The tappet23has two through-holes27is each one of which passes a link bar24. The tappet23is disposed between two link cheeks26. The tappet23is flush with edges of link cheeks, retaining the size of the lift column2. The tappet23is mounted on the side of the lift column2opposite the pinion3. The tappet23comprises, here, two parts28of similar shape separated by a plane passing through the axes of the two bars24engaged with the tappet23. Said parts28are in contact by said plane. Said parts28are in contact between the two bars24, and beyond each bar24. Said parts28are maintained together. Said parts28are tightened by at least one screw29that passes in a smooth through-hole of one of the parts and engages with a tapped hole of the other part. In the embodiment ofFIG.7, one of said parts has a smaller width that the other part, in the direction of the axis of the bars24. In coordination with the shape of the stabilizer fingers, this allows the tappet23ofFIG.7to lift the finger57ofFIG.7and to pass next to the finger57ofFIG.8. The tappet23ofFIG.7is capable of remaining inactive on a finger57of a lower stabilizer and to lift a finger57of an upper stabilizer, in the case of two stabilizers. The two stabilizers5are superimposed in the low position and spaced in the high position. In the embodiment ofFIG.8, said parts28have an equal width, in the direction of the axis of the bars24. The tappet23is provided to support a single stabilizer5or a lower stabilizer5. Each lift column2comprises at least two tappets23. The tappets23of each lift column2are disposed with an offset in a horizontal plane in such a way that a first tappet23supports a first finger57after having passed next to a second finger57and that a second tappet23supports the second finger57. The lifting device1comprises two guide rails8of the plateau6. The position in X and in Y of the plateau6is determined by the guide rails8. Alternatively, one guide rail8can be sufficient. Each movable stabilizer5is guided by at least one guide rail8. Each movable stabilizer5is provided with a member for cooperation with the corresponding guide rail8, for example in the form of pads. In the embodiment ofFIG.12, the stabilizer5is driven by an on-board motorization65on said stabilizer5and coupled to pinions66similar to the pinion3. The stabilizer5is then able to be displaced in autonomy along lift columns2. This embodiment makes it possible to adjust the height of the stabilizer5independently of the height of the plateau6, for example for work that uses the stabilizer5as a work platform. In the embodiment ofFIG.13, the stabilizer5is driven by a flexible connection67comprising an end fastened to the plateau6and an end fastened to the stabilizer5. In the embodiment ofFIG.14, the lifting device1comprises a lower pair of scissor supports9and an upper pair of scissor supports10. The movable stabilizer5is mounted between said pairs of scissor supports. The lower pair of scissor supports9is mounted between the movable stabilizer5and the base. The upper pair of scissor supports10is mounted between the movable stabilizer5and the plateau6. Each pair of scissor supports9,10has a structure as an articulated X at the center thereof, at a lower end and at an upper end and slidably mounted limited at the other lower end and at the other upper end. The displacement of the plateau6drives the upper pair of scissor supports10, then once the latter is in sliding abutment, the movable stabilizer5and the lower pair of scissor supports9. The pairs of scissor supports9,10provide suitable spaced, excellent lateral stability. In the embodiment ofFIG.15, the lifting device1comprises a pulley and cable mechanism that drives the movable stabilizer5. The pulley and cable mechanism comprises a pulley11mounted freely on the plateau6and a cable12that passes through the pulley11and fastened at one end to the movable stabilizer5and at the other end to a stationary portion of the lifting device1, near the base. The length of the cable12is such that the movable stabilizer5is located at mid-height when the plateau6is in the high position. Alternatively, said other end is driven by the shaft of the pinion3, coupled to a winding drum. In the embodiment ofFIG.16, the lifting device1comprises at least two additional lift columns200dedicated to the movable stabilizer5. The movable stabilizer5is independent in height of the plateau6and of the lift columns2that support the plateau6. The reduced stroke and the low mass of the movable stabilizer5make it possible for the lift columns200to be of a reduced model in relation to the model of the lift columns2. Advantageously, the orientations of the lift columns200in relation to the lift columns2are chosen for good stability. The embodiment ofFIG.17is similar to the embodiment ofFIG.14, the lifting device1comprising two movable stabilizers5and three pairs of scissor supports, lower9, intermediate11and upper10. Each movable stabilizer5is mounted between two pairs of scissor supports. A displacement with a high stroke is obtained. In the embodiments shown, the lifting device1comprises at least two, for example four, articulated lift columns2each provided with at least one meshing part20, and with at least one arm21directed upward from the meshing part20. Each lift column2is made up of links22with a link of rank1at the upper end of the upwardly directed arm21and running links of rank n, with n comprised between 2 and N the number of links22of the lift column. The lifting device1comprises at least two, for example four, rotary pinions3each driving the corresponding lift column2by said meshing part20meshing with the pinion3. The lifting device1comprises at least two, for example four, arms4opposite the upwardly directly arms respectively and formed from resting links22. Said resting links22are able to pass to the meshing parts and to the upwardly directed arms by rotation of the corresponding pinion3. The lifting device1comprises at least one movable stabilizer5along said upwardly directed arms. The movable stabilizer5is able to be driven by each one of the lift columns2. Each movable stabilizer5is disposed in the vicinity of the link of rank B/(p+1) or multiple of B/(p+1), in the high position of the lifting device, with B the number of links22of the upwardly directed arm21in the high position of the lifting device, and p the number of movable stabilizers, preferably p being equal to 1, 2 or 3. | 20,816 |
11858794 | DESCRIPTION OF EMBODIMENTS Preferred embodiments of the disclosure will be described in detail below with reference to the accompanying drawings. Note that the disclosure is not limited to these embodiments, and, when there are a plurality of embodiments, the disclosure is intended to include a configuration combining these embodiments. Overall Configuration of Movement Control System FIG.1is a schematic view of a movement control system according to a first embodiment. As illustrated inFIG.1, a movement control system1according to the first embodiment includes a movable body10, a management system12, and a computation device14. The movement control system1is a system that controls movement of the movable body10that belongs to a facility W. The facility W is a facility that is logistically managed, such as a warehouse. In the facility W of the present embodiment, a truck V is stopped in an area Ar. The movement control system1picks up a pallet (load) P mounted on the truck (vehicle) V with the movable body10, and drops the pallet P in a predetermined standby position. The movement control system1also picks up a pallet P disposed in a predetermined standby position with the movable body10, and drops the pallet P in the truck V. In other words, the movement control system1performs unloading work or loading work of the pallet P from or on the truck V. The area Ar is an area which is set as a stop position of the truck V, and is divided by, for example, a white line or the like. An area where the movable body10moves is provided around the area Ar. The standby place can be provided at any place of the facility W. Further, although only one area Ar is illustrated in the facility W of the present embodiment, a plurality of the areas Ar may be disposed. Further, the number of the movable bodies10is not limited to two, and may be one or three or more. Truck FIG.2is a schematic view illustrating a schematic configuration of the truck. The truck V of the present embodiment is a vehicle that travels by driving a plurality of tires VE. The truck V is a vehicle on which a plurality of pallets P can be mounted. In the truck V illustrated inFIG.1, four pallets P are arranged in two rows. The pallets P are mounted in the storage chamber VA of the truck V, as illustrated inFIG.2. The truck V includes a side door VB. The side door VB is a door provided on each side of the storage chamber VA. The side door VB of the truck V is opened to allow the storage chamber VA to communicate with the exterior, so that the pallets P can be carried out. The truck V of the present embodiment includes a position in the storage chamber VA where the pallets P are held. The plurality of pallets P are arranged side-by-side within the storage chamber VA of the truck V. In the truck V of the present embodiment, the pallets are arranged in two rows in the storage chamber VA. Note that there are various arrangement patterns such as a case where the pallets are placed without intervals therebetween on the front side of the truck, a case where the pallets are placed without intervals therebetween on the rear side, or a case where the pallets placed in the storage chamber VA at intervals. The truck V of the present embodiment includes the side doors VB on both sides, and the movable body10can access the pallets P from each of the two side. The truck V of the present embodiment has a structure in which each side door VB is a rigid body and opens and closes vertically, but the side door VB may also be a curtain type door formed of a deforming fabric or plastic which opens and closes by moving its one end horizontally. Movable Body The movable body10is an automatically movable device. In the present embodiment, the movable body10is a forklift, so called an Automated Guided Forklift (AGF) or Automated Guided Vehicle (AGV). The movable body10moves within the facility W. The movable body10moves to the vicinity of the truck V, for example, along a route R. The route R is information transmitted from the computation device14. When the movable body10has reached the vicinity of the vehicle V, the movable body10moves based on the set route and picks up each pallet P, based on the position information on the pallet P. The route R will be described in detail below. Hereinafter, one horizontal direction is referred to as a direction X, and a direction orthogonal to the direction X in the horizontal direction is referred to as a direction Y. Further, the direction orthogonal to the horizontal direction, that is, the direction orthogonal to the directions X and Y, is referred to as a direction Z. FIG.3is a schematic view of a configuration of the movable body. As illustrated inFIG.3, the movable body10includes a vehicle body20, a mast22, a fork24, a sensor26, and a control device28. The vehicle body20includes a wheel20A. The mast22is provided at one end portion in the front-back direction of the vehicle body20. The mast22extends along a vertical direction (here, the direction Z) orthogonal to the front-back direction. The fork24is attached to the mast22in a manner movable in the direction Z. The fork24may be movable with respect to the mast22in the lateral direction of the vehicle body20(the direction intersecting the vertical direction and the front-back direction). The fork24includes a pair of tabs24A,24B. The tabs24A,24B extend from the mast22toward the front direction of the vehicle body20. The tabs24A,24B are disposed away from each other in the lateral direction of the mast22. In the front-back direction, the direction where the fork24is provided in the movable body10is referred to as a first direction, and the direction where the fork24is not provided is referred to as a second direction. The sensor26detects at least one of the position and orientation of an object present around the vehicle body20. The sensor26can also detect the position of the object relative to the movable body10and the orientation of the object relative to the movable body10. In the present embodiment, the sensor26is provided in the mast22, and detects the position and orientation of an object on the first direction side of the vehicle body20. However, the detection direction of the sensor26is not limited to the first direction, and for example, the detection may be performed on both of the first direction side and the second direction side. In this case, as the sensor26, a sensor for detection on the first direction side and a sensor for detection on the second direction side may be provided. The sensor26is a sensor that emits a laser beam, for example. The sensor26emits a laser beam while performing a scan in one direction (here, the lateral direction), and detects the position and orientation of an object based on reflected light of the emitted laser beam. The sensor26is not limited to the above, and may be a sensor for detecting a target object using any method. For example, the sensor26may be a camera or the like. Further, the position at which the sensor26is provided is not limited to the mast22. Specifically, for example, a safety sensor provided on the movable body10may be also used as the sensor26. The use of the safety sensor eliminates necessity of newly installing the sensor. As the sensor26, a sensor provided with a mechanism that moves in the direction Z (vertical direction) with respect to the fork may also be provided. Thus, by moving the sensor in the direction Z, sensing can be performed without conjunction with the motion of the mast of the forklift. The control device28controls the movement of the movable body10. The control device28is a computer, and includes a control unit and a storage unit. The storage unit is a memory for storing various types of information such as the details of computations and programs of the control unit, and includes at least one of a RAM, a main storage device such as a ROM, and an external storage device such as a HDD. The control device28detects the position of the movable body10, moves based on the information on the route R supplied from the computation device14, and moves the pallet P. The control device28may also adjust the position of the fork24and the posture of the movable body10, based on the detection results of the position and orientation of the pallet P from the sensor26of the movable body10, and pick up and drop each pallet P. Further, the control device28outputs information detected by the sensor26to the computation device14. Management System FIG.4is a schematic block diagram of the management system. The management system12is a system that manages the flow of goods in the facility W. The management system12is a Warehouse Management System (WMS) in the present embodiment. However, the management system12may be any system not limited to the WMS, and may be a back-end system such as other production management systems. The management system12is provided at any position. The management system12may be provided in the facility W, or may be provided at a position away from the facility W to manage the facility W therefrom. The management system12is a computer, and as illustrated inFIG.3, includes a control unit30and a storage unit32. The storage unit32is a memory for storing various types of information such as the details of computations and programs of the control unit30, and includes at least one of a Random Access Memory (RAM), a main storage device such as a Read Only Memory (ROM), and an external storage device such as a Hard Disk Drive (HDD). The control unit30is the computation device, that is, a Central Processing Unit (CPU). The control unit30includes a work determination unit34. The control unit30implements the work determination unit34by reading and executing a program (software) from the storage unit32, and executes the processing. Note that the control unit30may execute the processing by one CPU, or may include a plurality of CPUs and execute the processing by the plurality of CPUs. The work determination unit34may be achieved by a hardware circuit. The work determination unit34determines each pallet P to be transported. Specifically, the work determination unit34determines the work details indicating the information on the pallet P to be transported, based on, for example, the input work plan. The work details are also considered to be information for identifying the pallet P to be transported. In the example of the present embodiment, the work determination unit34determines, as the work details, which pallet P (load) in which facility is to be transported, by when the pallet is to be transported and to where the pallet is to be transported. That is, the work details are information indicating the facility in which the target pallet P is stored, the target pallet P, the transport destination of the pallet P, and the time for transporting the pallet P. The work determination unit34transmits the determined work details to the computation device14. Computation Device FIG.5is a schematic block diagram of the computation device. The computation device14is a device that is provided in the facility W, computes information on the movement of the movable body10, or the like, and outputs the information to the movable body10. Further, the computation device14communicates with the truck V, and acquires information on the truck V that is stopped in the area Ar of the facility W. The information on the truck V includes information on whether to perform work in the facility W, and information on the type, position, or the like of each pallet P mounted on the truck V or each pallet P to be mounted on the truck V in the facility W. The computation device14is a computer, and as illustrated inFIG.4, includes a control unit40and a storage unit42. The storage unit42is a memory for storing various types of information such as the details of computations and programs of the control unit40, and includes at least one of a RAM, a main storage device such as a ROM, and an external storage device such as a HDD. The control unit40is a computation device, that is, a CPU. The control unit40includes a work details acquisition unit50, a truck information acquisition unit51, a movable body selection unit52, a route acquisition unit54, a reference position/posture acquisition unit56, and an information output unit60. The control unit40implements the work details acquisition unit50, the movable body selection unit52, the route acquisition unit54, the information output unit60, and the exclusive control unit58, by reading and executing a program (software) from the storage unit42, and executes the processing. Note that the control unit40may execute the processing by one CPU, or may include a plurality of CPUs and execute the processing by the plurality of CPUs. At least a part of the work details acquisition unit50, the truck information acquisition unit51, the movable body selection unit52, the route acquisition unit54, the reference position/posture acquisition unit56, and the information output unit60may be achieved by a hardware circuit. The work details acquisition unit50acquires information on the work details determined by the management system12, that is, information on each pallet P to be transported. The work details acquisition unit50identifies the pallet P to be unloaded from the truck V, based on the information on the pallet P in the work details, and identifies the place where the pallet P is provided, and the place to which the pallet P is to be transported. For example, the storage unit42stores information on the pallet P, the truck V, and the standby place in association with each other, and the work details acquisition unit50reads the information from the storage unit42to identify the work details. The movable body selection unit52selects the target movable body10. The truck information acquisition unit51communicates with the truck V to be stopped in the facility W, and acquires information from the truck V. The movable body selection unit52selects a target movable body10from the plurality of movable bodies belonging to the facility W, for example. The movable body selection unit52may select the target movable body10by using any method, but may select, as the target movable body10, for example, the movable body10suitable for transporting the pallet P, based on the place of the pallet P identified by the work details acquisition unit50or the type of the truck V. The route acquisition unit54acquires information on the route R to the area Ar identified by the work details acquisition unit50. The route acquisition unit54acquires information on the route R associated with each pallet P to be loaded or unloaded on or from the truck V. The route acquisition unit54also acquires information obtained by recalculating the route R, based on information from the reference position/posture acquisition unit56. The route acquisition unit54may acquire the route information from the management system12or may execute computing processing to acquire the route information. The first route R is preset, for example, for each area Ar, and, for example, the route acquisition unit54acquires, from the storage unit42, position (coordinate) information on the route R set for the area Ar identified by the work details acquisition unit50. The initial route R is set, for example, based on the position of the pallet P when the truck V is stopped in the set position in the area Ar. The route R is a path from the preset start position to the area Ar in the present embodiment. Here, the start position may be a position in which the movable body10is on standby. The route R is set in advance, based on map information on the facility W. The map information on the facility W is information including position information on an obstacle (such as a post) installed in the facility W or a passage through which the movable body10is capable of traveling. It can be said that the map information is information indicating an area in which the movable body10is movable in the area Ar. In addition to the map information on the facility W, the route R may be set based on vehicle specification information of the movable body10. The vehicle specification information is, for example, a specification which affects the movable path of the movable body10, such as the size and the minimum turn radius of the movable body10. In a case where the route R is set based on the vehicle specification information, the route R may be set for each movable body. Note that the route R may be manually set, based on the map information, the vehicle specification information, or the like, or may be automatically set by a device such as the computation device14, based on the map information, the vehicle specification information, or the like. When the route R is automatically set, for example, a desired pass point (Way point) may be designated. In this case, a shortest route R which avoids obstacles (such as a fixed object such as a wall) can be set while passing through the desired pass point. The reference position/posture acquisition unit56acquires information for identifying the position in the truck V of the first pallet P to be transported from or to the truck V, that is, the pallet P to be first unloaded from the truck V or the pallet P to be first loaded on the truck V. The reference position/posture acquisition unit56acquires, from the movable body10, position information on the first pallet P to be transported to the truck V. The position information on the pallet P in the truck V includes at least the position of the pallet P, and the horizontal orientation of the pallet P within the facility W. The position information on the pallet P in the truck V may include the height information on the pallet P. The information output unit60outputs the information acquired by the computation device14to the movable body10via a communication unit. The communication method between the movable body10and the computation device14is wireless communication in the present embodiment, but any communication method may be used. The information output unit60outputs the information on the route R acquired by the route acquisition unit54to the movable body10. Because the route R is a path toward the truck V, it can be considered to be information regarding the movement of the movable body10. Next, a processing operation by the movement control system1will be described usingFIGS.6to12. When transporting the pallets P to the truck V, the movement control system1acquires information on the first pallet P to be transported to the truck V, with the support of a worker. Then, the movement control system1sets the transport routes R for the second and subsequent pallets P, based on the acquired information on the first pallet P, and transports the pallets P by the movable body10. Hereinafter, the processing performed by the movement control system1will be described by describing processing by the truck, processing by the computation device, and processing by the movable body. Further, in the following, a case of unloading work will be described in which the movable body10carries out the pallets P in the truck V from the truck V after the truck V arrives at the facility W in a state where the pallets P are mounted on the truck V. FIG.6is a flowchart illustrating an example of processing performed by the truck. The processing illustrated inFIG.6is performed by a worker of the truck using various devices. First, the truck V outputs arrival information to the computation device14(step S12). Specifically, the truck V outputs information on a time to arrive at the facility W, and current position information. Note that when a schedule for arriving at the facility W, or the like is predetermined, the processing of step S12may not be executed. The truck V receives information on a stop position (step S14). The truck V acquires, from the computation device14, information on which position of the facility W the truck V is to stop. The truck V is stopped in the stop position (step S16). The worker stops the truck V in the designated area Ar. The truck V is stopped in the area Ar, and then outputs a position where the vehicle has been completely stopped to the computation device14(step S18). Next, the truck V prepares for transport of a pallet (load) and prepares for processing of identifying the first load (step S20). Specifically, in preparation for the transport of the pallet (load), the worker opens the side door VB to allow the pallets P to be carried out. Further, in preparation for the processing of identifying the first load, the worker makes it possible to notify the sensor26of the movable body10of the position of the pallet P to be carried out first. FIG.7is a schematic view illustrating an example of a position identifying device. The worker of the present embodiment disposes a position identifying device102in the vicinity of the loading platform on which the pallets P are installed. The position identifying device102is a mark detectable by the sensor26. Specifically, the position identifying device102is a mark formed of a material that reflects measurement light from the sensor26. The position identifying device102is formed in a two-dimensional pattern. By the sensor26detecting the position identifying device102of a two-dimensional pattern, the position and posture (orientation) of the pallet P associated with the position identifying device102can be detected. A unit that makes it possible to notify the sensor26of the movable body10of the position of the pallet P to be carried out first is not limited to the position identifying device102. As illustrated inFIG.7, a position identifying device104that can be gripped by a worker may be used. The position identifying device104is a portable mark that can be detected by the sensor26. The worker carries the position identifying device104and teaches the sensor26of the movable body10in the vicinity of the pallet P, which allows the position of the pallet P to be provided to the movable body10. Recognition processing in the movable body10will be described later. After the preparation is completed, the truck V outputs preparation completion information to the computation device14(step S22). Next, the processing performed by the computation device14will be described.FIG.8is a flowchart illustrating an example of the processing performed by the computation device. The computation device14acquires arrival information from the truck (step S32). The computation device14determines a truck stop position (step S34), and outputs information on the truck stop position to the truck (step S36). The computation device14determines whether the truck stop information has been acquired (step S38). The computation device14determines whether information indicating that the truck to which the stop position information has been provided has stopped in the designated position has been received. When the computation device14determines that the truck stop information has not been acquired (No in step S38), the processing returns to step S38. In other words, the computation device14repeats the processing in step S38until the truck stop information is acquired. When the computation device14determines that the truck stop information has been acquired (Yes in step S38), the computation device14acquires information from the management system and identifies a movable body (step S40). That is, a movable body carrying out the pallet P from the truck V is identified. The computation device14outputs a work instruction to the identified movable body (step S42). The work instruction includes information on a route for moving the movable body10that carries out the first pallet to the vicinity of the first pallet P in the area Ar, and an instruction to execute processing of detecting the position of the first pallet P. Next, the computation device14determines whether the information for identifying the position of the first load (pallet) has been acquired from the movable body (step S44). When the computation device14determines that the information for identifying the position of the first load (pallet) has not been acquired (No in step S44), the processing returns to step S44. In other words, the computation device14repeats the processing in step S44until information for identifying the position of the first load (pallet) is acquired. When the computation device14determines that the information for identifying the position of the first load (pallet) has been acquired (Yes in step S44), the computation device14generates an access path of the movable body for the first load, based on the information for identifying the first load (pallet)(step S46). That is, the computation device14generates a route along which the movable body10moves from the current position to the first pallet, based on the position information on the first pallet acquired by the movable body10. Upon setting the access path, the computation device14outputs the access path to the first load (pallet) to the movable body (step S48). Next, the computation device14generates the access paths for the second and subsequent loads, based on the information for identifying the first load (pallet) and the relative position information on the loads (pallets) (step S50). That is, the position of each pallet mounted on the truck V is calculated, based on the position information on the first pallet and the relative position information on each pallet mounted on the truck V, and the route along which the movable body10makes access is generated, based on the position of each pallet. The relative position information on each pallet can be acquired based on the information on the loading platform of the truck, the position of each pallet mounted, and the like, included in the information transmitted from the truck. Specifically, the computation device14acquires the position and posture of the first pallet. Further, the computation device14estimates the placement position of each pallet in the truck, for example, based on the number of the pallets mounted on the truck V obtained from the relative position information on the pallets and based on the information on the placement interval (for example, information on the thickness of a buffer material disposed between the pallets). The computation device14generates access paths for the second and subsequent pallets, based on the estimated position information and posture information of the second and subsequent pallets. Note that the computation device14may also acquire position information on the second and subsequent pallets, perform the same processing as in steps S46to S50, based on the acquired position information on the plurality of pallets, and regenerate (modify) access paths for the acquired transport target pallet and pallets subsequent thereto. Upon generating the access paths, the computation device14outputs the access paths for the second and subsequent loads (pallets) to the movable body (step S52). When the plurality of pallets P mounted on the one truck V are transported by the plurality of movable bodies10, the computation device14outputs respective access paths to the movable bodies10. Next, an operation of the movable body10will be described.FIG.9is a flowchart illustrating an example of processing performed by the movable body. The movable body10acquires work information transmitted from the computation device14(step S62). When acquiring the work information, the movable body10determines whether the information is for processing for the first load (pallet) (step S64). The movable body10may execute the processing in steps S64to S80by executing the processing included in the work information without executing the determination processing. In other words, the movable body10may perform the processing based on the work information and perform each of the processing operations inFIG.9. When the movable body10determines that the information is not for the processing for the first load (pallet) (No in step S64), the processing proceeds to step S76. When determining that the information is for the processing for the first load (pallet) (Yes in step S64), the movable body10moves to the vicinity of the target truck, based on the current access route (step S66). Next, the movable body10acquires information on an identification position, which is information for identifying the position of the first load (step S68). Specifically, as described above, the sensor26detects the position identifying device disposed by the worker in the vicinity of the first pallet. The position of the position identifying device detected by the sensor26is set as an identification position for identifying the first pallet. After detecting the identification position of the pallet, the movable body10outputs the identification position of the first load (pallet) to the computation device14(step S70). After outputting the identification position, the movable body10acquires the access path for the first load (pallet) (step S72). In other words, the route of movement from the current position to the pallet P, calculated based on the identification position by the computation device14, is acquired. The movable body10moves based on the access path, and transports the load (pallet) (step S74). After executing the processing in step S74or when making a determination of No in step S64, the movable body10acquires information on the access path for the target load (step S76). That is, the movable body10acquires information on the access paths for transporting the second and subsequent pallets and the route for moving to the target pallet. The movable body10moves based on the acquired access path, and transports each load (pallet) (step S78). Here, when approaching each of the second and subsequent pallets, the movable body10measures the position of the pallet during the approach, and acquires deviation information between the estimated pallet position and the measured pallet position. The pallets mounted on the truck may positionally deviated due to deviation when the pallets are mounted or variation in the thicknesses of buffer materials. Based on the calculation result of the positional deviation, the movable body10allows the fork to perform side-shift (move the position of the fork in the horizontal direction) and hold the pallet. In addition, the movable body10outputs information on the positional deviation of the pallet and the amount of side-shift to the computation device14. Further, in addition to the method of correcting the positional deviation by side-shift, the movable body10may use a method for updating and correcting an approach path, based on the positional deviation, or a method of correcting the positional deviation by using a servomechanism. The computation device14may regenerate or slightly modify the access routes, based on the acquired information on the transport of the second and subsequent pallets. Consequently, the influence due to the size variation of the buffer materials, the size variation of the pallets, and the load overhang on the pallet can be flexibly dealt with. The movable body10determines whether the processing has ended, that is, whether the transport of the pallets has ended (step S80). When the movable body10determines that the processing has not ended (No in step S80), the processing returns to step S76and the processing of transporting another pallet P is performed. When the movable body10determines that the processing has ended (Yes in step S80), the present processing ends. FIG.10is an explanatory diagram for describing processing performed by the movement control system.FIG.11is an explanatory diagram for describing processing performed by the movement control system.FIG.12is an explanatory diagram for describing processing performed by the movement control system. The movement control system1performs the processing inFIGS.6,8, and9in conjunction with the truck V, the computation device14, and the movable body10, thereby transporting pallets (loads) which are target objects. The movement control system1sets a standard access route R1for the movable body10to the area Ar in which the truck V is stopped. The access route R1is a route set in assumption that the truck V is stopped in the standard position in the area Ar. Here, because the truck V is driven and stopped by the worker, as illustrated inFIG.10, the truck V may not stop in the center of the area Ar, and may deviate from the presumed position. When the movable body10moves along the route R1in this deviated state, it takes a long time to find the first pallet P. It is also possible to mistakenly recognize another pallet. Further, the calculation load also increases when the plurality of pallets P are detected each time. In the movement control system1of the present embodiment, as illustrated in step S92ofFIG.11, the movable body10is moved to the vicinity of the truck V, based on the route R1when the first pallet P is picked up. Thereafter, the movable body10detects the position identifying devices102,104that the worker has arranged such that they are capable of being recognized by the movable body10, thereby detecting the position of the first pallet. The movement control system1calculates a route R2to the position of the first pallet, based on the detected results, and moves the movable body10as illustrated in step S94. This allows the movable body10to move to a position where it is easy to pick up the first pallet. The processing of picking up each pallet with the movable body10will be described below usingFIG.12. When picking up each pallet P, the movable body10moves from a position away from the pallet P as illustrated in step S102to the vicinity of the pallet P as illustrated in step S104. Next, the movable body10moves the fork24in the vertical direction to the hold position of the pallet P, as illustrated in step S108. The movable body10extends the fork24in the horizontal direction and inserts the tip of the fork24into the insertion position of the pallet P, as illustrated in step S110. The movable body10moves the fork24vertically upward with the fork24inserted into the pallet P and retracts the fork24to hold the pallet P with the fork24, as illustrated in step S112. The movable body10then retracts the fork24to hold the pallet P at the base portion of the fork24, as illustrated in step S114. Although the present embodiment has been described as a case in which the fork24is extended and retracted horizontally, the movable body10itself may move in the front-back direction without extending and retracting the fork24to bring the positional relationship between the fork24and the pallet to the above state. The movement control system1calculates access routes R3to other pallets, based on the position information on the first pallet P and the information on the relative position of the other pallets in the truck V, which are detected during transport of the first pallet P. Thus, as illustrated in step S96inFIG.11, the access routes R3whose positions are adjusted according to the posture of the truck V is calculated. The movement control system1moves the movable body10, based on the calculated access routes R3. Effects of Present Embodiment As described above, the movement control system1according to the present embodiment can move the movable body10with high accuracy to the pallets mounted on the truck, which is the target area, by calculating the access routes for the second and subsequent pallets, based on the position information on the first pallet. Further, during transport of the first pallet, the position information on the first pallet is detected based on the assistance of the worker, and the second and subsequent pallets can be automatically transported. Thus, the burden on the worker can be reduced and the accuracy of access to the pallets can be increased. According to the movement control system1, it is also possible to improve throughput by increasing the speed of access to the pallets. Because the movement control system1can identify the position by detecting the position identifying devices102,104by the sensor26, it is possible to reduce an increase in a work burden on the worker. Further, it is preferable that in the movement control system1, the movable body10be provided with a mechanism for sliding the fork24and a mechanism for tilting the fork24so that the position of the fork24holding the pallet P is finely adjusted. This can increase the allowable deviation amount of the information for identifying the position information on the first pallet using the position identifying devices102,104, and thus increase the workability. The movement control system1can finely adjust the position of the fork24holding each pallet P, even when the positions of the second and subsequent pallets are deviated. Thus, it is possible to absorb the positional deviation due to the size variation of the pallets, the size variation of the buffer materials, and the overhang of the load on the pallet, and further increase the flexibility and improve the operating ratio. Further, in the above embodiment, each pallet, which is the target object, is picked up from the truck, which is the target area, but the present disclosure can also be used in cases where each pallet, which is the target object, is dropped into the truck, which is the target area. In this case, when the movable body10drops the target objects, the position of each pallet Pin the target area is detected, the positions where the second and subsequent pallets are dropped are determined by using the result, and the access route is calculated. Note that when the pallet is dropped, the movement control system1detects the environment on both sides of the pallet drop position. For example, in the case of the first pallet, the positions of columns or walls of the loading platform of the truck is grasped. In the case of the second and subsequent pallets, the movement control system1estimates the position of an adjacent pallet load and the position of a buffer material and sets an access route. In the case of the last pallet, the movement control system1sets an access route on the basis of the load of the adjacent pallet and the information on the columns or walls of the loading platform. It is also preferable that the movable body move based on the information on the access route, and that the movable body drop the load while performing fine modification by the side shifting mechanism when finally dropping the load. FIG.13is an explanatory diagram for describing processing for dropping a target object in the movement control system.FIG.14is an explanatory diagram for describing processing for dropping a target object in the movement control system. In this case, as illustrated in step S132ofFIG.13, the movement control system1moves the movable body10holding the pallet P to be dropped, to the vicinity of the truck V to which the first pallet P is to be dropped, based on a route R4. Here, the route R4is the route when the truck V is stopped in an ideal position in the area. Thereafter, the movable body10detects the position identifying devices102,104that the worker has arranged such that they are capable of being recognized by the movable body10, thereby detecting the position where the first pallet is to be dropped. The movement control system1calculates a route R5to the position where the first pallet is to be dropped, based on the detected results, and moves the movable body10as illustrated in step S134. This allows the movable body10to move to a position where it is easy to drop the first pallet. The processing of dropping each pallet with the movable body10will be described below usingFIG.14. When dropping each pallet P, the movable body10moves from a position away from a drop position as illustrated in step S142to the vicinity of a position in the truck V where the pallet P is to be dropped as illustrated in step S144. Next, the movable body10moves the fork24in the vertical direction to the hold position of the pallet P, as illustrated in step S146. The movable body10extends the fork24in the horizontal direction, and moves the pallet P to immediately above the position in the truck V where the pallet P is to be dropped, as illustrated in step S148. The movable body10moves the fork24vertically downward with the fork24inserted into the pallet P to bring the pallet P into contact with the truck V, as illustrated in step S150. Thereafter, the fork24is retracted to leave the movable body10away from the pallet P, as illustrated in step S152. The movement control system1calculates access routes R6to other pallets, based on the position information on the first pallet P and the information on the relative position of the other pallets in the truck V, which are detected during transport of the first pallet P. Thus, as illustrated in step S136inFIG.13, the access routes R6whose positions are adjusted according to the posture of the truck V is calculated. The movement control system1moves the movable body10based on the calculated access routes R6to drop the pallets P at respective positions of the truck V. In this manner, even when dropping the target objects at the predetermined positions, the movement control system1can identify the drop position of the first pallet while obtaining the support of the worker, determine the drop positions of the second and subsequent pallets by using the result, and transport the pallets in an automatic operation, thereby transporting the target objects efficiently with high accuracy. In the above embodiment, the position of the first pallet is detected by the sensor of the movable body10, but the present disclosure is not limited thereto.FIG.15is a schematic view illustrating an overview of a movement control system according to another embodiment.FIG.16is a schematic view illustrating an example of a position identifying device. The movement control system illustrated inFIG.15includes cameras150,152. The movement control system detects the position of a position identifying device202with the cameras150,152. Here, as illustrated inFIG.16, the position identifying device202includes a tip portion corresponding to the tip of the fork24, and a gripping portion held by the worker. The position identifying device202includes marks210,212,214, and216on the externally exposed portion with the tip portion inserted into the pallet P. When the position identifying device202is inserted into the pallet P to the correct position, a switch220is disposed in a position that contacts the pallet P. When information for identifying the position of the first pallet P is acquired, the worker inserts the position identifying device202into the first pallet P and brings the switch220and pallet P into contact. When the movement control system1acquires information that the switch220and the pallet P are in contact with each other, the marks210,212,214and216of the position identifying device202are detected by the cameras150,152. In addition, although the marks are detected by the cameras150,152in the present embodiment, the method for detecting the marks is not limited thereto. For example, instead of the cameras, a laser sensor may detect the position of the object. Position information on the detected marks210,212,214, and216is detected as information for identifying the position of the first pallet P. The movement control system1calculates the position of the pallet P and determines an access route, by analyzing the image information in which the marks210,212,214, and216are captured. In this manner, the position of the pallet P may be calculated by capturing the position identifying device202associated with the first pallet P by the camera disposed in the facility W. Further, by using the position identifying device202, the position where the fork24is disposed when the pallet P is held can be detected with high accuracy. Thus, the position detection accuracy can be further improved. Note that the switch220may not be required. In the movement control system1of the above embodiment, the position identifying device is detected, and, based on the result, the information for identifying the position of the first pallet is acquired, but the method of acquiring the information for identifying the location of the first pallet is not limited thereto. In the movement control system1, the position of the first pallet may be detected based on information when the worker controls the operation of the movable body10to actually move the pallet.FIG.17is a flowchart illustrating another example of the processing performed by the computation device.FIG.18is a flowchart illustrating another example of the processing performed by the movable body. The computation device14acquires arrival information from the truck (step S32). The computation device14determines a truck stop position (step S34), and outputs information on the truck stop position to the truck (step S36). The computation device14determines whether the truck stop information has been acquired (step S38). The computation device14determines whether information indicating that the truck to which the stop position information has been provided has stopped in the designated position has been received. When the computation device14determines that the truck stop information has not been acquired (No in step S38), the processing returns to step S38. In other words, the computation device14repeats the processing in step S38until the truck stop information is acquired. When the computation device14determines that the truck stop information has been acquired (Yes in step S38), the computation device14acquires information from the management system and identifies a movable body (step S40). That is, a movable body carrying out the pallet P from the truck V is identified. The computation device14outputs a work instruction to the identified movable body (step S42). The work instruction includes information on the route for moving the movable body10that carries out the first pallet to the vicinity of the first pallet P in the area Ar, and an instruction to execute processing of detecting the position of the first pallet P. Next, the computation device14determines whether information on the transport route has been acquired from the movable body as information for identifying the position of the first load (pallet) (step S202). When the computation device14determines that the information for identifying the position of the first load (pallet) has not been acquired (No in step S202), the processing returns to step S202. In other words, the computation device14repeats the processing in step S202until the information for identifying the position of the first load (pallet) is acquired. When it is determined that the information for identifying the position of the first load (pallet) has been acquired (Yes in step S202), the computation device14generates access paths for the second and subsequent loads, based on the information for identifying the first load (pallet) and relative position information on the loads (pallets) (step S50). That is, the position of each pallet mounted on the truck V is calculated, based on the position information on the first pallet and the relative position information on each pallet mounted on the truck V, and the route along which the movable body10makes access is generated, based on the position of each pallet. The relative position information on each pallet can be acquired based on the information on the loading platform of the truck, the position of each pallet mounted, and the like, included in the information transmitted from the truck. Upon generating the access paths, the computation device14outputs the access paths for the second and subsequent loads (pallets) to the movable body (step S52). When the plurality of pallets P mounted on the one truck V are transported by the plurality of movable bodies10, the computation device14outputs respective access paths to the movable bodies10. Next, an operation of the movable body10will be described.FIG.18is a flowchart illustrating another example of the processing performed by the movable body. The movable body10acquires work information transmitted from the computation device14(step S62). When acquiring the work information, the movable body10determines whether the information is for processing for the first load (pallet) (step S64). The movable body10may execute the processing in steps S64to S80by executing the processing included in the work information without executing the determination processing. In other words, the movable body10may perform the processing based on the work information and perform each of the processing operations inFIG.9. When the movable body10determines that the information is not for the processing for the first load (pallet) (No in step S64), the processing proceeds to step S76. When determining that the information is for the processing for the first load (pallet) (Yes in step S64), the movable body10transports the first load (pallet) based on a control instruction (step S222). Here, the control instruction is input by the worker. As the input method by the worker, an input may be performed by a remote operation using a remote controller, or may be performed by operating the operation unit of the movable body10. When the remote controller is used, the remote operation may be performed while the site is checked using the monitor, or may be performed while the movable body10and the pallet are viewed on-site. Next, the movable body10outputs, to the computation device, the information on the route for transporting the first load (pallet) as information on an identification position which is information for identifying the position of each pallet (step S224). After executing the processing in step S224or when making a determination of No in step S64, the movable body10acquires information on the access path for the target load (step S76). That is, the movable body10acquires information on the access paths for transporting the second and subsequent pallets and the route for moving to the target pallet. The movable body10moves based on the acquired access path, and transports each load (pallet) (step S78). The movable body10determines whether the processing has ended, that is, whether the transport of the pallets has ended (step S80). When the movable body10determines that the processing has not ended (No in step S80), the processing returns to step S76and the processing of transporting another pallet P is performed. When the movable body10determines that the processing has ended (Yes in step S80), the present processing ends. The movement control system1may perform the transport of the first pallet by the worker's operation, identify the position of the first pallet, based on the information on the operated route, and calculate the access routes for the second and subsequent pallets. Thus, the worker transports only the first pallet, and it is possible to automatically detect the access routes for the remaining pallets. Further, in the case of the present embodiment, the movable body10operated by the worker may be provided with a driver seat. In addition, it is preferable that the movement control system1be provided with a monitoring device, and that the movable bodies10other than the target movable body10be not approach the worker when the worker is performing auxiliary operations for identifying the position of the first pallet. This increases the safety of a work operation. Other Examples of System Further, in the present embodiment, the management system12determines work details indicating information on each pallet P, and the computation device14identifies the target movable body10, and acquires the route R. However, the processing details of the management system12and the computation device14are not limited thereto. For example, the management system12may perform at least some of the processing of the computation device14instead, or the computation device14may perform at least some of the processing of the management system12instead. Further, the management system12and the computation device14may be configured as one device (computer). The embodiment of the disclosure is described above, but the embodiment is not limited by the embodiment above. Further, the constituent elements of the above-described embodiment include elements that are able to be easily conceived by a person skilled in the art, and elements that are substantially the same, that is, elements of an equivalent scope. Furthermore, the constituent elements described above can be appropriately combined. Further, it is possible to make various omissions, substitutions, and changes to the constituent elements within a range not departing from the scope of the above-described embodiment. For example, in the present embodiment, the target area is a vehicle such as a truck, but it is only required that the target objects (loads) be regularly arranged (aligned) within a predetermined range. The present disclosure can also be applied in cases where the target object is disposed in the area where a partition is provided. While preferred embodiments of the invention have been described as above, it is to be understood that variations and modifications will be apparent to those skilled in the art without departing from the scope and spirit of the invention. The scope of the invention, therefore, is to be determined solely by the following claims. | 53,646 |
11858795 | DETAILED DESCRIPTION Before any aspect of the present disclosure are explained in detail, it is to be understood that the present disclosure is not limited in its application to the details of construction and the arrangement of components set forth in the following description or illustrated in the following drawings. The present disclosure is capable of other configurations and of being practiced or of being carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of “including,” “comprising,” or “having” and variations thereof herein is meant to encompass the items listed thereafter and equivalents thereof as well as additional items. Unless specified or limited otherwise, the terms “mounted,” “connected,” “supported,” and “coupled” and variations thereof are used broadly and encompass both direct and indirect mountings, connections, supports, and couplings. Further, “connected” and “coupled” are not restricted to physical or mechanical connections or couplings. The following discussion is presented to enable a person skilled in the art to make and use aspects of the present disclosure. Various modifications to the illustrated configurations will be readily apparent to those skilled in the art, and the generic principles herein can be applied to other configurations and applications without departing from aspects of the present disclosure. Thus, aspects of the present disclosure are not intended to be limited to configurations shown but are to be accorded the widest scope consistent with the principles and features disclosed herein. The following detailed description is to be read with reference to the figures, in which like elements in different figures have like reference numerals. The figures, which are not necessarily to scale, depict selected configurations and are not intended to limit the scope of the present disclosure. Skilled artisans will recognize the non-limiting examples provided herein have many useful alternatives and fall within the scope of the present disclosure. It is also to be appreciated that material handling vehicles are designed in a variety of configurations to perform a variety of tasks. It will be apparent to those of skill in the art that the present disclosure is not limited to any specific material handling vehicle and can also be provided with various other types of vehicle configurations, including for example, order pickers, SWING-REACH®, and any other lift vehicles. The various systems and methods disclosed herein are suitable for any of driver controlled, pedestrian controlled, remotely controlled, and autonomously controlled material handling vehicles. As described herein, the present disclosure provides one or more pallet detection assemblies that may be configured to sense pallet loading on a material handling vehicle (MHV). In general, the pallet detection assemblies may include an actuation plate that is selectively movable relative to a body within which a proximity senor is housed. The actuation plate may be configured to move or displace non-pivotally relative to the body. That is, each point along the load detection plate moves in unison and travel the same amount of distance relative to the body. With reference toFIGS.1-3, a pallet detection assembly100is shown in accordance with one aspect of the present disclosure. The pallet detection assembly100may include a body102, an actuation plate104, an actuator106, a first spring assembly107, and a second spring assembly108. In general, the actuator106may movably couple the actuation plate104to the body102, so that the actuation plate104may displace non-pivotally relative to the body102against a biasing force of the first spring assembly107and the second spring assembly108. With specific reference toFIGS.3-6, the body102may define a cavity110within which a proximity sensor112may be at least partially housed. The body102may include a sensor mounting bracket132, a top wall134, a first side wall138, a second side wall140, a rear wall142, and a bottom wall144. In general, the top wall134, the first side wall138, the second side wall140, the rear wall142, and the bottom wall144may be coupled to one another or formed as a unitary component to define the cavity110. The rear wall142may define a first opening146, a second opening148, a third opening150, with the second opening148being arranged longitudinally between the first opening146and the third opening150. In the illustrated embodiment, a barrel152may be arranged generally concentrically with the third opening150and may extend from the rear wall142in a direction toward the actuation plate104. The sensor mounting bracket132may be engaged with the second side wall140longitudinally between the first opening146and the second opening148. The sensor mounting bracket132may support the proximity sensor112within the cavity110formed by the body102. In the illustrated embodiment, the proximity sensor112may include a sensor surface154arranged at one end thereof. The proximity sensor112may output a signal from the sensor surface154(e.g., a magnetic signal, an inductive signal, an electromagnetic sensor, etc.) and the proximity sensor112may be configured to detect if the output signal emitted from the sensor surface154is blocked or unblocked. It is to be appreciated that a variety of styles of sensors could be used in place of or in addition to a proximity sensor, including one or more mechanical or electrical switches, such as snap-action, or pressure switches or strain gauges, as non-limiting examples. In the illustrated embodiment, the actuation plate104may include a tab156coupled to the actuation plate104and that extends in a direction toward the body102. In general, the tab156may be arranged on the actuation plate104so that the tab156eventually aligns with and covers the sensor surface154of the proximity sensor112during non-pivotal displacement of the actuation plate104toward the body102. In the illustrated embodiment, the actuation plate104may include an angled portion157arranged an end thereof. The angled portion157may extend in a direction toward the body102. In some embodiments, the angled portion157may facilitate non-pivotal displacement of the actuation plate104relative to the body102if a load is dropped onto the forks of an MHV from above (i.e., not slide along the forks). The actuator106may include a cylinder158and a plunger160slidably received within the cylinder158. The cylinder158may be received within and coupled to the second opening148of the body102. The plunger160may be coupled to the actuation plate104. The slidable movement governed by the plunger160received within the cylinder158may provide a non-pivotal coupling between the actuation plate104and the body102. That is, the actuator106may be configured to movably couple the actuation plate104to the body102so that that actuation plate104is configured to non-pivotally displace relative to the body102. The first spring assembly107and the second spring assembly108may be configured to provide stability and a biasing force against which an input force may non-pivotally displace the actuation plate104in a direction toward the body102. The first spring assembly107and the second spring assembly108may be arranged on opposing sides of the actuator105. That is, the first spring assembly107may be coupled between the body102and the actuation plate104on one side of the actuator106and the second spring assembly108may be coupled between the body102and the actuation plate104on a longitudinally-opposing side of the actuator106. Each of the first spring assembly107and the second spring assembly108may include a spring162and a shaft164. Each of the springs162may be biased between the body102and the actuation plate104and may be configured to bias the actuation plate104in a direction away from the body102. In general, each of the shafts164may be slidably received within and arranged concentrically within the springs162. The shaft164of the first spring assembly107may be coupled to the first opening146of the body102. The shaft164of the first spring assembly107may be slidably received by one of the actuation plate104and the first opening146to enable the spring162of the first spring assembly107to compress during non-pivotal displacement of the actuation plate104in a direction toward the body102. The shaft164of the second spring assembly108may be configured to be slidably received within the barrel152of the body102to compress the spring162of the second spring assembly108during non-pivotal displacement of the actuation plate104in a direction toward the body102. In the illustrated embodiment, the shaft164of the second spring assembly108may extend partially toward but not into the barrel152, when the actuation plate104is in an extended position (seeFIG.5). In some embodiments, the shaft164of the second spring assembly108may at least partially extend into and through the barrel152, when the actuation plate104is in the extended position (seeFIG.21). With specific reference toFIG.6, during operation, the pallet detection assembly100may be mounted to an MHV in a location to ensure that a pallet supported on forks of the MHV engages the actuation plate104when the pallet is properly seated and received fully onto the forks. Prior to the MHV engaging a load, or when a load is not fully received on the forks, the actuation plate104may be in an extended position (seeFIG.6). As the MHV receives a palletized load, the pallet may engage the actuation plate104and provide an input force thereto that overcomes the biasing force of the first spring assembly107and the second spring assembly108, which results in the actuation plate104non-pivotally displacing toward the body102. As the actuation plate104non-pivotally displaces toward the body102, the tab156coupled to the actuation plate104may displace toward the sensor surface154of the proximity sensor112. Once the tab156displaces an amount sufficient to at least partially cover the sensor surface154, the proximity sensor112may transition from an unblocked state where the sensor surface154is unblocked by the tab156and a blocked position where the sensor surface154is at least partially blocked by the tab156. In some embodiments, when the proximity sensor112transitions to the blocked state, the MHV may have fully received the palletized load on the forks. With reference toFIGS.7-10, in some embodiments, the pallet detection assembly100may include one or more proximity sensors112. For example, as illustrated inFIGS.7-10, the proximity sensor112may be a first proximity sensor112and the pallet detection assembly100may include a second proximity sensor200having a sensor surface201. The body102may include a second sensor mounting bracket202engaged with the second side wall140longitudinally between the second opening148and the third opening150. The second sensor mounting bracket202may support the second proximity sensor200within the cavity110formed by the body102. In general, the first proximity sensor112and the second proximity sensor200may be axially aligned with and axially separated from one another. With specific reference toFIG.10, the body102may include a second tab204that is coupled to the actuation plate104and extends toward the body102. The second tab204may extend from the actuation plate104toward the body102a different distance than the tab156. In the illustrated embodiment, the second tab204may extend a further distance toward the body102than the tab156. In this way, for example, the pallet detection assembly100ofFIGS.7-10may define two pallet detection states. That is, when the second proximity sensor200transitions to the blocked state after the actuation plate104is displaced by an input force by a first distance d1, the MHV may be supporting a load on the forks but the load may not yet be fully received on the forks. If the actuation plate104is displaced further to a distance d2where the first proximity sensor112transitions to the blocked state, the MHV may have fully received the load on the forks. As described herein, the pallet detection assembly100may be installed on an MHV. Turning toFIGS.11-13, an MHV300may include one or more pallet detection assemblies100coupled to a fork carriage302. The fork carriage302may include a fork backrest304, a first fork306, and a second fork308each coupled to the fork carriage302, and a pair the pallet detection assemblies100. In the illustrated embodiment, the MHV300may include a one of the pallet detection assemblies100coupled to the fork carriage302adjacent to a laterally-outer edge310of the first fork306and another of the pallet detection assemblies100coupled to the fork carriage302arranged adjacent to a laterally-outer edge312of the second fork308. In some embodiments, the MHV300may include a controller314having memory316and a processor318. The controller314may be in communication with the first proximity sensor112and, in some embodiments, the second proximity sensor200. In some embodiments, the controller314may be in communication with a display320. In general, the arrangement of two or more of the pallet detection assemblies100on the fork carriage302may enable the detection of whether a load315is received on the first fork306and the second fork308and whether or not the load is askew. For example,FIG.14illustrates potential outputs of the proximity sensors112on both of the pallet detection assemblies100of the MHV300in the configuration of the pallet detection assemblies100that include one proximity sensor112. When both of the proximity sensors112are unblocked, the controller314may provide an indication, for example, to the display320, a warehouse management system (WMS) in communication with the controller314, or another external controller that a load is not received on the forks. If the only one of the pallet detection assemblies100is in the blocked state and the other is in the unblocked state, the controller may provide an indication that a load is arranged askew on the forks. If both of the pallet detection assemblies100are in the blocked state, then the controller314may provide an indication that the load is fully received on the forks and properly aligned. As described herein, in some embodiments, the pallet detection assembly100may include a first proximity sensor112and a second proximity sensor200.FIG.15illustrates potential outputs of the first proximity sensor112and the second proximity sensor200on both of the pallet detection assemblies100of the MHV300. That is, the MHV300may include a first pallet detection assembly and a second pallet detection assembly that both include a first proximity sensor112and a second proximity sensor200. When all of the proximity sensors are unblocked, the controller314may provide an indication that a load is not received on the forks. When one of the second proximity sensors200is in the blocked state and one of the second proximity sensor200is in the unblocked state (both of the first proximity sensors112are unblocked), the controller214may provide an indication that a load is arranged askew on the forks. When both of the second proximity sensors200are in the blocked state and both of the first proximity sensors112are in the unblocked state, the controller214may provide an indication that a load is centered but not fully received on the forks. When both of the second proximity sensors200are in the blocked state, one of the first proximity sensors112is in the blocked state, and one of the first proximity sensors112is in the unblocked state, the controller may provide an indication that a load is received on the forks but askew. When both of the second proximity sensors200and both of the first proximity sensors112are in the blocked state, the controller314may provide an indication that a load is fully received on the forks and properly aligned. In some embodiments, the pallet detection assembly100may be designed to include alternative shapes and configurations of the actuation plate104. For example,FIG.16illustrates an embodiment of the pallet detection assembly100that includes a spacer plate400coupled to an outer surface of the actuation plate104. The spacer plate400may provide a smooth surface against which a pallet or load may provide an input force to non-pivotally displace the actuation plate104relative to the body102. FIGS.17-18illustrated an embodiment of the pallet detection assembly100where the angled portion157extends vertically beyond a first end402of the body102(e.g., a top end from the perspective ofFIGS.17and18. In this way, for example, the angled portion157may further aid in non-pivotally displacing the actuation plate104relative to the body102when a load is vertically placed on the forks of the MHV300. FIGS.19-21illustrated an embodiment of the pallet detection assembly100where the tab156is integrated into the actuation plate104(e.g., integrally formed as a unitary component). In the illustrated embodiment, the actuation plate104may not include an angled portion. In the illustrated embodiment, the tab156is formed by a top surface404of the actuation plate104. In the illustrated embodiment, the proximity sensor112is moved (compared to the embodiment ofFIGS.1-6) within the cavity110to a top portion406of the cavity110. In this way, for example, as the actuation plate104is non-pivotally displaced toward the body102, the top surface404may eventually be displaced into a position where it blocks the sensor surface154of the proximity sensor112. While various spatial and directional terms, such as top, bottom, lower, mid, lateral, horizontal, vertical, front, and the like may be used to describe examples of the present disclosure, it is understood that such terms are merely used with respect to the orientations shown in the drawings. The orientations may be inverted, rotated, or otherwise changed, such that an upper portion is a lower portion, and vice versa, horizontal becomes vertical, and the like. Within this specification embodiments have been described in a way which enables a clear and concise specification to be written, but it is intended and will be appreciated that embodiments may be variously combined or separated without parting from the invention. For example, it will be appreciated that all preferred features described herein are applicable to all aspects of the invention described herein. Thus, while the invention has been described in connection with particular embodiments and examples, the invention is not necessarily so limited, and that numerous other embodiments, examples, uses, modifications and departures from the embodiments, examples and uses are intended to be encompassed by the claims attached hereto. The entire disclosure of each patent and publication cited herein is incorporated by reference, as if each such patent or publication were individually incorporated by reference herein. Various features and advantages of the invention are set forth in the following claims. | 19,111 |
11858796 | DETAILED DESCRIPTION This patent application relates to an apparatus for capping and decapping containers. In particular, this patent application relates to a container capper/decapper that can remove and replace a screw-on container cap. FIGS.1A and1Bdepict an exemplary embodiment of a capper/decapper system according to one embodiment of the present disclosure. As illustrated, the system100has four main components: the motor102, the transmission104, the driver mechanism106, and the coupler assembly108. The Motor In an exemplary embodiment, motor102is a DC-powered, brushless motor, such as those available Maxon Precision Motors, Falls River, MA. This type of motor offers a high-degree of controllability, when mated with a position controller, such as the EPOS and MAXPOS controllers available from Maxon Precision Motors, Inc. The position controller is interfaced with a capper/decapper control system (not illustrated), that may include one or more processors, component interfaces, and data storage/memory. It will be understood that any suitably controllable drive means could be utilized in place of the DC-powered, brushless motor. This could include other electric motors (stepper, AC-powered, etc.) or pneumatically driven motors. The Transmission Motor102is shown to be coupled to driver assembly106by transmission106. In one embodiment, transmission106is a 1:18 step-down ratio gearbox. This gearing ratio delivers a predetermined torque range and angular-positional accuracy to threaded drive shaft122facilitating the capping and uncapping of a particular container type. In a particular embodiment of the invention, the mean torque delivered by the motor is limited to a maximum of 56.8 mNm (millinewton meters). Other gear ratios, including 1:1, or direct drive are contemplated, and selection of a specific gear ratio depends from the particular motor and the types of caps/containers the system is intended to operate with. The Driver Mechanism As shown inFIG.1B, driver mechanism106includes ejector110, ejector nut112, coupler assembly sensor114, ejector sensor116, ejector nut sensor118, ejector nut alignment shaft120, and threaded drive shaft122. FIGS.2A,2B,2C and2Dprovide a bottom, top, side and perspective views, respectively, of ejector nut112. In one preferred embodiment of the invention, ejector nut112is shown to have six blades202extending radially from the threaded central channel204, and six alignment grooves206situated around the circumference of ejector nut base208. Although in this particular embodiment, six top blades and six alignment grooves are shown, only one of each is required for system operation. This feature redundancy is a design choice and simplifies the alignment of the ejector nut during assembly of driver mechanism106. Threaded central channel204is dimensioned to mate with threaded shaft122. FIGS.3A, and3Bshow a partial side view, and a partial cross-sectional side view, respectively, of driver mechanism106.FIG.3Ashows cowling302of the driver mechanism. A portion of ejector nut112can be viewed through cut-out304. As illustrated inFIG.3B, the outermost surface306of ejector nut112is preferably dimensioned so as to create a gap308between it and inner wall310of cowling302. Ejector110is shown, in cross-section, positioned below ejector nut112. This is further illustrated inFIG.3C, which provides a top cross-sectional view of driver mechanism106. As illustrated, the outermost radius312of ejector nut112is less than the inner radius314of cowling302. This creates gap308between ejector nut112and inner wall310of cowling302.FIG.3Calso illustrates the dimensional relationship between alignment groove206and ejector nut alignment shaft120. Groove206is contoured to conform to the shape of ejector nut alignment shaft120, so as to prevent the rotation of the ejector nut. However, alignment groove206is preferably dimensioned so as to allow for a gap308between the outer surface of the groove and the outer surface of ejector nut alignment shaft120. Gap308permits ejector nut112to translate along threaded shaft122as a function of the shaft's rotation (driven by transmission104), unimpeded by ejector nut alignment shaft120. FIGS.4A,4B,4C and4Dprovide a bottom, top, side and perspective views, respectively, of ejector110. In a preferred embodiment of the invention, ejector110is shown to have three elongated ejection rods402extending from the ejector's bottom surface403, which has a circular cross-section. Although three such rods are depicted in the figure, the number of rods is a design choice dictated by variables such as the type of element being ejected, as well as material, fabrication and assembly considerations. There is also a central, unthreaded channel404. As shown inFIG.5, the radius302of unthreaded channel404is greater than the outermost radius504of unthreaded channel404. This ensures a gap exists between unthreaded channel404and the outermost surface of threaded shaft122. This gap permits ejector110to translate along the longitudinal axis of threaded shaft122, without being impeded by that shaft.FIG.5also shows the dimensional relationship between ejector nut alignment shaft120and ejector110. The outer radius of ejector110must be limited to a dimension that ensures a gap506between ejector110and ejector nut alignment shaft120, thereby enabling ejector110to translate along the longitudinal axis of threaded shaft122, without impacting or otherwise contacting ejector nut alignment shaft120. As shown inFIG.6A, driver mechanism106includes three sensors: (i) coupler assembly sensor114, (ii) ejector sensor116, and (iii) ejector nut sensor118. In one example, coupler assembly sensor114is an optical fork sensor, mounted upon cowling302. One example of such a sensor is the PM-Y45-P Compact Photoelectric Sensor manufactured by the Panasonic Industrial Devices Company, a division of the Panasonic Corporation, Osaka, Japan. As shown inFIG.6A, this sensor is positioned to sense the rotation of coupler assembly108, via milled window602. Referring toFIG.6B, rotation is sensed by detecting radially-equidistant voids or notches604in the upper portion of coupler assembly116as they pass between the tines606of coupler assembly sensor114. Ejector sensor116is an inductive proximity sensor in one example. An example of a commercially available such sensor is a weld-field immune proximity sensor manufactured by Baluff, Inc., Florence, KY. As illustrated inFIG.6C, sensor116is mounted through cowling302, and positioned to sense when ejector110is translated along the longitudinal axis of threaded shaft122and brought into close proximity of coupler assembly108(position110′). The third sensor, ejector nut sensor118, is shown inFIG.6Amounted upon cowling302within milled window608. In one example, ejector nut sensor118is an optical fork sensor of the same type as was specified for coupler assembly sensor114. As illustrated inFIG.6D, ejector nut sensor118is positioned within the driver mechanism so that when ejector nut112is in its uppermost position along threaded shaft122, blade202interrupts the optical signal between tines610. The output of each sensor is transmitted via an interface to the capper/decapper control system (not illustrated). The information is processed and utilized by the controller system to govern the operation of the capper/decapper. In the above description, each of the sensors was described as being of a particular type (fork, optical, inductive) for purposes of illustration only. However, it will be understood that numerous types of sensors known in the art (e.g., optical, magnetic, inductive, mechanical, sonic, etc.) could be utilized in the capper/decapper described herein, so long as such sensors provide a reasonable means of monitoring the positions of ejector nut112and ejector110along the threaded shaft, and the rotational position of the coupler assembly114. Selection of a particular sensor is therefore largely a matter of design choice. The Coupler Assembly FIGS.7A and7Bprovide a side and front view, respectively, of coupler assembly108, which is shown to be connected to threaded shaft122. As shown, in one exemplary embodiment of the coupler three fingers702protrude from the bottom of the coupler assembly, and are equidistantly positioned in a circular interior section704having a diameter Ø. Other exemplary embodiments of the coupler have as few fingers, or as many as may prove practical for the dimensions of a given coupler assembly108. In this regard, a larger diameter could accommodate a greater number of fingers. The coupler assembly108is also shown to have three circular channels706. These channels are positioned and dimensioned to permit the three ejection rods402of ejector110to freely pass through. The specific configuration of the fingers is largely a matter of design choice. InFIG.7A-7D, each of three fingers702is illustrated as having a tapered, trapezoidal cross-section and terminates at a prismatic quadrilateral tip708. Housed inside a chamber710within each finger702is an engagement spline712. As illustrated inFIG.7C, engagement splines712have a circular cross-section in a particular embodiment of this invention. However, the specific geometric configuration of the splines is largely a matter of design choice that will depend upon the particular surface features of the element with which the engagement spline is intended to mate, and various other cross-sectional shapes are contemplated. The trapezoidal three-fingered configuration is particularly adapted to permit the insertion of the coupler assembly into densely-packed container carriers, as illustrated inFIGS.8A and8B. As shown, both the position and the cross-sectional shape of fingers702permit them to grasp a particular cap/container without contacting any of the surrounding caps/containers as the elongate fingers702fit easily in the interstices between containers in even densely packed arrays.FIG.8Bprovides a partial cross-sectional top view of fingers702engaging cap802. As previously explained, the capper/decapper described herein is configured to operate on an element, that element being one of a sample container or container cap. An internally-threaded cap802is illustrated inFIGS.8C and8D. This type of cap is similar to those typically employed on laboratory specimen containers such as the 8 ml Phoenix Broth products manufactured by the Becton Dickinson and Company of Franklin Lakes, NJ. Cap802is screwed onto threaded container804. As shown inFIGS.8C and8D, the lateral surface of cap802is ringed by longitudinal channels806, each of which has a substantially circular cross-section808. FIG.9Aprovides a cross-sectional view of the splines and coupler assembly108.FIG.9Bprovides a cross-section view of coupler assembly108engaging cap802. The base of engagement spline712is shown to be retained by vertical lip902within prismatic quadrilateral tip708of finger702. The top of engagement spline712is biased by circular spring904, urging the upper portion of spline inward and against wall906of chamber710.FIG.9Bis a cross-section view of coupler assembly108, but with cap802fully inserted between fingers702. As shown, engagement spline712is securely mated with longitudinal channel806. Circular spring904has been deformed outward by the upper portion of spline712, which is been pushed away from wall906of chamber710as a consequence of the insertion of cap802. The mating between the engagement splines712and the longitudinal channels806provides a secure interface enabling a significant torque to be applied to cap802by coupler assembly108as threaded shaft122is rotated in either a clockwise or counter-clockwise direction. All references to clockwise or counter-clockwise are from a reference point looking down onto the top of capper/decapper system. As illustrated inFIG.9B, cap802fits securely between the fingers702of upon insertion into coupler assembly108. To ensure this secure fit, and the resultant mating of the engagement splines712, coupler assembly108must be designed with a cap-specific diameter, Ø (seeFIG.7D). A cap of a particular diameter requires a similarly dimensioned coupler assembly to be connected to the driver mechanism and threaded shaft. Container Support For purposes of illustrating additional elements that will work in cooperation with the capper/decapper, the capper/decapper is described herein operating upon a capped container804, such as the one depicted inFIGS.8A-8D. This operation requires that container be supported during the uncapping and capping processes. The particular means for providing this support is tangential to the capper/decapper described herein. The capper/decapper described herein is configured to work with a variety of holders, as long as such holders do not hinder proper placement of the capper/decapper on the capped container. One illustration of a container holder1002is provided inFIGS.10A and10B. Holder1002is a representation of a holder that may be positioned in at least two states.FIG.10Adepicts the holder in a gripping state, wherein movable restraints1004and1006, supported by base1008, are held in contact with the exterior of a container804. The force exerted upon container804by these restraints is greater than the amount of torque required to be exerted upon cap802during a capping and/or decapping operation.FIG.10Bdepicts the holder in a retracted state, wherein restraints1004and1006are pulled away from the exterior of a container804. Thereby allowing the container, supported by spindle1010, to rotate freely about its longitudinal axis upon application of a sufficient rotational torque. Capper/Decapper Operation FIG.11Adepicts capper/decapper1102positioned above cap802of container804. It should be understood that capper/decapper1102can be affixed to a robotic or computer-controlled gantry or armature (not illustrated), enabling it to move, with at least one degree of freedom, relative to the position of a separate conveyance or support system for one or more containers. One such support system is holder1002, which is shown to be in a gripping state supporting container804. Capper/Decapper1102is in an initial state for commencing a decapping operation. In this state, ejector nut112is in an uppermost position along the axis of threaded shaft122. In this position, blade202interrupts the optical signal between the tines of ejector nut sensor118. The output of sensor118is transmitted via an interface to a capper/decapper control system (not illustrated) confirming the ejector nut positioning. Ejector110is in its lowermost position along the axis of threaded shaft122, resting upon the upper surface of coupler assembly108. The ejection rods402are fully extended, protruding through the circular channels706of coupler assembly108. Ejector sensor116detects this initial position of ejector110, and transmits a signal confirming such position to the capper/decapper control system. Coupler assembly110is positioned concentrically above cap802. The rotational position of coupler108, as recognized by coupler assembly sensor114, may be adjusted via actuation of motor102to rotate threaded shaft122while the capper/decapper is in this initial state. This could be done, for example, to position fingers708so that they do not obscure any labeling upon the exterior of container804. The minimal rotational adjustment required to accomplish this (less than a 60° shift given the three-fingered configuration of coupler assembly108), does not require any significant movement of ejector nut112along the axis of threaded shaft122. Consequently, blade202continues to interrupt the optical signal between the tines of ejector nut sensor118. As shown inFIG.11B, the next phase of the decapping operation requires capper/decapper1102to be moved downward so as to cause circular interior section704of coupler assembly108to come into direct contact with the top surface of cap802. Positioning capper/decapper1102in this manner causes the top of cap802to contact and push upward upon the lower surfaces of fingers708, and thereby push ejector110upward along the axis of threaded shaft122, and away from the proximity of ejector sensor116. In addition, as cap802is brought into contact with coupler assembly108, the engagement splines712mate with the longitudinal channels806of the cap802. This provides a secure interface enabling a significant torque to be applied to cap802by coupler assembly108. The position of ejector nut112remains unchanged for the initial state. A predetermined counter-clockwise torque1104is then applied to threaded shaft122via actuation of motor102by the capper/decapper control system (seeFIG.11C). In a preferred embodiment, the system applies this torque by actuating motor102to cause transmission104to rotate threaded shaft122through a specific angular rotation. This rotation is predetermined based upon the amount of rotation that is required to remove cap802from container804. As threaded shaft122rotates counter-clockwise, cap802is translated upwards. The aforementioned robotic or computer-controlled gantry or armature is programmed to raise capper/decapper1012a predetermined distance at a predetermined rate so as to compensate for upward translation. Systems providing such controlled mechanical manipulation are well-known in the art and will not be discussed here. The system will not initiate application of counter-clockwise torque1104unless sensors114,116and118provide signals indicative of the proper positioning of ejector nut112, coupling assembly108and ejector110, respectively. Failing the provision of such, the capper/decapper control system will default to an error-mode or actuate motor102and/or the aforementioned robotic or computer-controlled gantry or armature to bring the capper/decapper into a proper state of compliance. The operator can determine the default state of the capper/decapper in response to a signal from the sensors that the capper/decapper is not in the proper position for the capping/decapping operation. Once cap802has been fully removed, capper/decapper1102can be moved clear of container804under control of the capper/decapper control system (seeFIG.11D). This permits container804to be moved or otherwise processed. To begin the recapping process, capper/decapper1102is moved so that coupler assembly110is positioned concentrically above container804and lowered so that the internal threading of cap802comes into contact with the threads1108on container804(FIG.11E). As shown inFIG.11F, a predetermined clockwise torque1106is applied to threaded shaft122via actuation of motor102by the capper/decapper control system. In a preferred embodiment, the system applies this torque by actuating motor102to cause transmission104to rotate threaded shaft122through a specific angular rotation. This rotation is predetermined based upon the amount of rotation is will require to tighten cap802onto container804. This rotation also causes ejector nut112to translate upwards along the axis if threaded shaft122. In a preferred embodiment of the invention this translation is not sufficient enough to cause blade202to interrupt the optical signal between the tines of ejector nut sensor118. As threaded shaft122rotates clockwise, cap802is translated downwards, and capper/decapper controller lowers capper/decapper1012at a predetermined rate so as to compensate. In one embodiment of the invention, the system does not initiate application of clockwise torque1104unless sensors114,116and118had provided signals indicative of the proper positioning of ejector nut112, coupler assembly108and ejector110, respectively. Failing the provision of such, the capper/decapper control system as described defaults to an error-mode or actuates motor102and/or the aforementioned robotic or computer-controlled gantry or armature to bring the capper/decapper into a proper state of compliance. Once cap802has been fully tightened onto container804(seeFIG.11G), ejector nut112is in a position partially translated down the axis of threaded shaft122. However, this translation is not of such an extent that the bottom of ejector nut112comes into contact with the top surface of coupler assembly108. The capper/decapper is configured to prevent such contact, as such contact could result in the premature ejection of cap802. Unwanted contact is avoided by selecting the length of threaded shaft122, the spacing of the threads upon that shaft, and/or the horizontal dimensions of ejector nut112and/or ejector110. To cause the ejection of now tightened cap802/container804, threaded shaft122must be rotated in a counter-clockwise direction. During this counter-clockwise rotation in cap802, the cap channels806are still securely mated with engagement splines712of coupler assembly108. The application of the counter-clockwise force will cause the cap to be unscrewed from container804in the container remains secure from rotating with the cap802at this point. To avoid this undesirable result, holder1002is first placed into a retracted state, so that the cap802/container804assembly is free to rotate about its longitudinal axis upon application of a rotational torque. Shaft122is then rotated counter-clockwise (1110) via actuation of motor102by the capper/decapper control system (seeFIG.11H). In a preferred embodiment, the system rotates shaft122until ejector nut112is driven downward to a point along the axis of threaded shaft122that causes it to contact the top of ejector110and push ejector110down into position adjacent to ejector sensor116. The rotation of the threaded shaft122is stopped in response to a signal received by the capper/decapper system controller from ejector sensor116indicative of ejector being in the proximity of that sensor. However, this rotation could also be stopped after a predetermined number of rotations based upon the amount of previous clockwise and counter-clockwise rotation the shaft had been subjected to since ejector nut112left its initial position. As ejector110is pushed down, ejection rods402protrude downward through channels706in coupler assembly108, exerting a downward force upon cap802. This force disengages the cap from the engagement splines712. Prior to disengagement, cap802/container804is rotated counter-clockwise by coupler assembly108. As the threaded shaft122is rotated, ejector nut112is lowered. Capper/decapper1102, now fully disengaged from cap802/container804, is then returned to its initial state in order to begin another capping/decapping cycle. As shown inFIG.11J, to accomplish this, the system rotates shaft122in a clockwise direction1112until ejector nut112moves upward to a point along the axis of threaded shaft122that causes blade202to interrupt the optical signal between the tines of ejector nut sensor118. This rotation of threaded shaft122is stopped in response to a signal received by the capper/decapper system controller from ejector nut sensor116indicative the ejector nut being back in its initial position (seeFIG.11K). Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims. | 23,532 |
11858797 | As used herein, an effervescible liquid is a liquid that is capable of effervescing; for example, in response to a decrease in the pressure applied to the carrier liquid or an increase in its temperature. Effervescible liquid may comprise dissolved molecular species within a carrier liquid, in which the molecular species can come out of solution in the gaseous state in the form of gas bubbles. For example, effervescible water (or other liquid, such as dairy liquid) may consist of or comprise carbon dioxide or nitrogen or nitrous oxide dissolved and/or suspended within water (or other liquid). Carbonated beverages comprise carbon dioxide dissolved in the beverage, in which carbon dioxide gas bubbles will evolve from the solution during effervescence. Nitrogenated beverages may comprise nitrogen suspended in the beverage, in which nitrogen gas bubbles will evolve during effervescence. While nitrogen is substantially less soluble in water than carbon dioxide, relatively very small nitrogen gas bubbles may be held in suspension in water. The nitrogenated liquid may comprise nitrous oxide, nitrogen or air bubbles suspended in liquid. For example, nitrogen may be introduced into beer or coffee, and nitrogenated beer may be stored in kegs. Unless otherwise stated herein, the term ‘carbonated’ includes ‘carbonated’ or ‘nitrogenated’; that is a carbonated liquid may contain dissolved carbon dioxide or dissolved and/or suspended nitrogen. Carbonated liquid may be capable effervescing, the effervescence involving the evolution of carbon dioxide or nitrogen gas bubbles. The additive fluid may comprise or consist essentially of carbonated liquid, suitably carbonated water, nitrogenated liquid, suitably nitrogenated water or dairy liquid or other aqueous liquid, containing as much dissolved or suspended carbon dioxide or nitrogen as possible. The saturation level of carbon dioxide or nitrogen generally increases with increasing pressure and decreasing temperature, for example, the highest concentration in water being achievable by chilling water to just above freezing. When the temperature is raised or the pressure is reduced, bubbles of gas tend to form in the water or other liquid, which is known as effervescence. The rate of dissolution of gaseous carbon dioxide or nitrogen from the liquid depends on the number and size distribution of the gas bubbles introduced into the liquid, the pressure applied to the liquid, and the time allowed to reach the saturation level. With reference toFIG.1, an example in-line beverage dispenser assembly100for dispensing a beverage B may comprise an example dispenser head200and an example supplemental fluid system400. The dispenser head200may comprise a pump220, an inlet of which is connected to an outlet of a vessel300containing concentrate liquid C for the beverage B, such that the pump220can pump the concentrate liquid C from the vessel300. The supplemental fluid system400can supply a diluent liquid D for diluting the concentrate liquid C via a diluent channel420, and an additive fluid A via an additive channel430. In some examples, the supplemental fluid system400may be capable of supplying effervescible additive liquid A via the additive channel430. The pump220can pump concentrate liquid C from the vessel300as a series of quanta into a dilution chamber (not shown inFIG.1); and a diluent duct (not shown inFIG.1) can convey diluent liquid D from the diluent channel420into the dilution chamber, in which the concentrate liquid C can mix with the diluent liquid D to dilute the concentrate liquid C and thus reduce its viscosity. The diluted concentrate Cdcan flow from the dilution chamber into an additive chamber (not shown inFIG.1). If the viscosity or dilution ratio of the concentrate liquid C is sufficiently low, it may not be necessary to dilute it with diluent liquid D, and in such examples, the pumped concentrate liquid C may pass through the dilution mechanism that includes the dilution chamber, into the additive chamber comprised in an additive mechanism without being mixed with diluent. Whether or not the concentrate liquid C has been diluted with diluent liquid D, the liquid passing from the dilution mechanism to the additive mechanism will be referred to herein as the diluted concentrate Cd, unless otherwise stated. The additive mechanism may be configured for receiving the additive fluid A and combining it with the diluted concentrate Cdto provide the beverage B dispensed via outlet nozzle262into a receptacle (not shown). The beverage B may generally comprise predetermined or calculable quantities of the concentrate liquid C, the diluent liquid D and the additive fluid A. The dispenser assembly illustrated inFIG.1comprises a regulation system (not shown) operable to regulate at least one operating parameter of the pump (for example, whether the pump is activated or deactivated), the quantity of diluent liquid D that flows into the dilution mechanism and the quantity of additive fluid that flows into the additive mechanism. For example, the regulation system may comprise a diluent valve mechanism (not shown) for regulating whether or not diluent liquid D can flow from the diluent channel420into the dilution mechanism, and an additive valve mechanism (not shown) for regulating whether or not additive fluid A can flow from the additive channel430into the additive mechanism. The regulation system may comprise an electronic processor device such as a computer microprocessor (not shown) configured to control the operation of the diluent and additive valve mechanisms on the basis of input data received and processed by the electronic processor. For example, the supplemental fluid system400may comprise a radio-frequency identification (RFID) device capable of indicating the respective flow rates of each of the diluent liquid D and the additive fluid A. The regulation system may comprise a device capable of receiving data transmitted by the RFID device and converting the data into electronic form for processing by the electronic processor. In some examples, the electronic processor may be configured to determine the respective periods of time for which the diluent valve mechanism and the additive valve mechanism should be put in an open state to allow the diluent liquid D and the additive fluid A, respectively, to flow into the dilution mechanism and the additive mechanism, respectively, based on their respective flow rates. The electronic processor device may put each of the diluent valve device and the additive valve device into a closed state after the respective periods of time, by issuing respective electronic control signals. The quantities of the diluent liquid D and the additive liquid A to be combined with the concentrate liquid C may thus be determined and regulated. Means other than RFID devices, for example QR code or bar code readers, are also envisaged by this disclosure for inputting data into the regulation system. An effervescible additive liquid may be saturated with carbon dioxide or nitrogen to a known value, thus enabling calculation of the quantity of additive fluid to introduce. For example, effervescible additive liquid may be preferably provided at about 2° C., at which the saturation level may be known. In examples where the additive fluid A is an effervescible liquid such as carbonated or nitrogenated water or other aqueous liquid, it may be desirable for the beverage to exhibit a degree of effervescence. The degree of effervescence may be characterizable in terms of a quantity of gas bubble formation, potentially expressed in terms of a quantity of gas that evolves from the beverage B as the dissolved carbon dioxide or nitrogen comes out of solution in the form of gas bubbles. The effervesce may be characterizable in terms of a number and size distribution of evolved gas bubbles, and/or a rate of gas bubble formation, for example. It may be desirable for the effervescence to be within a certain range: too much effervescence may result in excess foam on the beverage B, and too little effervescence may result in the beverage B being too flat (that is, the quantity of gas that evolves within the beverage is too little). In some examples, the dispenser head may have the aspect of achieving a desired quantity of effervescence in beverage B. With reference toFIGS.2A to2E, an example dispenser head200may comprise an attachment mechanism210for attaching the dispenser head200to the vessel300containing the concentrate liquid C. The example attachment mechanism210includes a duct211for conveying the concentrate liquid C from the vessel300to an inlet221A of the pump220. The vessel300may be provided as part of the dispenser head200, either detachably or as an integrated unit, or it may be provided separately from the dispenser head200. The attachment mechanism210may be cooperatively configured with a counterpart mechanism comprised in the vessel300. With particular reference toFIG.2C, an example pump220may comprise a rotor225within a pump housing223, in which the rotor225can be driven by a motor (not shown) coupled to a rotor transmission mechanism222(inFIG.2C, the axis of rotation of the rotor225is perpendicular to the page). The pump housing223may have a cylindrical inner surface within which the rotor225can fit and rotate such that a surface area of the rotor225contacts the inner surface of the pump housing223. The pump housing223may comprise resilient material and the rotor225may slightly depress the inner surface of the pump housing223to ensure a sufficiently good seal between the rotor225and the pump housing223to prevent pumped concentrate liquid C from passing between the rotor surface area and the inner surface of the pump housing223where these abut each other. In the particular example illustrated, the surface of the rotor225includes two opposite surface areas that are spaced radially inward to form respective pump chambers226on diametrically opposite sides of the rotor225(only one of the pump chambers is indicated by226inFIG.2C). The volume of each pump chamber226will define the volume of each quantum of concentrate liquid C pumped into the dilution chamber232via the pump outlet221B. Each of the pump chambers226can receive concentrate liquid C when the respective pump chamber226is in fluid communication with the pump inlet221A. As the rotor225is driven to rotate in use (in a clockwise direction as illustrated inFIG.2C), concentrate liquid C within the pump chamber226will be conveyed around the pump housing223until the pump chamber226becomes in fluid communication with the pump outlet221B and the concentrate liquid C is expelled from the pump chamber226into the pump outlet221B. In the particular example illustrated inFIG.2C, the pump220comprises a seal membrane227, which may be formed as a unitary part of the pump housing223or joined to the rotor housing223by welding, adhesive or other means. The seal membrane227is sufficiently flexible and resilient that it can remain in contact with a relatively complex shaped rotor surface including the radially depressed area forming the pump chamber226. A resilient compression member213may be located within a rear chamber212behind the seal membrane227; that is, the compression member213may arranged on the side of the seal membrane227opposite the side that contacts the rotor225. In this example, the resilient compression member213is elongate and has a generally “U”-like shape when viewed in transverse cross-section, as shown inFIG.2C, having a pair of elongate leg members seated against a fixed backing wall214of the rear chamber212. A rib projecting from the opposite side of the resilient compression member213may abut the rear side of the seal membrane227; that is, the side of the seal membrane227facing the rear chamber212. The rear chamber212and the resilient compression member213are configured such that the resilient compression member213will be in compression between the backing wall214and the seal membrane227, so that the rib of the resilient member213can urge the seal membrane227against the surface of the rotor225as the rotor225is driven to rotate within the rotor housing223. The seal membrane227will thus be urged against the surface of the rotor225with sufficient force to prevent concentrate liquid C from passing between the seal membrane227and the rotor225and, consequently from passing from the pump outlet221B to the pump inlet221A, and to expel concentrate C from a pump chamber226into the pump outlet221B. The example pump220described with reference toFIG.2Ccan pump the concentrate liquid C from the vessel300as a series of quanta, each having a known volume and delivered to the dilution mechanism at a known rate, determined by the angular velocity of the rotor225and the total degrees of rotation. The volume of each quantum of concentrate liquid C will be defined by the volume of each pump chamber226. The quantity of concentrate liquid C delivered for producing a quantity of beverage B can be determined as a number of quanta. In other example dispenser heads, different kinds of pumps may be used, which may pump the concentrate liquid C as a continuous stream at a known or selectable flow rate. In various example arrangements, the pump220may be substantially as disclosed in any of international patent application publication numbers WO2006/027548, WO2010/122299, WO2013/050491, WO2014060418, WO2013/050488, WO2013/117486, or WO2014/135563; or in UK patent application publications number GB 2 551 663 or GB 2 507 029 (although example pump mechanisms are in no way limited to those disclosed in these publications). In certain examples, it may be desirable to reduce the viscosity of the concentrate liquid C before it is combined with the additive fluid A, by diluting the concentrate liquid C with a suitable diluent liquid D, particularly when the additive fluid A is an effervescible liquid. This may allow effervescible additive liquid A to be combined with the diluted concentrate Cdsufficiently gently to reduce, minimise or prevent premature or excessive effervescence of the additive liquid A or the dispensed beverage B. The illustrated example dilution mechanism comprises a dilution housing230that includes a dilution chamber232, and a diluent duct for conveying diluent liquid D from the diluent channel420of the supplemental fluid system400into the dilution chamber232. The dilution chamber232is in fluid communication with the pump outlet and can receive and mix together pumped concentrate liquid C as well as diluent liquid D. The diluent duct may comprise a number of chambers, orifices and passages that are in fluid communication with each other operable to convey the diluent liquid D from the diluent channel to the dilution chamber232; for example, the diluent duct may be formed of a diluent inlet234and an orifice235into the dilution chamber232. In the particular example illustrated inFIGS.2C and2D, the diluent duct may include the rear chamber212and is thus in fluid communication with the rear side of the seal membrane227. The pressure of the diluent liquid D may thus be transmitted onto the rear side of the seal membrane227, supplementing or replacing the force applied to the seal membrane227by the resilient compression member213for urging the seal membrane227against the surface areas of the rotor225. In some other examples, the diluent duct may be segregated from the rear chamber212and seal membrane227by a barrier means. Thus, the force applied onto the seal membrane227may be a combination of the force applied by the compression member213and the pressure differential across the restricted orifice235(which may be referred to as a ‘jet orifice’, particularly if its area is sufficiently small that liquid passing through it will emerge as a jet of liquid). With particular reference toFIGS.2C and2D, the diluent duct may include a jet orifice235, having a sufficiently small area that the diluent liquid D passing through it will spray into the dilution chamber232as a jet of diluent liquid D. This may have the aspect of promoting turbulence and rapid mixing of the pumped concentrate C with the jet of diluent liquid D. The area of the jet orifice235may be substantially smaller than the mean cross-section area of the rest of the diluent duct, resulting in a substantial increase in the velocity and a drop in pressure at which the diluent liquid D passes from the jet orifice235into the dilution chamber232. With further reference toFIGS.2C and2D, the example dispenser system may comprise a one-way valve250through which the diluted concentrate Cdwill pass, configured and arranged for promoting turbulence of the diluted concentrate Cdand consequently promoting the rapid and thorough mixing of the diluent liquid D and the concentrate liquid C. The one-way valve250is preferably located on the path of the diluted concentrate Cdas it passes from the dilution chamber232to the additive mechanism and suitably substantially prevents additive liquid A from flowing upstream into the dilution chamber232. The dilution mechanism or the additive mechanism may comprise the one-way valve250, or the one-way valve may be located between the dilution and additive mechanisms. With reference toFIG.2E, an example one-way valve comprises a flexible member250in the form of an annular disc or ring, such as a polymer washer, for example. The flexible member250may extend generally radially from a central axis, a peripheral area of the flexible member250abutting a seat area of the housing of the dilution mechanism when no fluid is passing from the dilution mechanism to the additive mechanism. When at least partially diluted concentrate Cdis contained within the dilution chamber232and in contact with a side of the flexible member250, and the pressure of the diluted concentrate Cdis sufficiently great, the peripheral area of the flexible member250may be deflected away from the seat and thus permit the diluted concentrate Cdto pass between the peripheral area and the seat, into a chamber268included in the additive mechanism. A radially outward component may thus be imparted to the velocity of the diluted concentrate Cd; the resulting increased turbulence within the at least partially diluted concentrate Cdmay have the effect of rapidly improving the homogeneity of the mixture of the diluent and concentrate liquids D, C before the diluted concentrate Cdis combined with the additive liquid A. In addition, the radially outwardly moving flow of diluted or undiluted concentrate Cdmay hit a radial wall of the additive chamber, causing turbulent flow of the diluted or undiluted concentrate Cdand thereby further promoting mixing. In some examples, diluent liquid may be introduced into the dilution chamber232at a pressure of about 150 kPa through the diluent orifice235. While this is likely to cause some mixing of the diluent liquid D with the concentrate liquid D, the diluted concentrate mixture may not be homogeneous. The relatively pressurised diluted concentrate is then forced past the flexible member250, which may comprise an elastomeric washer valve in some examples, which can flex to allow the diluted concentrate Cdto pass from the dilution chamber232. The extent to which the flexible washer250flexes will generally depend on the viscosity and pressure of the diluted concentrate Cd, and the flexibility of the washer250. In certain preferred example arrangements, the diluted concentrate Cdmay be forced into a relatively thin film. To allow a sufficient quantity of the diluted concentrate Cdto pass, the length of the thin film needs to sufficiently great relative to the thickness of the film, which may be achieves if the flexible washer valve150is circular and has a sufficiently long circumference. The diluted concentrate Cdin the film may travel at high velocity and consequently relatively low pressure. The film exits into a first volume268of an additive chamber, the first volume configured to direct the film of diluted concentrate Cdinto a centre region of the first volume268. The high velocity of the diluted concentrate Cdand the abrupt change of its direction of travel will likely cause further mixing and homogenisation, and upon exiting the first volume268of the additive chamber, the diluted concentrate may be a substantially homogeneous diluted mixture. With particular reference toFIG.2D, the regulation system of the dispenser system200may comprise a diluent flow control mechanism275for regulating the flow of the diluent liquid D through the diluent inlet passage234. For example, the diluent flow control mechanism275may comprise a shut-off valve that can be put into an open state, in which diluent liquid D can pass through it, or into a closed state, in which the diluent shut-off valve275will prevent the diluent liquid D from flowing into the dilution duct. The diluent shut-off valve275may be seated within a valve housing270, which may be attachable to the diluent inlet234. The diluent shut-off valve275may be electrically actuatable by means of a solenoid device (not shown), which may be controlled by an electronic processor device (not shown). When the dispenser head200is used and the concentrate C is pumped into the dilution chamber232, the diluent shut-off valve275may be put in the open state so that diluent liquid D can flow into the dilution chamber232and mix with the concentrate C. When the required quantity of the dilution liquid D has flowed into the dilution chamber232, the diluent shut-off valve275may be automatically closed. The required quantity of diluent liquid D may be determined as being proportional to the diluent flow rate (in terms of the mass of diluent liquid D flowing through a unit area per unit time, for example) multiplied by the time period for which the diluent shut-off valve275has been open. The additive mechanism may comprise an additive housing260including first and second volumes268,266of an additive chamber and an additive inlet264, which may be substantially free of corners or abrupt changes in direction in order to reduce or substantially prevent premature or excessive effervescence of effervescible additive liquid A such as carbonated water. Diluted concentrate liquid Cd(or undiluted concentrate, in some examples) can flow from the dilution chamber232into an uppermost volume268of the additive chamber via the one-way valve250, in some example arrangements. In addition, additive fluid A can flow from the additive channel430of the supplemental fluid system400, via the additive inlet264into a volume266of the additive chamber, where it may at least partly combine with the diluted concentrate Cdand pass through an outlet nozzle262into a cup or other receptacle (not shown). The additive liquid A and the diluted or undiluted concentrate Cdmay mix partly or substantially entirely in the additive chamber and/or in the receptacle. The additive mechanism may include a sieve (not shown) or other suitable agitation means for promoting the nucleation of gas and consequently the effervesce of the additive liquid A or the beverage B, particularly for use with certain liquids that need to be agitated in order to effervesce (that is, for gas bubbles to nucleate), such as nitrogenated liquid. For example, an agitation sieve may be located at or near the outlet nozzle262and may comprise sieve holes of about 750 microns in diameter or facetted hole of similar cross-sectional area. With particular reference toFIG.2D, the regulation mechanism may comprise an additive flow control mechanism285for regulating the flow of the additive fluid A through the additive inlet264. For example, the additive flow control mechanism285may comprise an additive shut-off valve that can be put into an open state, in which additive fluid A can pass through it, or a closed state, in which the additive shut-off valve285will prevent the additive fluid A from flowing into the volume266of the additive chamber. The additive shut-off valve285may be seated within close proximity to a valve housing280, which may be attachable in close proximity to the additive inlet264. The additive shut-off valve285may be electrically actuatable by means of a solenoid device (not shown), which may be controlled by an electronic processor device (not shown). When the dispenser head200is in use, the additive shut-off valve285may be put in the open state so that additive liquid A can flow into the volume266of the additive chamber. After the required quantity of additive fluid A has flowed into the additive chamber266, the additive shut-off valve285may be automatically closed. The required quantity of additive fluid A may be determined as being proportional to the additive liquid flow rate (in terms of the mass of additive liquid D flowing through a unit area per unit time, for example) multiplied by the time period for which the additive shut-off valve285has been open. The regulation system may comprise a pressure-responsive valve282located within a valve housing280. For example, the pressure-responsive valve282may comprise a passage through which carbonated water A can flow and be configured such that the rate at which the carbonated water at a temperature of about 1° C. to about 10° C. passes through passage will be substantially constant (for example, about 16 ml/s to about 24 ml/s, or about 20 ml/s) over a pressure range of about 140 kPa to about 1000 kPa (higher saturation may be achieved by using higher pressures of up to about 1000 kPa in some arrangements). In general, the pressure-responsive valve282may limit the variation of the flow speed of a chilled effervescible additive liquid A to no more than plus or minus about 10%, or plus or minus about 5%, as a function of the pressure of the additive liquid A in the range of about 100 kPa to about 1000 kPa. The effervescible additive liquid A may contain dissolved carbon dioxide or suspended nitrogen at, or slightly less than, the saturation solubility under prevailing conditions. The quantity of additive liquid A may be thus controlled by the timing of operation of the shut off valve. In examples where the additive fluid A is an effervescible liquid, it may be desirable for the content of dissolved carbon dioxide or suspended nitrogen to be at or close to the saturation solubility level, and for the saturation solubility level to be as high as practically possible. This may be achieved by providing the effervescible additive liquid A at a low temperature (for example, only slightly above the freezing point of the liquid) and at a relatively high pressure. The mean diameter (or, more generally, transverse cross-section area) of a supply tube (not shown) conveying the additive liquid A to the pressure response valve282may be substantially greater than the mean diameter (or transverse cross-section area) of the passage through the pressure-response valve282, for the pressure of the additive fluid A upstream of the pressure-response valve282to be sufficiently high to keep the liquid saturated with effervescible gas whilst reducing or substantially preventing effervescence at this stage. The additive inlet264may have a smaller diameter to reduce the magnitude of the pressure drop across the pressure-responsive valve282, which would create excessive breakout of gas. In some example arrangements, the flow rate and quantity of diluent liquid D may be controlled by similar mechanisms as disclosed for the additive fluid A. With reference toFIGS.3A to3C, an example dispenser head200may comprise a pump220, a connection adapter210for connecting an inlet of the pump220in fluid communication with a vessel containing concentrate liquid C for a beverage, a dilution mechanism, an additive mechanism and a regulation system. The example dilution mechanism may comprise a dilution chamber232within a dilution housing230, a diluent duct comprising a diluent inlet234and orifice235through which the diluent liquid D can pass into the dilution chamber234, and a one-way diluent valve250. The additive mechanism may comprise an additive housing260, and additive inlet244, an additive chamber including a first additive volume268, a second additive volume267, a third additive volume266, a fourth additive volume269and an outlet nozzle262for dispensing beverage B. The additive housing260can be releasably coupled with the dilution housing230by means of a connection mechanism238. FIGS.3B and3Cillustrate a particular example additive mechanism in more detail. Diluted concentrate fluid Cd(which may consist of diluted or undiluted concentrate liquid C) can pass from the dilution chamber232, through a one-way valve250into the first volume268and subsequently through the second volume266towards the fourth volume269of the additive chamber. The second volume266includes a generally cylindrical volume extending longitudinally between the first volume268and the fourth volume269; the fourth volume269being located adjacent the outlet nozzle262. The third volume267of the additive chamber surrounds the second chamber266, extending coaxially with the second chamber266. Additive fluid A can be conveyed through the additive inlet244into the generally annular third volume267and distributed azimuthally around the second volume266conveying the diluted concentrate Cd, the second and third volumes266,267being separated by a generally annular wall. A one-way additive valve270may be located between the third volume267and the fourth volume269such that the additive fluid A within the third volume267can pass into the fourth volume269, but fluid cannot pass from the fourth volume269to the third volume267. The one-way additive valve may comprise a flexible washer270and may operate similarly to the one-way valve250located upstream, through which the diluted concentrate Cdpasses; that is, the pressure of the additive fluid A in the third volume267can deflect a peripheral portion of the flexible washer270away from a seat and pass between the flexible washer270and the seat. The additive fluid A can combine with the diluted concentrate Cdin the fourth volume269before being dispensed through the outlet nozzle262. Effervescible additive fluid A may be introduced into the second volume266of the additive chamber at a pressure of approximately 900 kPa, before flowing past the flexible washer270between the second volume266and the fourth volume269. To reduce or substantially avoid premature or excessive effervescence of the additive liquid A (that is, to reduce nucleation of gas bubbles), the pressure of the effervescible liquid A should be decreased from the 900 kPa to ambient pressure as gently as possible. The flexible washer valve270may be conical in shape and its valve seat should be correspondingly conical; a preferred example cone angle may be approximately 45°. The diameter of the washer valve270may be relatively large so that the effervescible additive liquid A emerges from between the washer valve270and its seat in the form of a film having a relatively large cross-sectional area. In an example arrangement, the additive liquid A may strike the wall of the fourth volume269of the additive chamber at about 45°, and subsequently flow against the walls of the chamber. Since the diameter of the fourth volume269of the additive chamber is significantly larger than that of the additive inlet244(for example, an order of 15 times greater) the velocity of the effervescible liquid A is substantially less within the fourth volume269that it is in the additive inlet244. In the illustrated example, the walls of the fourth volume269are conical (or funnel-shaped) towards the outlet nozzle262to converge the effervescible additive liquid A at a relatively low speed, forming a smooth, low speed stream. The additive valve means270does not need to comprise a thermoplastic washer, and in some examples, it may comprise two concentric cones, between which there is a precise gap for the passage of the effervescible liquid A. However, a flexible washer may exhibit advantageous self-compensation for different flow rates; in addition, a double cone arrangement may need to be manufactured to a substantially higher precision than a flexible washer. The diluted (and substantially homogeneous) concentrate liquid Cdwithin central second volume266of the additive chamber may be at a relatively low pressure so that it can combine in the fourth volume269with the effervescible additive liquid A, which is also at a relatively low pressure because the fourth volume269is open to ambient pressure. Further mixing of the diluted concentrate liquid Cdand the effervescible additive liquid A may occur within a receptacle into which the liquids are dispensed via the outlet nozzle262. The outlet nozzle262may be fitted with a length of tube to direct the liquids to a receptacle some distance from the outlet nozzle262. With reference toFIGS.4A to5B, an example pressure-responsive flow control value assembly282may comprise a resilient annular valve body284and a valve holder286, the valve body284including a central passage288connecting a proximal end283and a distal end285of the valve body284coaxially with a longitudinal axis L. The valve holder286is configured to accommodate the valve body284, comprising a generally annular side wall289and having a seat287which the distal end285of the valve body284will abut when assembled as in use. The valve holder286includes a central exit passage286E connecting the seat287to a distal end of the valve holder286. In the particular example illustrated inFIG.4A, the exit passage286E is substantially coaxial with, and has a larger diameter than, the passage288through the valve body284. In use, liquid (for example, effervescible additive liquid A) will flow through the passage288of the valve body284from the proximal end283to the distal end285, at least a radially outer area of which abuts the seat287, and then exit the pressure-responsive valve assembly282through the exit passage286E of the valve holder286. When the additive mechanism260is assembled as in use, the valve holder287will be seated within the valve housing280(shown inFIG.2D). The valve body284comprises or consists essentially of a flexible, resilient material and is configured such that it will flex longitudinally in response to an increase in the pressure of fluid against the proximal end283. In an unflexed state, the distal end285of the valve body282in the particular example illustrated inFIG.4Awill be spaced apart from at least an inner annular area of the valve seat287so that when the valve body284flexes in response to the pressure of the fluid passing through the passage288, its distal end285can flex towards the seat285. In the particular example illustrated inFIG.4A(disclosed in U.S. Pat. No. 7,225,829 B2), the valve holder further includes an annular bypass channel281A formed into the valve seat287and coaxial with the exit passage286E, and a longitudinal bypass channel inlet281B, configured such that when the valve body284is unflexed as illustrated, fluid can flow through the bypass channel inlet281B into the annular bypass channel281A and then through the space between the spaced-apart inner distal end285of the valve body284and into the exit passage286E. Thus, there is provided a bypass channel281B,281A through which fluid can pass when its pressure against the proximal end283of the valve body284is sufficiently low for the annular bypass channel281A to be in fluid communication with the exit passage286E of the valve holder286. As the fluid pressure increases, the valve body284will flex such that its distal end285will move closer towards the inner area of the seat285and reduce the effective area of the bypass channel281B,281A. Consequently, the pressure-responsive valve assembly282will respond to an increase in fluid pressure by reducing the effective area through which the fluid can flow, thus counter-acting the tendency for the fluid flux to increase as its pressure increases. Other example pressure-responsive valve assemblies282have different configurations and arrangements of the valve body284and the valve housing286. The valve body284may comprise or consist essentially of flexible rubber material and is configured to deform in response to an increase in the pressure of the flowing fluid such that the effective passage diameter through the pressure-responsive valve assembly282will reduce in size, thus limiting the rate at which the fluid passes through it. As the fluid pressure increases above a certain value, the size of the aperture decreases just enough to maintain a substantially constant flow rate. An example of a potentially suitable pressure responsive valve may be VL3007XXXXX™, obtainable from Vernay®; other examples of potentially suitable pressure-responsive valves are disclosed in U.S. Pat. Nos. 4,609,014, 7,222,643 and 7,225,829. In examples where the additive fluid is effervescible liquid, premature effervescence can be triggered by a number of factors. For example, the nucleation of gas bubbles can be caused by the presence of sharp edges and asperities, agitation of the effervescible liquid, an increase in the temperature of the effervescible liquid and a relatively rapid decrease in its pressure. A decrease in the pressure will result in a decrease in the saturation concentration of the dissolved gas to decrease, resulting in the formation of gas bubbles. Since the pressure of the effervescible additive liquid may be about 690 kPa when it is introduced into the additive chamber, it will need to decrease before being dispensed into a receptacle. To reduce premature effervescence, the decrease in pressure may be deferred until the effervescible liquid is as close as possible to the outlet nozzle of the additive mechanism. In addition, a rapid decrease in the pressure would tend to increase the agitation of the liquid. Preferably, the outlet nozzle may be kept at a relatively low temperature, by keeping the outlet nozzle within a refrigerated environment, for example. This reduces effervescence and may also be desirable for maintaining hygiene. The capability of the pressure-responsive valve to reduce the variation in flow speed in response to a change in the pressure of the fluid may have the aspect of reducing the variation in effervescence (that is, frothing or foaming) of effervescible additive liquid A, were the pressure of the additive liquid A supplied by the supplemental fluid system may be uncertain, or differ between various systems. This effect may arise from a phenomenon in which increasing the flow speed of an effervescible liquid may directly or indirectly cause the liquid to effervesce, potentially as a result of an increased risk of turbulence within the flowing liquid. The dispenser head200may be an assembly of parts, which may be provided assembled or in kit form, or separately-provided parts. For example, one or more of the valve housings270,280, flow control means275,285, and the pressure-responsive valve282may be provided as separate parts that can be assembled and functionally interconnected. Preferably, the dispenser head200is provided as a unitary construction. In addition, the additive housing260may be provided as a fixture that can be reversibly coupled to the dilution housing230. The dispenser head200may comprise an attachment mechanism238, formed of cooperatively configured end portions of the dilution housing230and the additive housing260, such that the respective end portions can be inter-engaged with each other. For example, the end portions may be cooperatively threaded so that that the additive housing260can be screwed onto the end portion of the dilution housing230; or inter-locked with it in some other way. In some examples, the additive mechanism may be provided as a kit comprising the additive housing260, the additive valve housing280, the pressure-responsive valve282and the shut-off valve285. By controlling the respective time periods over which the concentrate liquid C is pumped from the vessel300, and the diluent and effervescible additive fluids D, A are allowed to flow into the dilution mechanism and the additive mechanism, respectively, to mix with the concentrate liquid C, a desired quantity of the beverage B having the desired concentration and carbonation or nitrogenation can be dispensed. In some examples, the pumping rate of the concentrate C, and/or the operation of the shut-off valve275for the diluent D and the shut-off valve285for the additive liquid A, and potentially other operating parameters of the pump220, may be controlled by means of an RFID chip or QR code or similar that contains the recipe for that particular concentrate (not shown), which may be provided as part of the pump220. The dispenser head200may contain a reader device that may be capable of reading the recipe of the beverage B and adjusting the ratios of the concentrate liquid C, the diluent liquid D and the additive liquid A according to the recipe. The dispenser head200may include information about the liquid product for the user, and potentially information such as the quantity of concentrate remaining in the vessel300, an expiry date (or “use-by” or “best-by”) for the concentrate liquid C, the compatibility of the concentrate liquid with the dispenser head for the dispenser operator, which may be displayable on a graphic interface provided on or with the dispenser head200. This arrangement is particularly advantageous when the dispenser head200is fitted to the concentrate vessel300, for single use with only the concentrate vessel300. The electronic processor may be capable of receiving electronic input data indicative of the pumping rate and/or the diluent flux and/or the additive flux, and of the quantities of the concentrate C, diluent D and additive liquid A, and the quantity of the beverage B. The electronic processor may be capable of processing this data to determine at least the time periods for which the diluent D and/or additive are to flow into the dilution chamber232and/or additive chamber; and may control the operation of the shut-off valves275,285independently from each other by outputting respective electronic control signals. In some examples, a dispenser assembly including the dispenser head200may include a computer processor capable of reading radio-frequency identification devices (RFID) data and automatically setting operating parameters of the dispenser head, such as the respective timings of the opening and closing of the diluent and additive shut-off valves. At least some of the electronic input data may be entered manually by an operator or transmitted from sensors comprised in the pump means and/or the dilution mechanism and/or the additive mechanism; and/or transmitted by one or more devices such as RFID, which may be comprised in the supplemental fluid system400, and/or provided with the concentrate vessel300. In some examples, the dispenser head200, which may include the concentrate vessel300, or the concentrate vessel300specifically may be provided with a means of indicating the relative proportions of concentrate C, diluent D and additive A should be to provide a desired beverage B. For example, the dispenser head may include an RFID means capable of providing this information. The concentrate liquid may be a concentrated form of any of a variety of beverages B, for example fruit juice, beer, milk, coffee, or soft drinks such as cola drinks. In some examples, the concentrate liquid C may be relatively viscous and need to be diluted before being mixed with carbonated or nitrogenated water (or other aqueous liquid) A to provide the beverage B with a desired carbonation or nitrogenation, whilst avoiding excessive foam or froth. The diluent liquid D may comprise or consist essentially of water (or other aqueous liquid) that is substantially free of added carbon dioxide or nitrogen in a form that can effervesce, and/or the additive fluid A may comprise or consist essentially of carbonated or nitrogenated water that can effervesce when combined into the beverage B. In some examples, the additive fluid A may be substantially free of carbon dioxide and nitrogen. In some examples, a certain amount of froth may be desirable (for example, in a coffee latte) in which case the additive mechanism may be configured to promote controlled nucleation. A user may expect the beverage B to be dispensed into a cup or other receptacle within a relatively short period of time; for example, in about the time it would take to manually pour the beverage B directly into the cup. This requires the concentrate C to be diluted and carbonated as it flows from the pump through the outlet nozzle262and into the receptacle. In some examples, such as where the beverage B is apple juice or other fruit juice, the concentrate C may have a relatively high viscosity and needs to be diluted with diluent D before it can be effectively mixed with carbonated additive liquid A in a sufficiently short time period. A sufficient amount of diluent fluid D, such as still water, may be mixed into the juice concentrate C to sufficiently reduce the viscosity of the diluted concentrate Cdfor carbonated water A to be mixed with it sufficiently quickly for convenient dispensing. In some examples, the concentrate liquid C (for example concentrate syrup for a cola drink or beer) may have sufficiently low viscosity that it is not necessary to dilute it before combining it with carbonated or nitrogenated water or other aqueous liquid. In such cases, the diluent shut-off valve275may be kept in the closed state while the beverage B is being dispensed. For example, cola syrup may be mixed with carbonated water in a ratio of about 5:1; and for some alcoholic beers 4:1; and for some non-alcoholic beers, the ratio of concentrate to carbonated water may be about 25:1. The supplemental fluid unit400may be configured to chill the water to about 2° C. and to pressurise it to about 700-1000 kPa just prior to being introduced into the dispenser head200. Therefore, when the carbonated water A is introduced into the additive mechanism260, the content of dissolved carbon dioxide should be close to the highest level that can be practically achieved. The additive channel430transporting the carbonated liquid or nitrogenated liquid A may be configured to promote as laminar flow as possible to reduce or prevent effervescence until the carbonated fluid A is introduced into the additive mechanism260. Laminar flow may be enhanced by configuring the additive duct430such that it changes direction gradually, without having abrupt corners. Since carbon dioxide (or nitrogen) bubbles may nucleate and evolve in response to a decrease in pressure of the carbonated liquid A when it enters to the additive mechanism, the additive mechanism may be configured to provide a certain rate of depressurisation to control the rate of gas bubble formation and size distribution of the gas bubbles. The carbonated liquid A may be passed through a gauze as it flows into or through the additive mechanism to control the number and size distribution of bubbles and to promote controlled foaming of the beverage. In some examples, when the dispenser head200is not being used, sanitising fluid may be introduced into the dilution or additive mechanism to clean at least a portion of the dispenser head200open to the environment. It may be desirable to use the diluent liquid to flush the outlet nozzle during mixing. The supplemental fluid system may be capable of chilling the diluent liquid D and the additive fluid A to the same or different temperatures in the range of about 1° C. to about 10° C., and of pressurising at least the additive liquid A to a pressure of about 600 kPa to about 1000 kPa. In some examples, the supplemental fluid system may be configured to introduce carbon dioxide or nitrogen gas bubbles into a carrier liquid such as water, which is to be carbonated or nitrogenated, and then treat the gas-containing carrier liquid such that substantially all the gas in the bubbles dissolves into or is suspended in the carrier liquid to provide the additive liquid that is capable of effervescing (that is, effervescible). The supplemental fluid system may reduce the temperature of the gas-containing carrier liquid to slightly greater than its freezing point by passing it through a heat exchanger, thus increasing the saturation solubility of the carbon dioxide or nitrogen within the carrier liquid. The diluent, which may be the same kind of liquid as the carrier liquid (for example, still water) may be passed through the same heat exchanger, which may be a twin-coil heat exchanger, to reduce its temperature as well, before the diluent and additive liquids D, A are supplied in separate streams at known flow rates into the diluent inlet234and the additive inlet264, respectively. The pumped concentrate C may be aggressively mixed with the chilled diluent liquid D and thus rapidly diluted to produce diluted concentrate Cdhaving a sufficiently low viscosity for subsequent mixing with the chilled effervescible additive liquid A. The effervescible additive liquid A can then be relatively gently combined with the diluted concentrate Cdin the additive chamber and the effervescible beverage B dispensed directly into a cup without excessive frothing. When introducing effervescible gas into carrier liquid to provide effervescible additive liquid within the supplemental fluid unit, the differential pressure between the gas (for example, carbon dioxide or nitrogen) and the water or other carrier liquid may generally be important for the effective and rapid dissolution of the gas into the carrier liquid. For example, if carbon dioxide gas is at a pressure of 700 kPA and the pressure of the water is 200 kPa, then the differentia pressure is 500 kPa. Once the water carrier liquid has been saturated with carbon dioxide, for example, the reduction in its pressure from 700 kPA should be as gradual as practically possible up to the point at which it is dispensed (at ambient pressure), to reduce the risk of excessive foaming. This may be achieved by conveying the effervescible liquid by means of a relatively long tube having a relatively small diameter, or which that is slightly tapered from a small diameter to a larger diameter so that at the flow rate of the liquid is relatively low where it is dispensed. A preferred method may be to convey the effervescible liquid in a relatively short tube having a relatively large diameter and to locate a flow control valve as close to the outlet nozzle as possible. Any dissolution of the gas as it passes through the flow control valve is immediately mixed with the concentrate liquid or a pre-diluted concentrate liquid. The concentrate liquid, having a higher density, can absorb a higher level of dissolved gas. In general, if effervescible liquid is combined too aggressively with concentrate liquid, then excessive frothing or foaming may occur; the effervescible additive liquid should generally be subject to as little agitation as possible. Certain example dispenser heads have the aspect that the steps of aggressively diluting concentrate liquid C and gently combining it with effervescible liquid A are separated to provide an in-line means of sufficiently rapidly dispensing effervescible beverage B with reduced frothing. In addition, the supplemental fluid system400can be used to produce different beverages B from different respective concentrate liquids C, in which beverages B can be quickly switched with substantially reduced risk of cross-contamination. For example, a first assembly comprising the dispenser head connected to the vessel containing a first concentrate liquid can relatively easily and quickly be disconnected from the supplemental fluid system and replaced with a second assembly of dispenser head and vessel containing a second concentrate liquid. In some examples, it may be desirable for the dispensed beverage to have a high degree of effervescence (that is, to be very ‘fizzy’), requiring a relatively large quantity of effervescible liquid to be combined with concentrate liquid. In general, the higher the concentration of the concentrate liquid, the more effervescence can be introduced in-line; and in general, the more concentrated the concentrate liquid, the higher its viscosity and the more it may need to be diluted. In general, since the desirable serving temperature of chilled beverages may be approximately 8° C. (5-10° C.), and the concentrate liquid C may be stored in a refrigerated compartment at approximately 6° C., and since the cup is likely to be at ambient temperature (about 15-30° C.), the supplemental fluid unit may need to introduce the diluent liquid at a temperature close to its freezing point; for example, about 2° C. for water diluent. The effervescible additive liquid may include the highest possible content of dissolved effervescent gas. In some examples, the ratio of concentrate liquid to still water diluent may be about 1:1; and the ratio of effervescible water to the diluted concentrate may be about 4:1. The viscosity of the diluted concentrate may be sufficiently low that the final stage of mixing of the effervescible additive liquid and the diluted concentrate can take place in the cup, after being dispensed. For a given pressure differential between the gas and liquid, a given temperature and a given time, the maximum saturation level is a constant value. The dispenser head may be capable of using this known constant value to dispense the correct ratios of concentrate, diluent and saturated carbonated water. Some example dispenser heads may have the aspect of avoiding concentrate being supplied by the supplemental fluid unit, which may produce, chill and/or pressurise, and convey only diluent fluid such as still water and/or additive fluid such as carbonated or nitrogenated water. A dispenser head, comprising or connected to a concentrate vessel, can be connected to the supplemental fluid unit such that the diluent and/or the additive fluids can be conveyed from the supplemental fluid unit into the dispenser head. The type of beverage to be dispensed can be changed by disconnecting the dispenser head from the supplemental fluid unit and attaching a different dispenser head that is attached or attachable to a vessel containing a different concentrate liquid that is suitable for the desired beverage. Alternatively, the concentrate vessel may be detached from the pump and a different vessel, containing a desired concentrate, can be connected to the pump. This avoids the need to clean the supplemental fluid unit to remove residual concentrate and avoids cross-contamination of the desired beverage by a residual amount of a previous concentrate. An example dispenser head may be configured such that a source of sanitising liquid can be connected with the diluent inlet for introducing the sanitising fluid in such a way that it will flow through all passageways downstream of the pump outlet. Example dispenser heads which are provided attached to the concentrate vessel may have the aspect of avoiding the risk of cross-contamination of different concentrates that may arise if the pump assembly were used for pumping different concentrates. In other examples, the dispenser head may be provided separately from the concentrate vessel, to which it may be attached for use and subsequently detached for use with a different vessel containing a concentrate of the same or a different kind. The pump assembly may be cleaned before attaching it to a concentrate vessel for use. | 55,744 |
11858798 | DETAILED DESCRIPTION Reference now will be made in detail to embodiments of the invention, one or more examples of which are illustrated in the drawings. Each example is provided by way of explanation of the invention, not limitation of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment can be used with another embodiment to yield a still further embodiment. Thus, it is intended that the present invention covers such modifications and variations as come within the scope of the appended claims and their equivalents. As used herein, the terms “first,” “second,” and “third” may be used interchangeably to distinguish one component from another and are not intended to signify location or importance of the individual components. The terms “upstream” and “downstream” refer to the relative direction with respect to fluid flow in a fluid pathway. For example, “upstream” refers to the direction from which the fluid flows, and “downstream” refers to the direction to which the fluid flows. Terms such as “inner” and “outer” refer to relative directions with respect to the interior and exterior of the refrigerator appliance, and in particular the food storage chamber(s) defined therein. For example, “inner” or “inward” refers to the direction towards the interior of the refrigerator appliance. Terms such as “left,” “right,” “front,” “back,” “top,” or “bottom” are used with reference to the perspective of a user accessing the refrigerator appliance. For example, a user stands in front of the refrigerator to open the doors and reaches into the food storage chamber(s) to access items therein. As used herein, terms of approximation such as “generally,” “about,” or “approximately” include values within ten percent greater or less than the stated value. When used in the context of an angle or direction, such terms include within ten degrees greater or less than the stated angle or direction, e.g., “generally vertical” includes forming an angle of up to ten degrees in any direction, e.g., clockwise or counterclockwise, with the vertical direction V. FIG.1provides a perspective view of a refrigerator appliance100according to an exemplary embodiment of the present subject matter. Refrigerator appliance100includes a housing or cabinet102that extends between a top104and a bottom106along a vertical direction V, between a left side108and a right side110along a lateral direction L, and between a front side112and a rear side114along a transverse direction T. Each of the vertical direction V, lateral direction L, and transverse direction T are mutually perpendicular to one another and form an orthogonal direction system. Cabinet102defines chilled chambers for receipt of food items for storage. In particular, cabinet102defines fresh food chamber122positioned at or adjacent top104of cabinet102with a freezer chamber124and a convertible chamber123arranged at or adjacent bottom106of cabinet102. As such, refrigerator appliance100is generally referred to as a bottom mount refrigerator. It is recognized, however, that the benefits of the present disclosure apply to other types and styles of refrigerator appliances such as, e.g., a top mount refrigerator appliance or a side-by-side style refrigerator appliance. As another example, although the illustrated example embodiment depicts the freezer chamber124on the left side and the convertible chamber123on the right side, it is recognized that such configuration is provided by way of example only and not limitation, e.g., the freezer chamber124and the convertible chamber123may be transposed in some embodiments. Consequently, the description set forth herein is for illustrative purposes only and is not intended to be limiting in any aspect to any particular refrigerator chamber configuration. Refrigerator doors128are each rotatably hinged to a corresponding edge of cabinet102for selectively accessing fresh food chamber122. Similarly, freezer door130and convertible chamber door131are rotatably hinged to an edge of cabinet102in the illustrated example embodiment for selectively accessing freezer chamber124and convertible chamber123. As another example, one or both of the freezer door130and the convertible chamber door131may instead be a front portion of a slidable drawer which can be selectively moved in and out of the respective chamber123and/or124along transverse direction T. To prevent leakage of cool air, the doors128,130,131, and/or cabinet102may define one or more sealing mechanisms (e.g., rubber gaskets, not shown) at the interface where the doors128,130,131meet cabinet102. Refrigerator doors128, freezer door130, and convertible chamber door131are shown in the closed configuration inFIG.1and in the open configuration inFIG.2. It should be appreciated that doors having a different style, position, or configuration are possible and within the scope of the present subject matter. In an exemplary embodiment, cabinet102also defines a mechanical compartment60at or near the bottom106of the cabinet102for receipt of a hermetically sealed cooling system configured for transporting heat from the inside of the refrigerator to the outside. One or more ducts may extend between the mechanical compartment60and the chilled chambers122,123, and/or124to provide fluid communication therebetween, e.g., to provide chilled air from the hermetically sealed cooling system, e.g., from an evaporator thereof, to one or more of the chilled chambers122,123, and/or124. As is generally understood by those of skill in the art, the hermetically sealed system contains a working fluid, e.g., refrigerant, which flows between various heat exchangers of the sealed system where the working fluid changes phases. For example, the hermetically sealed system includes at least one evaporator where the working fluid absorbs thermal energy and changes from a liquid state to a gas state and at least one condenser where the working fluid releases thermal energy and returns to the liquid state from the gas state. As is understood, because the system is sealed, the working fluid is contained within the system and travels between the heat exchangers of the hermetically sealed system. A fan is typically provided at each heat exchanger of the sealed system. For example, a fan may force air across and around the at least one evaporator to transfer thermal energy from the air to the evaporator (and more particularly, to the working fluid therein), thereby generating a flow of chilled air which may be provided to one or more of the chilled chambers122,123, and/or124. In some embodiments, some components of the sealed system may be located on different sides of a thermally insulated barrier, e.g., the at least one condenser may be positioned outside of the thermally insulated barrier with respect to the chilled chambers such that heat released from the working fluid as it condenses is directed away from the chilled chambers and to an ambient environment around the refrigerator appliance100, and the at least one evaporator may be positioned on the same side of the thermally insulated barrier as the chilled chambers, whereby the flow of chilled air from the evaporator(s) to the chilled chambers may be entirely contained within a thermally insulated enclosure. Refrigerator appliance100also includes a dispensing assembly132for dispensing liquid water and/or ice. Dispensing assembly132includes a dispenser134positioned on or mounted to an exterior portion of refrigerator appliance100, e.g., on an outer surface of one of refrigerator doors128. Dispenser134includes a discharging outlet136for accessing ice and liquid water. An actuating mechanism138, shown as a paddle, is mounted below discharging outlet136for operating dispenser134. In alternative exemplary embodiments, any suitable actuating mechanism may be used to operate dispenser134. For example, dispenser134can include a sensor (such as an ultrasonic sensor) or a button rather than the paddle. A control panel140is provided for controlling the mode of operation. For example, control panel140includes a plurality of user inputs (not labeled), such as a water dispensing button and an ice-dispensing button, for selecting a desired mode of operation such as crushed or non-crushed ice. Discharging outlet136and actuating mechanism138are an external part of dispenser134and are mounted in a dispenser recess142. Dispenser recess142is positioned at a predetermined elevation convenient for a user to access ice or water and enabling the user to access ice without the need to bend-over and without the need to open refrigerator doors128. In the exemplary embodiment, dispenser recess142is positioned at a level that approximates the chest level of an adult user. According to an exemplary embodiment, the dispensing assembly132may receive ice from an icemaker disposed in a sub-compartment of the fresh food chamber122. Refrigerator appliance100further includes a controller144. Operation of the refrigerator appliance100is regulated by controller144that is operatively coupled to control panel140. In some exemplary embodiments, control panel140may represent a general purpose I/O (“GPIO”) device or functional block. In some exemplary embodiments, control panel140may include input components, such as one or more of a variety of electrical, mechanical or electro-mechanical input devices including rotary dials, push buttons, touch pads, and touch screens. Control panel140can be communicatively coupled with controller144via one or more signal lines or shared communication busses. Control panel140provides selections for user manipulation of the operation of refrigerator appliance100, e.g., whereby a user may provide one or more set point temperatures for the various compartments122,123, and124. In response to user manipulation of the control panel140, controller144operates various components of refrigerator appliance100. For example, controller144is operatively coupled or in communication with various airflow components, e.g., dampers and fans, as discussed below. Controller144may also be communicatively coupled with a variety of sensors, such as, for example, chamber temperature sensors or ambient temperature sensors. Such chamber temperature sensors and/or ambient temperature sensors may be or include thermistors, thermocouples, or any other suitable temperature sensor. Controller144may receive signals from these temperature sensors that correspond to the temperature of an atmosphere or air within their respective locations. Controller144includes memory and one or more processing devices such as microprocessors, CPUs or the like, such as general or special purpose microprocessors operable to execute programming instructions or micro-control code associated with operation of refrigerator appliance100. The memory can represent random access memory such as DRAM, or read only memory such as ROM or FLASH. The processor executes programming instructions stored in the memory. The memory can be a separate component from the processor or can be included onboard within the processor. Alternatively, controller144may be constructed without using a microprocessor, e.g., using a combination of discrete analog and/or digital logic circuitry (such as switches, amplifiers, integrators, comparators, flip-flops, AND gates, and the like) to perform control functionality instead of relying upon software. The controller144may be positioned in a variety of locations throughout refrigerator appliance100. In the illustrated embodiment, the controller144is located within a control panel area140of one of the refrigerator doors128, as shown inFIG.1. In other example embodiments, the controller144may be positioned at or near the rear side114and/or the bottom106of the refrigerator appliance100. FIG.2provides a front view of refrigerator appliance100with refrigerator doors128, freezer door130, and convertible chamber door131shown in an open position. According to the illustrated embodiment, various storage components are mounted within fresh food chamber122, convertible chamber123, and freezer chamber124to facilitate storage of food items therein as will be understood by those skilled in the art. In particular, the storage components include bins146, drawers148, and shelves150that are mounted within fresh food chamber122, convertible chamber123, or freezer chamber124. Bins146, drawers148, and shelves150are configured for receipt of food items (e.g., beverages and/or solid food items) and may assist with organizing such food items. As an example, drawers148of fresh food chamber122can receive fresh food items (e.g., vegetables, fruits, and/or cheeses) and increase the useful life of such fresh food items. It is to be recognized that the benefits of the present disclosure apply to other types and styles of refrigerator appliances such as, e.g., a top mount refrigerator appliance, a side-by-side style refrigerator appliance or a standalone refrigerator-only or freezer-only appliance, compact, and any other style or model of refrigerator appliance. Consequently, the description set forth herein is for illustrative purposes only and is not intended to be limiting in any aspect to any particular configuration, such as not limiting to any particular refrigerator chamber configuration. Accordingly, the description herein of features such as the convertible chamber123, among other features, are by way of example only. Using the teachings disclosed herein, one of skill in the art will understand that the present subject matter can be used with any other style or model of refrigerator appliance. Turning now toFIG.3, a schematic illustration of a dispensing assembly132according to one or more exemplary embodiments of the present disclosure is provided. The dispensing assembly132may include a dispenser recess142with a platform143defined therein for receiving a vessel1000, and the dispensing assembly may provide, e.g., water, to the dispenser recess142and/or the vessel1000therein. As illustrated inFIG.3, the dispensing assembly132may include a vibration generator204. In various embodiments, as described in more detail below, the vibration generator204may be a mechanical vibration generator, e.g., a motor, or an acoustic vibration generator, e.g., a speaker. The vibration generator204may be connected to the controller144of the refrigerator appliance100and/or the actuating mechanism, e.g., paddle,138, by a first communication line200. Thus, the vibration generator204may be activated when the actuating mechanism138is activated, e.g. when the paddle is depressed or when the sensor (in embodiments where the actuating mechanism138is or includes a sensor) detects a vessel1000in the dispenser recess142. The vibration generator may, in various embodiments, be located adjacent to and/or in contact with a flexible hose202. The flexible hose202may comprise any suitable flexible material, such as silicone. As illustrated inFIG.3, the flexible hose202may be in fluid communication with a water supply to deliver water to the dispenser recess. For example, as those of ordinary skill in the art will recognize, the water supply may be a well, a municipal water system, or other suitable source of drinking water that is connected to a plumbing system in the building, e.g., residence or office, etc., in which the refrigerator appliance100is located. As is generally understood by those of ordinary skill in the art, the refrigerator appliance100may include a fitting (not shown) and a valve (not shown) for connecting to the plumbing system and may thereby receive water from the water supply. Thus, when the actuating mechanism138is activated, the valve may be opened, e.g., by the controller144, to deliver a flow of water from the water supply to the refrigerator appliance100, e.g., to the dispensing assembly132thereof via the flexible hose202. As mentioned above, the vibration generator204may be connected to the actuating mechanism138and/or controller144via a first communication line200, e.g., such that the vibration generator204is activated when the actuating mechanism138is activated. Thus, in response to the actuating mechanism138being activated, water may flow to the flexible hose202and from the flexible hose202to the dispenser recess142and a vessel1000placed therein, while the vibration generator204is also activated, and the vibration generator204may move the flexible hose202relative to the dispenser recess142, causing a wave pattern flow of water206to be provided to the dispenser recess142and the vessel1000therein. Thus, it is understood that the term “flexible” in the context of the flexible hose202means a material which transmits vibrations from the vibration generator204to water flowing through the hose202sufficiently to produce the wave pattern with the characteristics, e.g., wavelength, described below without damage to the hose202and without damaging or loosening connections between the hose202and the water supply. In some embodiments, e.g., as illustrated inFIG.3, the dispensing assembly132may include one or more arrays of light-emitting diodes (LEDs). For example, a first array of LEDs210may be positioned within the dispenser recess142on one side of the dispenser recess142and a second array of LEDs212may be positioned opposite the first array of LEDs210within the dispenser recess142. One or both of the arrays of LEDs may be interconnected with the actuating mechanism138and/or controller144, e.g., by a second communication line201, such that the array(s) of LEDs210,212are activated at the same time the vibration generator204is activated. Additionally, in some embodiments, the array(s) of LEDs210,212may be synchronized with the vibration generator204, such that the LEDs turn on and off at the same time and same rate as the vibration generator204generates pulses. In some embodiments, e.g., as illustrated inFIG.3, the dispensing assembly132may include a loudspeaker208. In embodiments where the vibration generator204is a speaker218, the loudspeaker208is in addition to the speaker218. The loudspeaker208may be configured to play music when the actuating mechanism138is activated. The loudspeaker208may also be connected in series with the array(s) of LEDs210,212, whereby the array of light emitting diodes210,212and the loudspeaker208are activated at the same time, e.g., each is activated whenever the other is activated. In some embodiments, the wave pattern flow of water206from the flexible hose202may be a sinusoidal wave pattern. In some embodiments, the wave pattern flow of water206from the flexible hose202may have an amplitude and a wavelength. The wavelength may be determined, for example, based on the velocity of water flowing from the flexible hose202divided by the frequency of vibration provided by the vibration generator204. Thus, the vibration generator204may be configured to vibrate the flexible hose202at a predetermined frequency to provide the wave pattern flow of water206with a predetermined wavelength. For example, the predetermined frequency may be between about 20 Hz and about 40 Hz, such as between about 25 Hz and about 35 Hz, such as about 25 Hz, about 30 Hz, or about 35 Hz. A predetermined frequency of vibration of about 25 Hz may result in a wavelength of the wave pattern flow of water206of about 64 mm, a predetermined frequency of vibration of about 30 Hz may result in a wavelength of the wave pattern flow of water206of about 54 mm, and predetermined frequency of vibration of about 35 Hz may result in a wavelength of the wave pattern flow of water206of about 46 mm. In such embodiments, the wave pattern flow of water206may include between about four cycles, e.g., four peaks and four troughs, and about six cycles, e.g., six peaks and six troughs, as the wave pattern206traverses the vertical distance of the dispenser recess142. Turning now toFIGS.4through6, in various embodiments, the flexible hose202may move relative to the dispenser recess142along at least the lateral direction L, e.g., as may be seen inFIGS.4and5, and may also move relative to the dispenser recess142along the transverse direction T, e.g., as seen inFIG.6. Thus, the wave pattern flow of water206may be a flat wave or may be a spiral pattern. The spiral shape of the wave pattern flow of water206is best seen inFIG.6. In some embodiments, e.g., as illustrated inFIG.4, the vibration generator204may be a motor214. As may be seen inFIG.4, in such embodiments, the vibration generator204, e.g., motor214, may be directly connected to the flexible hose202, such as by linkage216. The flexible hose202may pass through the linkage216, such that the flexible hose202is in contact with the linkage216around an entire outer perimeter, e.g., circumference, of the flexible hose202. For example, in such embodiments, the linkage216may thereby transfer vibration directly from the motor214in at least two directions, e.g., both to the left and to the right on the page inFIG.4, such as back and forth along the lateral direction L. In some embodiments, e.g., as illustrated inFIG.5, the vibration generator204may be a speaker218. In such embodiments, the flexible hose202may not be constrained, e.g., in contrast to embodiments where the linkage216is provided as described above. The flexible hose202may contact the speaker218, e.g., as illustrated inFIG.5, and may thereby receive vibrations directly from the speaker218. For example, in some embodiments wherein the vibration generator204is a speaker218, the flexible hose202may contact the speaker218on only one side of the flexible hose202. This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they include structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims. | 22,508 |
11858799 | DETAILED DESCRIPTION OF THE INVENTION Certain exemplary embodiments will now be described to provide an overall understanding of the principles of the structure, function, manufacture, and use of the device and methods disclosed herein. One or more examples of these embodiments are illustrated in the accompanying drawings. Those skilled in the art will understand that the devices and methods specifically described herein and illustrated in the accompanying drawings are non-limiting exemplary embodiments and that the scope of the present invention is defined solely by the claims. The features illustrated or described in connection with one exemplary embodiment may be combined with the features of other embodiments. Such modifications and variations are intended to be included within the scope of the present disclosure. Further, in the present disclosure, like-numbered components of the embodiments generally have similar features, and thus within a particular embodiment each feature of each like-numbered component is not necessarily fully elaborated upon. Additionally, to the extent that linear or circular dimensions are used in the description of the disclosed systems, devices, and methods, such dimensions are not intended to limit the types of shapes that can be used in conjunction with such systems, devices, and methods. A person skilled in the art will recognize that an equivalent to such linear and circular dimensions can easily be determined for any geometric shape. Further, to the extent that directional terms like top, bottom, up, or down are used, they are not intended to limit the systems, devices, and methods disclosed herein. A person skilled in the art will recognize that these terms are merely relative to the system and device being discussed and are not universal. According to certain exemplary embodiments of the invention as described herein, the present disclosure provides an ergonomic, high flow rate, self-venting dispensing tap for a high-viscosity, flowable fluid or liquid formulation, such as a laundry detergent. Referring generally toFIGS.1-10, and according to some embodiments of the invention, a dispensing tap100may generally include a body102having a peripheral skirt104for connection to the neck902(SeeFIG.11) of a container900. Referring toFIGS.1and11, an exemplary embodiment of the container900includes a neck902or opening for connection of the dispending tap100. In some embodiments, the container neck902and skirt104may include complementary threads106where the tap structure100may be threaded or rotated into place on the container900, or the neck902and skirt102may be provided with a bayonet or other connection. The dispensing tap100may further include a dispensing head108, and a throat110connecting the body102to the dispensing head108where the throat110provides a fluid flow path112from an interior of the body102to an interior of the dispensing head108. The exemplary dispensing head108is oriented vertically and may include a dispensing outlet or mouth114at a lower end thereof. Referring toFIGS.8-10, a shut off valve116may be configured for sealing engagement with the mouth114of the dispensing head108. The shut off valve116may be elastomeric or other material suitable for forming a fluid seal with the mouth114. Still referring toFIGS.8-10, a piston118may be axially guided within the dispensing head108. The piston118may include a peripheral seal120which is slidably engaged with an interior surface of the dispensing head108at the upper end thereof. A valve stem122extends downwardly from the piston118and is further guided by a guide cylinder124formed within the lower end of the dispensing head108. A terminal end of the valve stem122extends below the guide cylinder124and may be coupled to the shut off valve116. In the exemplary embodiments, a nipple126on the upper surface of the shut off valve116is press fit into a bore128in the terminal end of the valve stem122. In use, the piston118may be selectively actuable or depressible (see arrows inFIGS.9-10) by a button structure130which is integrated with the upper surface of the piston118. The piston118may be actuated between a normally closed position (SeeFIGS.2-8) wherein the shut off valve116is seated within the mouth114, and an open position (SeeFIGS.9and10) wherein the shut off valve116is disengaged from the mouth114. The button structure130may be integrally formed with the piston118or may be molded separately and attached. According to some embodiments of the invention, the dispensing head108may include external finger holds132to facilitate depression of the actuator button130connected to the piston118. The exemplary finger holds132extend radially outwardly from the exterior surface of the dispensing head108and facilitate the depression of the button actuator130with the users thumb by providing a leverage point for the user's index and middle fingers straddling the dispensing head108. Referring toFIGS.8and10, a spring134may be captured between the piston118and the dispensing head108normally biasing the piston118and shut off valve116to the closed position. In some embodiments, the spring134may comprise a slotted tubular spring element formed from a tensile polymer. The slotted tubular spring element134may be captured between opposing loading cones136,138formed on the piston118and the dispensing head108. In the exemplary embodiments, the slotted tubular spring element134is cylindrical in shape and the loading cones136,138are generally conical in shape. The exemplary embodiments of the loading cones include a first frustoconical pre-loading wall section having a steeper wall angle greater than 11 degrees, and a second frustoconical primary loading wall section having a shallower wall angle of less than 11 degrees. In some exemplary embodiments, all of the components of both the dispensing tap and the spring assembly are molded from the same plastic material making the entire dispensing tap easily recyclable in a single plastic material classification. Exemplary plastic materials include polypropylene (PP), high-density polyethylene (HDPE), and low-density polyethylene (LDPE). However, the disclosure should not be considered to be limited to these materials. As seen inFIGS.8and10, the piston loading cone136is axially compressible towards the lower fixed cone138within the open ends of the slotted tubular spring element134whereby the slotted tubular spring element134radially expands in tension to create an opposing radial contraction force. Deformation of the tubular spring walls elastically stores energy which will return the spring to its normal at rest shape when released. When released, the spring element134elastically contracts, in turn creating an axial extension force, and returns the upper piston cone136to its normal at rest position. Some embodiments of the spring assembly include a spring element134having strain reducing ribs extending along the opposing edges of the longitudinal slot (SeeFIG.20). The ribs may include outwardly convex surfaces extending both radially outward and circumferentially outward from the slot edges. This embodiment further includes a first thinner wall thickness at the slot edges and a second thicker wall thickness diametrically opposed from the slot edges. The arcuate surface along with the increasing wall thickness moving away from the slot edges, more evenly distributes strain throughout the spring element and extends the life cycle of the polymer spring element. Referring now toFIG.11, and according to other embodiments, the spring134may comprise a conventional coil spring134A captured between the piston118and dispensing head108. In this regard, the upper and lower loading cones136,138act as spring guides. In some embodiments, an atmospheric vent140may be provided in communication with an interior of the body102and in some embodiments, the vent140may be opened and closed with movement of the piston118and shut off valve116. As best seen inFIGS.8and10, a vent140extends between an interior surface of the dispensing head108and the interior of the body108. The vent140may include ball valve142disposed on the interior of the body108to prevent fluid from escaping in at rest conditions. In certain embodiments of the invention the peripheral piston seal120is configured with a v-shaped multiple lip (chevron) seal for engagement with the vent opening formed on the interior surface of the dispensing head. In this regard, the peripheral chevron seal120may be engaged with, or overlie, the vent opening when the piston is in the closed position (SeeFIG.8) and may be disengaged from the vent opening (SeeFIG.10) when the piston is in the open position. This arrangement creates a self-venting system wherein the vent140and the shut off valve116are opened and closed simultaneously. Referring toFIGS.12and13, some embodiments200of the invention may exclude the ball valve structure and rely on only the chevron seal220to prevent fluid from escaping in at rest conditions. The embodiment200is structurally and functionally similar to tap100, and includes body202, dispensing head208, throat210, mouth214, shut off valve216, piston218, button230and spring234. Other embodiments of the invention300, as illustrated inFIGS.14and15may include an airless vent system310. The vent340in these embodiments extends from an opening in the body302into the interior by means of an extension tube350, and an expandable vent bag352is positioned on the terminal end thereof. The embodiment300is otherwise structurally and functionally similar to tap100. In other embodiments400, as illustrated inFIGS.16and17, a ball valve442may be located at the terminal end of an extension tube450which would extend into the interior of the container900when mounted. The embodiment400is otherwise structurally and functionally similar to tap100. Referring back toFIGS.1-10, in order to provide a high flow rate from the dispensing head108, the cross-sectional flow area of the outlet or mouth MAmay be greater than the cross-sectional flow area of the throat TA. As best seen inFIGS.4and7, the flow area of the throat TA(dashed lines inFIG.4) is smaller than the flow area provided by the mouth MA(dashed lines inFIG.7). The constricted throat area TAaccelerates fluid flow through the throat and into the dispensing head108where the fluid can freely flow out of the larger diameter mouth114. In some embodiments, the diameter (PD) of the peripheral seal120on the piston118is larger than the diameter (VD) of the shut off valve116. In this configuration, normal fluid head pressure is greater on the piston seal120than the shut off valve116, and naturally exerts a higher force in the closed direction to keep the shut off valve116closed. The arrangement further works advantageously when external pressure is exerted on the container900to prevent leaks from the shut off valve116. The configuration is visible inFIGS.1-10which show the upper piston portion of the dispensing head having a slightly larger diameter than the lower mouth portion. However, the features are best illustrated inFIG.11showing the two different internal diameters. Referring toFIGS.18-22, another exemplary embodiment500of the invention is illustrated. The illustrated embodiment500is nearly identical to the exemplars100,200with the exception of an elongated radial finger flange532to facilitate actuation of the button actuator530. The tap500includes a body502, dispensing head508, throat510, shut off valve516, piston518, peripheral seal520, valve stem522, button530, spring532, vent540and ball valve542. Referring toFIG.21, the dispensing head508includes internal guide channel524and loading cone538which are integrally formed with the dispensing head508and suspended therein by radial support fingers560. Referring toFIG.22, the piston518includes integrally formed conical loading cone536and chevron peripheral piston seal520. Referring toFIGS.23-31, some embodiments600of the invention may include an actuator lever670which engages with the top of the piston. The embodiment is similar in internal functional structure as the previous embodiments100,200,500, with the exception of the lever670and finger hold structures632. The tap600includes a body602, dispensing head608, throat610, mouth614, shut off valve616, piston618, seal620, valve stem622, button630, spring634, vent640and ball valve642. The670lever may be L-shaped and pivotably anchored at one end672on the exterior of the body602. A first leg674of the lever670extends over the top of the dispensing head608and is engaged with a raised shoulder676on the top surface of the piston618. A second leg678of the lever670then depends downwardly and forwardly therefrom in front of the dispensing head608. As best seen inFIGS.23and27, the finger hold structures632are also L-shaped with a horizontal leg680and a vertical leg682. In use, the operator may actuate the tap600by either pressing downwardly on the top (first leg674) of the lever670or inwardly on the front (second leg678) of the lever670. In the first instance the horizontal legs680of the finger holds632may be used as a leverage point for the operator's index and middle fingers as the first leg674is pressed downwardly by the thumb. In the second instance, the vertical legs682of the finger holds632may be used as leverage points for the same index and middle fingers as the operator pressed inwardly on the second leg678. The lever670and finger holds632provide an improved ergonomic system and better user experience. Referring toFIGS.32-34, an alternative embodiment700is shown. The alternative embodiment700can be used in conjunction with any of the above embodiments. As shown inFIGS.32-34, some embodiments700are adapted for improved sealing around the venting passages and a modified stroke length for accommodating different flow rates. The exemplary illustrated tap700includes a body702, a dispensing head708, a throat710, a mouth714, a shut off valve716, a piston718, a seal720, a valve stem722, a button730, a spring734, a vent740, and a ball valve742. As best seen inFIG.34, the button730has a larger and polished peripheral seal720for better sealing and vent coverage. The seat of the ball valve742also has an improved seat angle (35 degrees) which is more easily molded. The seat angle can be defined as the angled face at the terminal end of the vent740disposed in the inner surface of the dispensing head708relative to the longitudinal axis of the dispensing head708. The angled seat surface is better seen in connection withFIG.31where the check ball642sits against adjacent the valve seat. The exemplary angle may range from 30 to 45 degrees for optimal functionality and ease of molding. The body702has also been provided with a larger plug seal790for engagement with the bottle neck. Referring to bothFIGS.33and34, it can be seen that the shut off valve716has been improved with a steeper engagement angle for contacting the mouth714and that the valve stem722is secured within the shut off valve716. The redesigned valve shape keeps fluid from having an exaggerated outward flowing “umbrella shape” when the fluid is flowing over the valve716. The shape of the valve716can be described as a flared bell-shape having a steeper slope than the valves116,216,516,616of the prior embodiments. The flared bell-shaped valve716allows fluid to flow downward, relative to the tap700as opposed to the flatter valves116,216,516,616described above. The downward flare prevents a flowing fluid from creating an “umbrella shape.” The exemplary valve716can be molded from MDPE (medium-density polyethylene) NA285 or other suitable materials. Another feature to be noted is that the dispensing head708, valve716and valve stem722are slightly elongated in this embodiment as compared to the earlier embodiments. The elongated design provides a longer stroke length of the push button730during actuation and accommodates user with both vented and non-vented versions. The present design allows for a stroke length range of about 5.8 mm to about 7 mm. Another similar embodiment (not shown) removes the ball vent structure740for a non-vented version, but as noted above is otherwise the same. It can therefore be seen that the present disclosure provides for a novel dispensing system and a liquid dispensing tap having an ergonomic design, high flow rate, and self-venting dispensing tap for a high-viscosity, flowable fluid or liquid formulation, such as a laundry detergent. Having thus described certain particular embodiments of the invention, it is understood that the invention defined by the appended claims is not to be limited by particular details set forth in the above description, as many apparent variations thereof are contemplated. Rather, the invention is limited only be the appended claims, which include within their scope all equivalent devices or methods which operate according to the principles of the invention as described. | 16,994 |
11858800 | DETAILED DESCRIPTION Subject matter is described throughout this Specification in detail and with specificity in order to meet statutory requirements. But the aspects described throughout this Specification are intended to be illustrative rather than restrictive, and the description itself is not intended necessarily to limit the scope of the claims. Rather, the claimed subject matter might be practiced in other ways to include different elements or combinations of elements that are similar to the ones described in this Specification and that are in conjunction with other present, or future, technologies. Upon reading the present disclosure, alternative aspects may become apparent to ordinary skilled artisans that practice in areas relevant to the described aspects, without departing from the scope of this disclosure. It will be understood that certain features and subcombinations are of utility and may be employed without reference to other features and subcombinations. This is contemplated by, and is within the scope of, the claims. At a high level, this disclosure describes systems and methods related to a fluid exchanger that exchanges fluid (e.g., coolant) in a reservoir (e.g., radiator or other coolant reservoir). Vehicle maintenance includes changing the fluid in a fluid system by removing old fluid and adding new fluid. In some systems, a negative pressure may be applied to the reservoir to vacuum or suction old fluid from the reservoir. New fluid may then be added to the reservoir by using a negative pressure held in the reservoir, a positive pressure applied to a new fluid storage tank, or a combination thereof. Conventional fluid-exchange systems may include an old-coolant tank and a new-coolant tank, housed together on a cart or other transport assembly with a control panel for changing operations between vacuum and pressure. In addition, these systems often include a hose extending from each tank to one or more nozzles or dispensers, which are used to connect to a reservoir (e.g., radiator), such that the nozzle(s) may be stretched some distance away from the control panel to service a vehicle. Conventional approaches often include a control on the control panel for switching between vacuum and pressure; however, because the control panel is positioned away from the dispenser during the service, a technician may have to perform extra steps at the control panel, which take time and focus away from other tasks. The present disclosure describes a fluid exchanger that includes fluid circuitry, plumbing, conduit, etc. to draw a first fluid (e.g., old coolant) from a reservoir (e.g., coolant system) into a first tank, to introduce a second fluid (e.g., new coolant) from a second tank into the reservoir, and if desired, to discharge the first fluid from the first tank for disposal. In contrast to conventional systems that can be complex with more user controls, the present disclosure includes a minimal number of controls for easier and more efficient operation. In addition, the present disclosure includes a multi-functional, hand-held nozzle that combines multiple operations into a single tool, including sealingly connecting to the reservoir, changing between a first operation mode (e.g., drawing fluid) to a second operation mode (e.g., introducing fluid), and viewing a status of operations (e.g., whether fluid is flowing to or from the reservoir). Furthermore, the system of the present disclosure quickly and efficiently transitions from servicing a first reservoir to a second reservoir (e.g., on the same vehicle or on a different vehicle) without requiring manipulation of controls on the control panel—i.e., the system can be operated using only the nozzle. In contrast, conventional systems often include multiple tools, each having separate and limited functionality that independently seal, change modes, and indicate a flow status. In addition, conventional systems often require a technician to operate controls on the control panel before and after servicing each reservoir. With reference toFIG.1,FIG.1is an example fluid exchanger110in accordance with one aspect of the present invention. At a high level, the fluid exchanger110includes a first tank112for holding a first fluid (e.g., used coolant) and a second tank114for holding a second fluid (e.g., new coolant). The first tank112and the second tank114may include at least a portion that is transparent to permit the fluid inside to be viewed (e.g., to view the fluid level, whether the fluid level is raising or lowering, etc.). For example, each tank may be constructed of a clear fiber glass material, or a portion of each tank may include a longitudinal viewing window. In another aspect, each tank112and114includes a tube (e.g., clear fiber glass tube) that is capped at a top end by a top plate116and capped at a bottom end by a bottom plate118. As depicted inFIG.1, the fluid exchanger110includes tie rods (e.g.,120) that couple the top plate116to the bottom plate118and generally hold the various portions of the fluid exchanger110together. In addition, the bottom plate118includes wheels for transporting the fluid exchanger, including fixed direction wheels124and caster wheels126. As such, the fluid exchanger110may be transported by rolling (e.g., like a hand truck or dolly), such as by using the tie rods as handles. In a further aspect, the fluid exchanger110includes a control housing128containing various components for controlling operation of the fluid exchanger110. For example, the control housing128includes a port130for connecting to a source132of pressurized air (e.g., shop air other compressed air source). In addition, the control housing128includes a first switch134and a second switch136for controlling operations of the fluid exchanger110that leverage pressurized air from the source132. For example, the first switch134and the second switch136may control the flow of pressurized air through various fluid conduits to control whether either positive pressure or suction is applied to each of the first tank112and the second tank114.FIG.2illustrates an example of components that might be controlled by the switches134and136and that might be at least partially contained in the control housing128, in accordance with one aspect of the present disclosure. Referring toFIG.2,FIG.2depicts a block diagram of a system210of components of the fluid exchanger110according to one aspect. Some components of the system210that are depicted inFIG.2may not be shown inFIG.1, and these components may be obscured from view or housed in the control housing128. Among other things,FIG.2depicts various pathways extending from the port130to the first tank112and the second tank114. These pathways are configured to transport positively or negatively pressurized air or gas and may include various structures, such as conduit, hose, lines, etc. coupled by connectors, fittings, etc. FIG.2includes the port130for connecting to a source132of pressurized air. In addition, the system210includes a pressure regulator138for regulating a pressure of the air provided from the source132. The system210includes a first-switch fluid pathway140transporting air from the port130to the first switch134and a second-switch fluid pathway142transporting air from the port130to the second switch136. The first-switch fluid pathway140and the second-switch fluid pathway142may split off from a common conduit or trunk extending from the port130and/or the pressure regulator138. In accordance with one aspect of the present disclosure, the first switch134controls flow to a first fluid circuitry of the system210, and the second switch136controls airflow to a second fluid circuitry of the system210. In one aspect, the first fluid circuitry includes fluid pathways fluidly coupled with the first tank112and the second tank114and includes various components to leverage the pressurized air to apply a positive pressure or a negative pressure (vacuum or suction) on the tanks112and114. For example, the first fluid circuitry may include a first tank pathway148that imparts a positive or negative pressure on the first tank112and a second tank pathway150that imparts a positive or negative pressure on the second tank114. In one aspect, the first tank pathway148and the second tank pathway150split from a common trunk or conduit at or near the first switch134. In one aspect, the first tank pathway148includes one or more fluid conduits extending from the first switch134to the first tank112. In addition, the first tank pathway148includes an ejector144positioned along the first tank pathway148, and the ejector144receives positively pressurized air passing through the first switch134and creates a vacuum pulled on the first tank112. The first tank pathway148may also include another pressure regulator146controlling a pressure applied to the first tank112. In another aspect, the second tank pathway150includes one or more fluid conduits extending from the first switch134to the second tank114. Furthermore, the second tank pathway150may include a low-pressure regulator147for maintaining a relatively low pressure (e.g., 2-3 psi) applied to the second tank114. In accordance with this disclosure, when the system210is pressurized (e.g., receiving pressurized air from the source132) and the first switch134is open, then a vacuum is pulled on the first tank112and a positive pressure is applied to the second tank114. In accordance with another aspect, the second fluid circuitry of the system210that is controlled by the second switch136is also coupled with the first tank112. For example, the second fluid circuitry may include one or more fluid conduits extending from the second switch136to the first tank112, and also controlled by the pressure regulator146. At least some of the conduits of the second fluid circuitry may also be part of the first tank pathway148of the first fluid circuitry (e.g., the conduits may merge or join into one another at a fitting or other connection). In accordance with one aspect, when the system210is pressurized (e.g., receiving pressurized air from the source132) and the second switch136is open, then a positive pressure may be applied to the first tank112. Referring toFIGS.1and2,FIGS.1and2both show a first fluid line152extending from the first tank112and a second fluid line154extending from the second tank114, and the fluid lines152and154are configured to carry fluid (e.g., coolant) to or from the tanks112and114. For example, each fluid line may connect to the respective tank at a port (obscured from view) near or below the bottom plate118. In accordance with one aspect of the present disclosure, both fluid lines152and154connect to a hand-held nozzle156, which may be used to dispense fluid from the first tank112and the second tank114or to vacuum fluid to the first tank112. The first fluid line152and the second fluid line154may include various types of conduits or hoses, such as metal spiral wrapped hoses. The hand-held nozzle156may include various components. For example, the hand-held nozzle includes a handle158for grasping and manipulating the nozzle156. In addition, the nozzle156includes a valve housing160containing components for selecting between fluid lines, as well as a reservoir connector162(e.g., tapered rubber stopper or cone with through hole) for interfacing with an opening of a reservoir (e.g., fill port for radiator cap) and an insert tube164for insertion into the reservoir. Referring now toFIGS.3A-3D, an example hand-held nozzle156, and components thereof, is illustrated in more detail. In general, the nozzle156includes connections to the first and second lines152and154; a connection to the insert tube164; and a valve assembly for selectively fluidly connecting the first and second lines152and154to the insert tube164. In one aspect, the nozzle156includes a first nozzle port166for connecting to the first line152and a second nozzle port168for connecting to the second line154. For example, the ports166and168may include a barbed fitting that inserts into the lines152and154. The nozzle ports166and168are depicted in the end of the handle158, and in other aspects, the ports166and168may be positioned at other locations, such as on opposing sides of the valve housing160. In addition, the nozzle156includes a first nozzle fluid channel167(e.g.,FIG.3Cshowing a cross section of the handle) extending from the first nozzle port166to the valve housing160and a second nozzle fluid channel169(e.g.,FIG.3C) extending from the second nozzle port168to the valve housing160. The first nozzle fluid channel167and the second nozzle fluid channel169are obscured from view inside the handle158inFIG.3Aand are shown in a cross section inFIG.3C. Each nozzle fluid channel may terminate at a sealed connection to the valve housing160, such as at the respective seal170and172shown inFIG.3B(in which the handle158is omitted) and3C. For example, each nozzle port166and168may include a threaded connection that couples to a through hole in the handle158, thereby forming the first and second nozzle fluid channels167and169, and when the handle158is connected to the valve housing160, then each through hole may seat against a respective seal170and172. As indicated above, the valve housing160also includes an insert-tube port174for connecting the insert tube164to the valve housing160. For example, the valve housing160may include a threaded connection or other quick-connect fitting attaching the insert tube164to the valve housing160. In accordance with an aspect of the present disclosure, the insert tube164includes a first segment176that extends from the connection174and extends externally to the valve housing160. In addition, the insert tube164passes through an aperture178in the valve housing160(viewable inFIG.3Bwhere the insert tube164inserts into the valve housing and also identified in the cross sectional view ofFIG.3C), extending entirely through the valve housing160. As such, after exiting the valve housing160, the insert tube164includes a second segment179extending from the valve housing160to a terminal end. Furthermore, the second segment179may extend through a through hole in the reservoir connector162, such that when the reservoir connector162is coupled to an opening of a reservoir, the second segment179inserts into the reservoir. In an aspect of this disclosure, a length of the second segment179is adjustable to fit reservoirs having different depths. For example, to increase a length of the second segment179, at least part of the first segment176may be fed into the aperture178, and to decrease a length of the second segment179, at least part of the insert tube164(e.g., along the first segment176) may be pulled from the aperture178. Among other things, this adjustability permits the length of the second segment179to increase or decrease to adjust to the size of the reservoir and to improve the likelihood that fluid will be drawn from at or near the lowest region of the reservoir. In another aspect of the disclosure, at least a portion of the insert tube164(e.g., at least a portion of the first segment176) is made of a transparent material (e.g., nylon tubing), which permits an operator to view the status of fluid flow through the nozzle. For example, if fluid is being drawn from a reservoir, an operator may view the clear portion of the first segment176to determine when lower amounts (or no further amounts) of fluid are flowing, which may indicate all or most of the fluid has been removed from the reservoir. The valve housing160may include various components to selectively connect the first nozzle fluid channel167or the second nozzle fluid channel169to the insert tube164. For example, as illustrated inFIG.3C, the valve housing160may include a first valve chamber180fluidly coupled with the first nozzle fluid channel167by way of a first valve fluid channel181. In addition, the valve housing160may include a second valve chamber182fluidly coupled with the second nozzle fluid channel169by way of a second valve fluid channel183. Furthermore, as depicted in the cross-sectional view provided byFIG.3D, the valve housing160may include a third valve fluid channel184that fluidly connects the first valve chamber180with the insert-tube port174. That is, the insert-tube port174may include a through hole185that fluidly connects with the third valve fluid channel184. In addition, as depicted in the cross-sectional view provided byFIG.3D, the valve housing160may include a fourth valve fluid channel186that fluidly connects the second valve chamber182with the through hole185of the insert-tube port174. In one aspect, the valve housing160includes a third valve chamber187abutted by the insert-tube port174, and the third valve chamber187may provide an interface between the third and fourth valve fluid channels184and186and the through hole185. In a further aspect of the disclosure, the valve housing160includes a first valve control188(FIG.3B) and a second valve control190(FIG.3B) that may be independently depressed by an operator to selectively connect the first nozzle fluid channel167or the second nozzle fluid channel169to the insert tube164. For example, the first valve control188is coupled to a spring biased plunger that is seated in the first valve chamber180and is biased outward in a closed position (depicted inFIG.3B) that blocks fluid connection between the first valve fluid channel181and the third valve fluid channel184. When the first valve control188is depressed, the plunger moves to an open position that opens fluid connection between the first valve fluid channel181and the third valve fluid channel184. Similarly, the second valve control190is coupled to another spring biased plunger that is seated in the second valve chamber182and is biased outward in a closed position that blocks fluid connection between the second valve fluid channel183and the fourth valve fluid channel186. When the second valve control188is depressed (as shown inFIG.3B), the plunger moves to an open position that opens fluid connection between the second valve fluid channel183and the fourth valve fluid channel186. In a further aspect, each valve control188and190(and/or each respective plunger) includes a respective catch mechanism that allows the plunger to be set in an open or closed position, such that the operator may activate the control (by depressing) and release the nozzle156while the valve remains in the set position. The fluid exchanger110may include various other elements. For example, a fill cap115may be used to add fluid (e.g., new coolant) to the second tank114. In addition, the reservoir connector162may be a first size (e.g., range of diameters based on the taper), and the fluid exchanger110may include one or more additional reservoir connectors that are other sizes, smaller or larger than the first size (e.g., smaller or larger tapered cone shape). The reservoir connector162may be disconnected from the valve housing160and replaced by another reservoir connector having a different size. For example, the valve housing160may include a barb or other connector on the bottom that attaches to the reservoir connector162. Moreover, the insert tube164may include a first length, and the fluid exchanger may include one or more other insert tubes that are either shorter or longer than the first length, such that the insert tube164may be disconnected from the valve housing160and replaced by a different insert tube having a different length. The alternatively sized reservoir connector(s) and the alternatively sized insert tube(s) may be selected based on the size of the reservoir being serviced. In another aspect, the fluid exchanger110may include one or more additional tanks (e.g., tank(s)113inFIG.2) for holding other fluid, in which case the system210may include one or more other switches for selecting between the second tank114and the other tanks. The fluid exchanger110may operate in various manners. For example, in one aspect the fluid exchanger110is used to draw used fluid (e.g., coolant) from a reservoir (e.g., radiator) and to dispense new fluid to the reservoir. When initiating the service, the reservoir cap (e.g., reservoir cap) may be removed and the reservoir connector162may be inserted into the reservoir fill port. In addition, a length of the insert tube164may be adjusted so that the terminal end of the insert tube164is at or near the bottom of the reservoir. The port130may already be connected to the pressurized air source132, or if not, then the port130is coupled to the air source132. In addition, the nozzle156may already be energized, if the first switch134is open, or alternatively the first switch134may then be moved to an open position. Once the first switch is open, a vacuum is pulled on the first tank112and on the first fluid line152, and the second tank114is pressurized (relatively low pressure via the low-pressure regulator147) to disperse fluid from the second tank114into the second fluid line154. At that point, the operator may depress the first valve control188to fluidly connect the first valve fluid channel181and the third valve fluid channel184, which in turn pulls the vacuum on the insert tube164and the reservoir to draw old fluid into the first tank112. The first valve control188may be latched in the open position to allow the used fluid to be drawn without an operator continually pressing the first valve control188. The operator may observe various conditions to determine when the old fluid has been removed, such as when bubbles may appear stagnant in the first segment176of the insert tube164. Once the old fluid has been removed from the reservoir, the second valve control190may be depressed in order to fluidly connect the second valve channel183and the fourth valve channel186. The valve housing160may include a mechanism that closes the first valve control188when the second valve control190is depressed, or the operator may unlatch the first valve control188to close it. Once the second valve channel183fluidly connects to the fourth valve channel186, then new fluid may be dispersed from the second tank114to the reservoir using the low positive pressure in the second tank114, a negative pressure held in the reservoir when the old coolant is drawn out, or a combination thereof. The operator may observer various conditions to determine when new coolant is no longer flowing to the reservoir (e.g., when the bubbles or fluid in the first segment176appear stagnant; when a fluid level in the second tank is no longer decreasing), and at that point, the operator may close the second valve control190. In accordance with an aspect of the disclosure, the low pressure maintained by the low-pressure regulator147in a range of about 1 psi to about 5 psi (and in one embodiment between 2 psi and 3 psi) helps to improve the likelihood that the radiator will be completely filled using the nozzle (as opposed to having to complete an extra top-off step). In addition, with the system already energized, the operator can seamlessly transition to another reservoir (e.g., another reservoir on the same vehicle or on another vehicle) to repeat the process. At that point, the operator only needs to remove the reservoir cap on the next reservoir to be serviced, insert the nozzle156, and open the first valve control188. As such, an aspect of the present disclosure may be used in change fluid in systems or vehicles that have multiple reservoirs, such as an additional exhaust gas recirculation system; an electric vehicle with multiple reservoirs (e.g., coolant reservoirs); a hybrid electric vehicle with multiple reservoirs (e.g., coolant reservoirs); etc. Again, the multi-functional, hand-held nozzle provides controls directly at the nozzle, which allows a technician to remove and add fluid quickly, and quickly transition from one reservoir to the next without having to move to, and operate, a separate control panel. Moreover, the relatively low pressure (e.g., 2-3 psi by the low-pressure regulator147) may enhance usability with systems having low pressure cooling systems. For example, some electric and hybrid electric vehicle systems may include low pressure cooling systems, and the relatively low pressure imparted through the second line154may be reduce the likelihood that these systems could be damaged during servicing. In a further aspect, the fluid in the first tank112may be easily dispensed to a waste container. For example, with the port130connected to a source132, the second switch136is opened to apply a positive pressure to the first tank112and disperse the old coolant from the first tank112and into the first fluid line152. By opening the first valve control188the old coolant can then be dispensed through the nozzle156. As used herein, a recitation of “and/or” with respect to two or more elements should be interpreted to mean only one element, or a combination of elements. For example, “element A, element B, and/or element C” may include only element A, only element B, only element C, element A and element B, element A and element C, element B and element C, or elements A, B, and C. In addition, “at least one of element A or element B” may include at least one of element A, at least one of element B, or at least one of element A and at least one of element B. Further, “at least one of element A and element B” may include at least one of element A, at least one of element B, or at least one of element A and at least one of element B. From the foregoing, it will be seen that this subject matter is well adapted to attain all the ends and objects hereinabove set forth together with other advantages, which are obvious and which are inherent to the structure. It will be understood that certain features and subcombinations are of utility and might be employed without reference to other features and subcombinations. This is contemplated by and is within the scope of the claims. Since many possible alternative versions of the subjected matter might be made without departing from the scope thereof, it is to be understood that all matter herein set forth or shown in the accompanying drawings is to be interpreted as illustrative and not in a limiting sense. | 26,292 |
11858801 | DETAILED DESCRIPTION A fuel cell, or fuel canister, for a combustion powered tool, in accordance with implementations described herein, may be removably coupled to a combustion powered tool. The fuel cell may be removed from the tool, and coupled to a fuel transfer station. A fuel transfer station, in accordance with implementations described herein, may provide for refilling, or replenishment, of fuel in the fuel cell, so that the refilled fuel cell, or fuel canister, may be re-attached to the tool. In some implementations, the fuel cell may be refilled or replenished with a liquid hydrocarbon fuel such as, for example, propane, from the fuel transfer station. In some implementations, the fuel cell, or fuel canister, may be received in a housing of the tool. In some implementations, the fuel cell, or fuel canister, may be coupled to a housing of the tool. In some implementations, a metering valve coupled to the fuel cell, or fuel canister, may dispense a previously defined amount, or volume, of liquid fuel from the fuel cell, or fuel canister, to the tool in response to an actuation of the tool. In some implementations, a flow through valve coupled to the fuel cell, or fuel canister, may provide a substantially continuous flow of fuel from the fuel cell, or fuel canister, to the tool for sustained operation of the tool. Numerous different types of tools may be powered by a hydrocarbon fuel, such as, for example, propane, delivered by a fuel cell, or fuel canister, and fuel transfer station, in accordance with implementations described herein. For example, handheld combustion powered equipment, such as, for example, an impact tool, a crimping tool, a fastening tool, and the like may receive a metered flow of fuel provided by a refillable fuel canister for operation, in accordance with implementations described herein. Other types of combustion powered equipment, such as, for example, cutting tools, surface finishing tools, driving tools, and the like, as well as equipment such as lawnmowers, blowers, trimmers, power washers, and the like, may receive a continuous, or free flow of fuel provided by a refillable fuel canister, in accordance with implementations described herein. A fuel canister, and a fuel transfer station, in accordance with implementations described herein, may allow a depleted fuel canister to be refilled and reconnected to the combustion powered equipment, rather than discarded and replaced with a new fuel canister. This may provide substantial cost savings, may enhance user convenience and utility, and may reduce waste. Additionally, operation of this type of combustion powered equipment on a hydrocarbon based fuel such as propane, rather than a traditional gasoline powered arrangement, may allow for indoor operation of the combustion powered equipment, further enhancing user convenience and utility. In some situations, a main tank, or a supply tank, and a fuel canister to be refilled may be connected in an open loop fuel transfer system, to provide for refilling of the fuel canister from the supply tank. In many situations, the supply tank and the fuel canister may be at substantially the same pressure and temperature, generating a vapor lock condition between the supply tank and the fuel canister, and inhibiting fluid flow between the supply tank and the fuel canister. In this situation, a flow of fluid, for example, a flow of fuel in a liquid state, from the supply tank to the fuel canister, may be facilitated by, for example, allowing a direct vent to atmosphere (or to a secondary pressure vessel) from the fuel canister. This venting to the atmosphere may lower the pressure in the fuel canister, generating a pressure differential that allows for fluid flow from the supply tank to the fuel canister. However, this venting of a fluid fuel at high vapor pressure may create a combustible mix with air, may pose a freeze/frostbite hazard due to off-gassing, may lead to asphyxiation, may waste fuel, and may have other undesirable consequences. A closed loop fuel transfer system may provide for safer, more effective, more efficient transfer of fluid, for example, liquid fuel, from a supply tank to a fuel canister to be refilled. A schematic view of an example closed loop transfer station100is shown inFIGS.1A-1B. A fluid flow line110, such as, for example, a tube or pipe, may connect one or more supply tanks200and a fuel canister300. The supply tank(s)200may contain fuel, for example, fuel in a fluid state such as, for example, liquid propane, for refilling of the fuel canister300. A pump120may be connected to the fluid flow line110. The pump120may be, for example, a piston type, air cylinder manual pump, as illustrated in the example shown inFIGS.1A-1B, or other type of pumping mechanism that can generate a sufficient pressure gradient needed to push fuel into the fuel canister300. As shown in the exemplary arrangement illustrated inFIG.1A, a first check valve130may be positioned adjacent to a connection between the supply tank200and the fluid flow line110, for example, between an outlet of the supply tank200and an inlet of the pump120. The first check valve130may prevent unintended, or inadvertent, flow of fuel between the supply tank200and the fluid flow line110. A second check valve140may be positioned adjacent to a connection between the fuel canister300and the fluid flow line110, for example, between an outlet of the pump120and an inlet of the fuel canister300, and also between the first check valve130and an inlet of the fuel canister300. The second check valve140may prevent unintended, or inadvertent, flow of fuel between the fuel canister300and the fluid flow line110. A quick disconnect coupler150may facilitate the connection of the fuel canister300to the line fluid flow110, and the detachment of the fuel canister300from the fluid flow line110. A pressure relief valve184may be coupled to the fluid flow line110, to provide for pressure relief in the event of over-filling, or over pressurization in the fuel transfer station100. In some implementations, one or more filter(s)112may be coupled to the fluid flow line110. In the exemplary arrangement shown inFIG.1A, the filter112is coupled at a portion of the fluid flow line110proximate the outlet of the supply tank200. As shown in the arrangement illustrated inFIG.1B, in some implementations the closed loop fuel transfer station100may provide for connection of more than one supply tank200to the fluid flow line110. In the example shown inFIG.1B, the fuel transfer station100provides for connection of a first supply tank200A and a second supply tank200B to the fluid flow line110. In this arrangement, backflow at a first inlet portion110A of the fluid flow line110may be prevented by the check valve130A, and backflow at a second inlet portion110B of the fluid flow line110may be prevented by the check valve130B. This arrangement may allow for only the first supply tank200A to be connected to the fuel transfer station100, to transfer fuel from the first supply tank200A to the fuel canister300, without backflow at the second inlet portion110B. Similarly, this arrangement may allow for only the second supply tank200B to be connected to the fuel transfer station100, to transfer fuel from the second supply tank200B to the fuel canister300, without backflow at the first inlet portion110A. In a situation in which both the first supply tank200A and the second supply tank200B are connected to the fuel transfer station100, operation of the pump120in the manner described above may draw substantially equivalent amounts of fluid from the first supply tank200A and the second supply tank200B simultaneously. If one of the supply tanks200A,200B is emptied or disconnected (i.e., fluid flow from one of the supply tanks200A,200B is in some manner interrupted or discontinued) then operation of the pump120may draw fluid from the remaining supply tank200A,200B. Placement of the first and second supply tanks200A,200B at respective inlet sides of the check valves130A,130B, and placement of the fuel canister300at an outlet side of the check valve140, ensure that fluid can only flow into a canister300connected to the fuel transfer station100at the outlet side of the check valve140. FIG.2Ais a top perspective view of an example fuel transfer station, in accordance with implementations described herein.FIG.2Bis a bottom perspective view of the example fuel transfer station shown inFIG.2A, with portions of a base housing and pump housing removed.FIG.2Cprovides a cross sectional view of a pump installed in the base housing.FIG.2Dis a cross sectional view of the fuel transfer station, taken along line A-A ofFIG.2A.FIG.2Eis an exploded perspective view of the fuel transfer station. As shown inFIGS.2A-2E, the fuel transfer station100may include a frame170coupled to a base160. The frame170may provide a support structure for the supply tank200and the pump120. Fluid flow line(s)110may be housed within the base160and/or coupled beneath the base160. Connection ports165may be included in the base160, and may be coupled to the fluid flow line110. For example, a first connection port165A may provide for connection of the supply tank200to the fuel flow line110, and a second connection port165B may provide for connection of the fuel canister300to the fuel flow line110. As shown in more detail inFIGS.2B-2E, the example pump120may include a piston122received in a cylinder124, and coupled to a handle126, with an interior of the cylinder124being in communication with the fluid flow lines110. The example pump120may be actuated through manual manipulation of the handle126, causing reciprocation of the piston122in the cylinder124. Upward movement or expansion of the piston122in the cylinder124may decrease pressure in the flow lines110behind check valve140in connection with the pump120to draw fluid from the supply tank200into the cylinder124and into the flow lines110. Conversely, downward movement or contraction of the piston122in the cylinder124may increase a pressure of fluid contained in the cylinder124, and force the fluid from the cylinder124through the fluid flow lines110and into a fuel canister300removably connected to the second connection port165B. The alternate opening and closing of the first check valve130and the second check valve140during cycling of the pump120may facilitate the transfer of fluid from the supply tank200to the fuel canister300. A pressure relief valve184(seeFIG.1B) may be actuated to provide for pressure relief in the event of over-filling, or over-pressurization. The pressure relief valve184may be set to a prescribed pressure, for instance, by selection of a spring constant to set a cracking pressure. During actuation of the pump120, pressure may be increased in the transfer station100and in the fuel canister300. Exposure of a pressure that is greater than or equal to the previously prescribed cracking pressure may cause the pressure relief valve184to open and/or vent to atmosphere. In some implementations, the pressure relief valve184may be manually actuated, for example, by depression of a pressure relief button186provided on the base160of the fuel transfer station100. For example, in some implementations, the pressure relief valve184may be a spring loaded poppet valve, that is actuated, or opened, in response to an applied force, for example, an external force applied at the pressure relief button186and transferred to the pressure relief valve184. Upon removal of the external force, the spring may bias the pressure relief valve184back to a closed state, to maintain pressure in the fluid flow lines110. The fluid flow line(s)110may be made of a rigid material, or a semi-rigid material, or a flexible material that is capable of maintaining structural integrity while conveying fluid under pressure, and that is capable of supporting connections with check valves and couplings with connectors to the supply tank200and the fuel canister300, to be described in more detail below. The example pump120shown inFIGS.2A-2Eemploys a manual, piston or air cylinder type pumping mechanism, simply for ease of discussion and illustration. However, a fuel transfer station, in accordance with implementations described herein, may employ other types of pumping mechanisms, such as, for example, electro-mechanical pumps, pneumatic pumps, and the like, to generate a pressure gradient that causes fuel to flow between the supply tank200and the fuel canister300. In some implementations, the pressure gradient to cause the fuel to flow between the supply tank200and the fuel canister300may be generated by a thermal device that, for example, applies heat to the supply tank200and/or applies cooling to the fuel canister300. For example, as shown inFIG.2F, in some implementations, a thermal device400, in accordance with implementations described herein, may include a thermal jacket420that may be coupled to the supply tank200. The thermal jacket420may be detachably coupled to an outer peripheral portion of the supply tank200by a fastening device such as, for example, hook and loop fasteners, clips, snaps, elastic fittings, and other such fastening devices. As shown inFIG.2F(a), in some implementations, a power supply cord422may convey power from an external source of power to the thermal jacket420. As shown inFIG.2F(b), in some implementations, a power storage device424such as, for example, a battery, may supply power to the thermal jacket420. The thermal jacket420may selectively apply heat to the supply tank200, to increase the temperature of the supply tank200and generate a pressure gradient between the supply tank200and the fuel canister300. The resulting pressure gradient may cause fuel to flow from the supply tank200to the fuel canister300. In some implementations, the heat applied by the thermal jacket420to the supply tank200may cause the temperature of the supply tank200to increase by a relatively small amount, for example, just a few degrees warmer than the fuel canister300. This relatively small increase in the temperature of the supply tank200may generate a temperature gradient sufficient to cause fuel to flow from the supply tank200to the fuel canister300, and provide for relatively rapid filling of the fuel canister300without the need for a pump as described above. As shown inFIG.2G, in some implementations, the thermal device400may include a thermal jacket430that may be coupled to the fuel canister300. The thermal jacket430may be detachably coupled to an outer peripheral portion of the fuel canister300by a fastening device such as, for example, hook and loop fasteners, clips, snaps, elastic fittings, and other such fastening devices. As shown inFIG.2G(a), in some implementations, a power supply cord432may convey power from an external source of power to the thermal jacket430. As shown inFIG.2G(b), in some implementations, a power storage device434such as, for example, a battery, may supply power to the thermal jacket430. The thermal jacket430may selectively apply cooling to the fuel canister300, to decrease the temperature of the fuel canister300and generate a pressure gradient between the supply tank200and the fuel canister300. The resulting pressure gradient may cause fuel to flow from the supply tank200to the fuel canister300. In some implementations, the cooling applied by the thermal jacket430to the fuel canister300may cause the temperature of the fuel canister300to decrease by a relatively small amount, for example, just a few degrees cooler than the supply tank200. This relatively small decrease in the temperature of the fuel canister300may generate a temperature gradient sufficient to cause fuel to flow from the supply tank200to the fuel canister300, and provide for relatively rapid filling of the fuel canister300without the need for a pump as described above. FIG.3Aillustrates the example fuel transfer station100with a supply tank200positioned for connection to the first connector165A, and a fuel canister300connected to the second connector165B. The supply tank200may also be oriented in a substantially inverted position so as to induce fluid flow from an outlet of the fuel tank200into the first connector165A. In the example shown inFIG.3A, the supply tank200has a relatively large capacity compared to that of the fuel canister300. For example, in the example arrangement shown inFIG.3A, the supply tank200may have a bulk fuel capacity of approximately 20 pounds of liquid fuel (for example, propane), whereas the fuel canister300may be sized for use in a handheld tool.FIG.3Billustrates that the fuel transfer station100may accommodate supply tanks200A and200B, having a variety of different fuel capacities, based on, for example, storage constraints, fuel requirements for a particular job site, and the like. Similarly, the fuel transfer station100may accommodate fuel canisters300A,300B and300C for refilling that have a plurality of different fuel capacities based on, for example, the types of equipment in use, storage constraints and other such factors. Hereinafter, refilling of an exemplary fuel canister300such as the fuel canister300A shown inFIG.3A, which is sized for use with a piece of handheld equipment, such as a cordless combustion powered hand tool, will be described, simply for ease of discussion and illustration. FIGS.4A-4Dillustrate an exemplary fuel canister assembly that may be connected to the fuel transfer station100for refilling. A cap portion330may be positioned at a top end portion of the fuel canister300. An adapter350may be removably coupled to the cap portion330, as shown inFIG.4B. The cap portion330of the canister300may be adapted to allow for connection of a plurality of different types of adapters350to the fuel canister300, depending on, for example, the tool and/or piece of equipment to which the fuel canister300is to deliver fuel. In some implementations, a fuel metering valve which provides a previously defined amount, or volume, of fuel, may be housed within the cap portion330of the canister300. In some implementations, a free flow of fuel may pass through the cap portion330of the fuel canister300. In some implementations, a release mechanism provided on the cap portion330may be manipulated or actuated to release the adapter350from the cap portion330of the fuel canister300, as shown inFIG.4C. In some implementations, a quick disconnect coupler355including a body portion355A (in one of the cap portion330or the adapter350) and a stem portion355B (in the other of the cap portion330or the adapter) may provide for the quick coupling of the adapter350to the cap portion330of the fuel canister300, and the quick decoupling of the adapter350from the cap portion330of the fuel canister300. A plurality of different cap portions330and/or different adapters350may interface with various different pieces of equipment to deliver fuel to the combustion powered equipment. A similar arrangement of a quick disconnect coupler355including a body portion355A (in one of the fuel canister300or the connection port165B) and a stem portion335B (in the other of the fuel canister300or the connection port165B) may be used to releasably couple the fuel canister300to the fuel transfer station100. In some implementations, the connection between the adapter350and the cap portion330of the fuel canister300, and the connection between the fuel canister300and the connection port165B of the fuel transfer station100, may be specifically keyed, or patterned, so that only designated adapters350may be connected to the fuel canister300, and only designated fuel canisters300may be coupled to the fuel transfer station100, by inserting the stem portion355B into the body portion355A of the quick disconnect coupler355, for example in the correct orientation and/or in the correct sequence of movements. For example, when connecting the fuel canister300to the fuel transfer station100for filling (as shown inFIG.3A), the connection between the cap portion330of the fuel canister300and the connection port165B may be specifically keyed, or patterned, so that only designated fuel canisters300may be connected to the fuel transfer station100by inserting the stem portion355B into the body portion355A of the quick disconnect coupler355, for example in the correct orientation and/or in the correct sequence of movements. In some implementations, the keying, or patterning, between the body portion355A and the stem portion355B of the quick disconnect coupler355may include a unique geometry, a unique interface including geometric alignment such as insertion of spaced prongs into a corresponding cavity, and the like. In some implementations, engagement between the body portion355A and the stem portion355B of the quick disconnect coupler355may rely on the insertion of the stem portion355B into the body portion355A, followed by a movement, such as a relative rotation of the stem portion355B and the body portion355A, for full engagement. Keyed engagement in this manner may, in turn, allow for a secure connection during the flow of fluid, such as, for example, fuel in a pressurized state, into the fuel canister300in a filling operation, and out of the fuel canister300in a dispensing operation. FIG.5illustrates an example interface between the fuel canister300and the fuel transfer station100, for example, between the fuel canister300and the connection port165B of the fuel transfer station100. The fuel canister300may be aligned with the connection port165B of the fuel transfer station100, for example in an inverted position with respect to the fuel transfer station100, as shown inFIG.3A. In the example interface shown inFIG.5, the keying features to ensure proper connection of an appropriate fuel canister300to the fuel transfer station100may include the alignment of pins163(in one of the connection port165B or the fuel canister300) with corresponding recesses363(in the other of the connection port165B or the fuel canister300). This alignment may also include alignment of a geometry, or surface contour162of the connection port165B with a corresponding geometry, or surface contour362, of the fuel canister300. In the example shown inFIG.5, the keyed interface includes two pins163, and two corresponding recesses363, simply for ease of discussion and illustration. However, more, or fewer, pins163and corresponding recesses363may be included in the keyed interface. Further, in the example shown inFIG.5, the two pins163are provided in the connection port165B, and the two corresponding recesses363are formed in the fuel canister300, simply for ease of discussion and illustration. However, the pins may be provided on the fuel canister300, and the corresponding recesses363may be formed in the connection port165B, and/or some of the pins163may be provided on the fuel canister300and some of the pins163in the connection port165B, with corresponding recesses formed in the connection port165B and the fuel canister300. In some implementations, the keying of the interface may include, for example, a contouring of an outer peripheral portion of the fuel canister300, for example, a contouring of an outer peripheral portion of the cap portion330of the fuel canister300, mated with a complementary contouring of an inner peripheral portion of the connection port165B. For example, in some implementations, the cap portion330of the fuel canister300may include a contoured portion334(see, for example,FIGS.4B and4C), for example, at an outer peripheral portion of the cap portion330. The connection port165B may include a contoured portion164(see, for example,FIG.7A), for example, at an inner peripheral portion of the connection port165B. A shape, or contour, of the contoured portion164of the connection port165B may correspond to, or be complementary to, the contoured portion334of the fuel canister300, so that the contoured portion334of the fuel canister300and the contoured portion164of the connection port165may be engaged when the fuel canister300is coupled in the connection port165(see, for example,FIG.7B). This complementary contouring of the outer peripheral portion of the fuel canister300and the inner peripheral portion of the connection port165B may help to ensure that only appropriate fuel canisters300are coupled to the fuel transfer station100for refilling, and may provide for proper alignment of the fuel canister300in the connection port165B. In some implementations, or in addition to keyed interface described previously, the quick disconnect coupler355may have unique geometry for mating the body portion355A with the stem portion355B. Furthermore, other variations separate from or in addition to the examples described above may also be considered. As described above, fuel canisters300having various different sizes and/or capacities, such as, for example, the exemplary fuel canisters300A,300B and300C shown inFIG.3A, may be connected to the fuel transfer station100for refilling. In particular,FIGS.6A-6Eillustrate the exemplary fuel canisters300A,300B and300C, having different sizes and/or capacities, coupled to a common connection port165B or interface at the outlet of the fuel transfer station100. InFIG.6A, the smallest fuel canister300A, is coupled in the connection port165B, and is secured in the connection port165B through mechanical engagement of the valve structure extending between the connection port165B and the fuel canister300A, including, for example, the keyed interface described in detail with respect toFIG.5. In some implementations such as those with a quick disconnect coupler355, shut-off features may be integrated into valve mechanisms of the stem portion355B and/or the body portion355A. The shut-off features may be spring loaded, and may allow fluid flow when the stem portion355B is engaged with body portion355A, and may shut-off the fluid flow path upon disengagement of, or a break in connection between the body portion355A and the stem portion355B of the coupler355. As shown inFIG.6D, in some implementations, the fuel canister(s)300B/300C may be inserted in to the connection port165B of the fuel transfer station100, and then turned, or twisted, for example in the direction of the arrow A, to complete the connection or engagement between the fuel canister300B/300C and the connection port165B. In this arrangement, the fuel canister300B/300C may be disengaged from the connection port165B by turning or twisting the fuel canister300B/300C in the direction opposite the arrow A. As shown inFIG.6E, in some implementations, the fuel canister(s)300B/300C may be snapped into the connection port165B of the fuel transfer station100to complete the connection or engagement between the fuel canister300B/300C and the connection port165B. In this arrangement, the fuel canister300B/300C may be disengaged from the connection port165B by, for example, manipulating a release button167on the base160of the fuel transfer station100. FIGS.7A and7Billustrate the connection of the fuel canister300into the connection port165B of the fuel transfer station100, andFIG.7Cis a cross sectional view taken along line B-B ofFIG.3A, illustrating a connected state of the fuel canister300to the fuel transfer station100.FIG.7Dis a cross sectional view taken along line C-C ofFIG.3A, illustrating a connected state of the supply tank200to the fuel transfer station100. Once the fuel canister300to be filled is securely connected to the fuel transfer station100, fuel may be transferred from the supply tank200to the fuel canister300. As described above, the pump120may be actuated to generate a pressure gradient, or pressure differential, between the supply tank200and the fuel canister300, that pushes, or urges, or guides fluid, for example, liquid fuel such as propane, from the supply tank200to the fuel canister300. In response to the connection of the supply tank200and the connection of the fuel canister300to the fuel transfer station, and the pressure gradient generated by the pumping action of the pump120, the first check valve130may be opened to allow flow from the supply tank200, through the first check valve130into the fluid supply line100toward the fuel canister300. The pressure gradient may continue to urge the flow of liquid fuel in the direction of the fuel canister300, through the second check valve140, and into the fuel canister300. The pressure gradient may be maintained, for example, through sustained pumping if necessary, and fuel may continue to flow into the fuel canister300in this manner until the fuel canister300is full, and/or until the fuel canister300has reached a desired fill level. In some implementations, the desired fill level may be visually detected through a clear portion (for example, transparent or translucent) of the outer wall305of the fuel canister300(see, for example,FIGS.8A-8C). In some implementations, the fill level of the fuel canister300may be measured by a pressure gauge and/or assessment of force applied to the handle126of the pump120. To avoid over-filling, or over-pressurization, the pressure relief valve184may have a prescribed cracking or opening pressure that causes the pressure relief valve184to be actuated, or opened, to relieve pressure in the fluid flow lines110. In the event that the fuel canister300approaches an over-filled or over-pressurized state, the fuel canister300may include a pressure relief valve365, or vent365(see, for example,FIGS.4A-4B), having a prescribed cracking or opening pressure. In some implementations, a release mechanism180may be actuated to release the engagement between the fuel canister300and the connection port165B of the fuel transfer station100. The release mechanism180may be installed in the base160of the fuel transfer station100. The release mechanism180may include a release button182accessible from an exterior of the fuel transfer station100. The release button182may be coupled to, or extend into, a release arm183. In response to depression of the release button182, a distal end portion of the release arm183may contact, and exert a corresponding force on a release pad320of the cap portion330of the fuel canister300. The force exerted on the release pad320of the cap portion330of the fuel canister300may release engagement of the fuel canister300in the connection port165B, allowing for disengagement of the fuel canister300from the fuel transfer station100. When the release pad320of the cap portion330of the fuel canister300is pushed, a sliding lock of the quick disconnect coupler355that attaches the body portion355A with the stem portion355B, may allow for separation and disengagement. Other quick disconnect mechanisms or attach/detach mechanisms may also be utilized that include locking shafts, collars, spring loaded detents, and the like for release of coupled connectors. As shown inFIGS.8A-8B, In some implementations, at least a portion of an outer wall305of the fuel canister300may be made of an optically transparent, or translucent material such as, for example, a polycarbonate, polyvinyl chloride, chlorinated polyvinyl chloride, and like materials. This may allow a level of fuel in the fuel canister300to be visually detected. Visual detection of the amount of fuel in the fuel canister300may allow the user to determine how much equipment operation time remains before the fuel canister300will have to be replaced and/or refilled, allowing the user to more accurately schedule tasking, plan work flow and the like. Similarly, visual detection of the amount of fuel in the fuel canister300may allow the user to determine when the fuel canister300has reached a desired fill level during the refilling process on the fuel transfer station100, also preventing over-filling of the fuel canister300. In some implementations, essentially the entirety of the outer wall305of the fuel canister300may be made of a transparent, or translucent material, as shown inFIG.8A. In some implementations, one or more previously defined portions of the outer wall305of the fuel canister300may be made of a transparent, or translucent material, defining windows315providing for visibility into the interior of the fuel canister300through which a fuel level may be visually detected, as shown inFIG.8B. In some implementations, portions of the outer wall of the fuel canister300may be covered by a sleeve325, or over-mold325to, for example, improve handling and installation, while leaving other portions of the transparent, or translucent outer wall305of the fuel canister300exposed, as shown inFIG.8C, so that a fuel level in the interior of the fuel canister300may be visually detected. In some implementations, a fuel canister300having an outer wall305made of a transparent, or translucent material as described above may be designed to provide for pressure relief through, for example, controlled cracking at a particular pressure differential versus atmospheric pressure, thus enhancing safety when filling and maintaining a pressurized fluid in the fuel canister300. Use of these types of materials in the outer wall305of the fuel canister300may also provide advantages in cost and/or weight when compared to metals used in pressure vessels. In some situations, fuel may exist in the fuel canister300in a liquid and gaseous mixture. Particularly, in the case of propane fuel, propane may have a relatively high vapor pressure and may be subject to volume change due to varying density n accordance with changes in environmental conditions such as temperature, causing the fluid volume in the fuel canister300to expand or contract in response. Over-fill protection, included in the design of the fuel canister300may help alleviate these effects, providing a measure of safety against a failure, or burst of the pressure vessel defined by the fuel canister300. In some implementations, a compressible material may be incorporated into the fuel canister300, to account for expansion of the fuel contained in the fuel canister due to environmental changes. For example, a compressible material310such as, for example, a compressible rubber, a compressible polymer, and the like, may be incorporated into the fuel canister300, as shown inFIGS.9A-9E. In the example shown inFIGS.9A-9C, the compressible material310is positioned on an outer circumferential portion of a dip tube312inside the fuel canister300. In this example, the compressible material310is in the form of pieces, or strips, or masses, of compressible material310surrounding, or partially surrounding, the dip tube312. An empty fuel canister300, as shown inFIG.9A, may be filled with fuel, for example, from the fuel transfer station100as described above, at a first temperature Ti. At the first temperature T1, the fluid in the fuel canister is at a first pressure P1, as shown inFIG.9B. Elevation of the temperature to a second temperature T2(greater than the first temperature T1) may cause the fluid in the fuel canister300to expand, so that the fluid is at a second pressure P2(greater than the first pressure P1). In response to the elevated pressure P2, the compressible material310may contract. This contracting of the compressible material310increases the volume inside the fuel canister300, making this additional volume available to absorb the expansion of the fluid in the fuel canister300due to the elevated pressure, thus avoiding an over pressure condition, or an over fill condition, which may cause a safety hazard. FIGS.9D-9Fare cross sectional views of the fuel canister300, with compressible material310in the interior of the fuel canister300. In the example shown inFIG.9D, the compressible material310is positioned along an inner circumferential surface of the fuel canister300. In the example shown inFIG.9E, portions, or pieces, or strips, of the compressible material310are positioned intermittently along the inner circumferential surface of the fuel canister300. In the example shown inFIG.9F, the compressible material310is in the form of spherical balls or discs in the interior of the fuel canister300. However, the compressible material310may be in the form of other types of three-dimensional masses having different shapes and/or contours, and are not necessarily spherical balls. In each of these examples, as the temperature and pressure increase, from T1to T2, and from P1to P2, respectively, the compressible material310in the fuel canister300is compressed in response to the increased pressure, providing additional volume to accommodate the corresponding expansion of the fluid in the fuel canister300. The compressible material may have properties that are compatible with the fuel to be contained in the fuel canister300. The type, and configuration and/or volume of compressible material310may be designed so as to accommodate a previously set change in volume due to increased pressure after filling. For example, in some implementations, the type and/or configuration and/or volume of the compressible material310may be set to accommodate sufficient change in volumetric mass density (e.g., greater than 10%) of the fluid in the canister300after filling. Similarly, mechanical properties of the compressible material310may be taken into consideration, so that the compressible material310responds elastically in a relatively high pressure range (expected to be experienced from the fluid in the fuel canister300), and continue to compress up to an expected vapor pressure before yielding. As noted above, the use of polycarbonate, polyvinyl chloride, chlorinated polyvinyl chloride, and like materials for the outer wall305of the fuel canister300. These types of materials may provide for pressure relief in the event of an over-fill, or over-pressurization condition in the fuel canister300, through, for example, controlled cracking at a particular pressure differential. In this situation, the fuel canister300and material of the outer wall305may be such that a small crack propagates in response to a particular pressure differential, resulting in a controlled release of fuel when heated or over-pressurized, thus avoiding a comparatively violent burst or tear and sudden release of gas which may be experienced with a metal canister in a similar situation. To achieve similar effects, a burst disc, perforated side wall, or previously thinned or weakened portion of fuel canister300may be included to provide for preferential failure of said device during over-pressurization. As described above, in some implementations, the fuel canister300may include a pressure relief valve365. In some implementations, the pressure relief valve365may be included in the outer wall portion of the fuel canister, as shown in the example illustrated inFIG.4A. In some implementations, the pressure relief valve365may be included in the cap330, as shown in the example illustrated inFIG.10. The pressure relief valve365may be, for example, a spring loaded poppet valve, or other similar type of valve. The pressure relief valve365may be actuated to provide for pressure relief in the event of over-filling, or over-pressurization. For example, the pressure relief valve365may be actuated in response to detection that pressure in the fuel canister300is greater than or equal to a previously defined pressure level. Once the pressure level in the fuel canister300is below the previously defined pressure level, the spring may bias the pressure relief valve365back to a closed state. In some situations, a smaller and/or more portable device for transferring fuel from a supply tank to a fuel canister to refill the fuel canister may further enhance utility and convenience for the user. As shown inFIG.11, in some implementations, a fuel transfer station1000or device may include a pump1120attached to a base1175. The base1175may be positioned on a support surface such as, for example, a floor surface, a work bench surface, and the like. A supply tank1200may be coupled to a first connection port1165A of the frame1170, in an inverted manner to facilitate the selective flow of fuel out of the supply tank1200. A refillable fuel canister1300may be coupled to a second connection port1165B of the frame1170. Fluid flow lines (not shown in detail inFIG.11) may be housed within the connecting structure, extending between the first connection port1165A/supply tank1200and the second connection port1165B/fuel canister1300, to facilitate the selective flow of fuel from the supply tank1200to the fuel canister1300. The pump1120may include a piston shaft1122having a piston (not shown inFIG.10) at an end portion thereof that reciprocates within a cylinder1124in response to reciprocal movement of a handle1126. Fluid flow lines may be defined within the frame1170to connect the first connection port1165A/supply tank1200and the second connection port1165B/fuel canister1300. A first check valve (not shown in detail inFIG.11) and a second check valve (not shown in detail inFIG.11) may be positioned in the fluid flow lines, to selectively control the flow of fluid between the first connection port1165A/supply tank1200and the second connection port1165B/fuel canister1300. A pressure relief valve1184may be in communication with the fluid flow lines, to relieve system pressure in the event of an over-filling or over-pressurization condition. With the base1175supported on the support surface, the user may grasp the handle1126and operate the pump1120, causing fluid to flow from the supply tank1200to the fuel canister1300. The flow of fluid between the first connection port1165A/supply tank1200and the second connection port1165B/fuel canister1300may be controlled in a similar manner previously described in detail with respect toFIGS.1through10. Similarly, the features of the fuel canister1300and the connection thereof to the fuel transfer station1000via the connection port1165B may be similar to the features of the fuel canister300and the connection thereof to the fuel transfer station via the connection port165B described in detail with respect toFIGS.1through10. In the fuel transfer station1000shown inFIG.11, the more substantial frame170described above with respect toFIGS.1-10is replaced by rigid fluid flow lines connected to the pump1120. The use of a relatively small supply tank1200, for example, a one pound supply tank1200, may allow the fuel transfer station1000shown inFIG.11to be easily transported, easily utilized, and easily stored. In some implementations, the transfer of fuel from a supply tank to a fuel canister to be filled may be further simplified by one or more adapters which may provide for the transfer of fuel, essentially directly, from the supply tank to the fuel canister. For example, as shown inFIGS.12A and12B, a fuel transfer nozzle2210may be coupled to a supply tank2200. A fuel canister2300may then be coupled to, or connected to the supply canister2200, such that a nozzle tip2220of the fuel transfer nozzle2210is inserted into a fill valve2310(seeFIGS.14A and14B) in an end portion of the fuel canister2300. Insertion of the nozzle tip2220into the fill valve2310and depression of the nozzle tip2220may actuate, or open, the fuel transfer nozzle2210, and may actuate, or open, the fill valve2310, allowing fuel to flow from the supply tank2200, through the fuel transfer nozzle2210and the fill valve2310, and into the fuel canister2300. An exemplary fuel transfer nozzle2210will be described in more detail with respect toFIGS.13A-13D. An exemplary fill valve2310will be described in more detail with respect to14A and14B. The insertion of the nozzle tip2220of the fuel transfer nozzle2210into the fill valve2310, to provide for the flow of fuel from the supply tank2200, through the fuel transfer nozzle2210and the fill valve2310and into the fuel canister2300, is illustrated schematically inFIGS.15A and15B. FIGS.13A and13Bare perspective views of the exemplary fuel transfer nozzle2210, in accordance with implementations described herein.FIG.13Cis a cross sectional view of the exemplary fuel transfer nozzle2210in an unactuated state.FIG.13Dis a cross sectional view of the exemplary fuel transfer nozzle2210in an actuated state.FIG.15Ais a schematic illustration of the supply tank2200and the fuel canister2300in a disconnected state, andFIG.15Bis a schematic illustration of the supply tank2200and the fuel canister2300in a connected state, in which fuel can flow from the supply tank2200to the fuel canister2300, and may be aided by the effects of gravity. A coupler2270may provide for coupling, for example, threaded coupling, of the fuel transfer nozzle2210to an outlet port of the supply tank2200. An inlet tip2280may engage an outlet flow passage of an outlet port of the supply tank2200, to selectively allow fuel to flow from the supply tank2200into the fuel transfer nozzle2210. In some implementations, the fuel transfer nozzle2210may include a lubrication port2290, allowing for the periodic lubrication of the internal components of the fuel transfer nozzle2210, and for the addition of lubricant to the fuel canister2300. In some situations, it may be advantageous when lubricant is mixed with the fuel and/or dissolved into the fuel, as the lubricant may then be transferred from the fuel canister300to the attached equipment, providing lubricity as fuel is dispensed. In the unactuated state shown inFIGS.13C and15A, a valve2230positioned in a flow path2240within the fuel transfer nozzle2210may remain closed, such that fuel does not flow from the supply tank2200, through the flow passage2240and out through the nozzle tip2220. An application of force on the nozzle tip2220in the direction of the arrow F1, i.e., depression of the nozzle tip2220in a direction into the fuel transfer nozzle2210, may cause the valve2230to open, and allow fuel to flow through the fuel transfer nozzle2210and out through the nozzle tip2220, as shown inFIGS.13D and15B. The nozzle tip2220may move in the direction F2, due to the biasing force of a spring2250at the end portion of the nozzle tip2220, in response to removal of the force applied to the nozzle tip2220(for example, removal of the nozzle tip2220from the fill valve2310), closing the valve2230and returning the fuel transfer nozzle2210to the unactuated state shown inFIG.13C. As shown inFIG.15B, insertion of the nozzle tip2220into the fill valve2310compresses the spring2250of the fuel transfer nozzle2310and the spring2350of the fill valve2310, allowing fuel to flow from the supply tank2200into the fuel canister2300. Removal of the nozzle tip2220from the fill valve2310releases the spring2250of the fuel transfer nozzle2310such that fuel no longer flows through the fuel transfer nozzle2310, and releases the spring2350of the fill valve2310, such that fuel no longer flows through the fill valve. In some implementations, it may be advantageous that the nozzle tip2220not create a gas tight seal with the fill valve2320, such that some gas pressure may be relieved as liquid fuel is transferred. FIG.14Ais a perspective view of an exemplary fill valve2310, andFIG.14Bis a bottom view of an exemplary fuel canister2300, in accordance with implementations described herein. As shown in14A and14B, the fill valve2310may be installed in an end portion, for example, a base portion, of the fuel canister2300. The fill valve2310may include an inlet portion2320that receives the nozzle tip2220of the fuel transfer adapter2210. The fill valve2310may be selectively actuated by the spring2250, to allow fuel to selectively flow through the fill valve2310and into the fuel canister2300. When the nozzle tip2220of the fuel transfer nozzle2210is received in the inlet portion2320of the fill valve2310, and a force is applied to overcome the applicable spring and gas pressure forces, as shown inFIG.15B, both the valve2230of the fuel transfer nozzle2210and the fill valve2310of the fuel canister2300may be open. With both valves2230,2310in the open position, fuel may flow from the supply tank2200to the fuel canister2300. In some implementations, the flow of fuel from the supply tank2200to the fuel canister2300may be facilitated by the force of gravity (based on, for example, a relative positioning of the supply tank2200in a somewhat inverted position above the fuel canister2300), as illustrated in the relative orientation of the supply tank2200and the fuel canister2300shown inFIGS.15A and15B. The exemplary fuel transfer system shown inFIGS.12A-15Bmay provide for provide a simplified mechanism for fuel transfer, and may simplify the filling of an individual fuel canister, particularly in a usage environment in which time and/or space and/or equipment availability are limited. However, in some situations, it may be difficult to achieve a substantially complete filling of the fuel canister2300using the exemplary fuel transfer system shown inFIGS.12A-15B. In situations in which such a smaller, inline type fuel transfer system may be desired, a fuel transfer station, in accordance with implementations described herein, may include a manual inline pumping system including as few as one single check valve, as illustrated inFIGS.16A-17B. Such a fuel transfer system including an inline pumping system may provide for essentially complete filling of the fuel canister, in a relatively compact form, while utilizing a reduced number of parts. As shown inFIGS.16A and16B, a fuel transfer station, in accordance with implementations described herein, may include an inline fuel transfer pump3000connected between the supply tank3200and the fuel canister3300. In some implementations, a single check valve3130may be installed along an inlet portion3120of the inline fuel transfer pump3000. For example, in some implementations, the single check valve3130may be coupled between the inlet portion3120and a piston3150of the inline transfer pump3000, as shown inFIG.16A. In some implementations, the single check valve3130may be coupled at a connection between the supply tank3200and the inlet portion3120of the inline transfer pump3000, as shown inFIG.16B. In either of the exemplary installation positions shown inFIGS.16A and16B, the single check valve3130may allow for flow in a single direction, for example in the direction of the arrow A. That is, in either of the exemplary arrangements illustrated inFIGS.16A and16B, the single check valve3130may only allow fuel to flow from the supply tank3200to the fuel canister3300. The manual inline transfer pump3000may include the piston3150reciprocally received in a cylinder3160. The inlet portion3120may be coupled between the outlet of the supply tank3200and the piston3150, to direct fuel from the supply tank3200into an interior of the cylinder3160. A fuel transfer nozzle3220may be coupled to an outlet end portion of the cylinder3160. The fuel transfer nozzle3210may be selectively engaged with a fill valve3310provided in an end portion of the fuel canister3300, so as to selectively direct fuel from the interior of the cylinder3160into the fuel canister3300. In some implementations, the fuel transfer nozzle3210described with respect toFIGS.16A-17Bmay be similar to the fuel transfer nozzle2210described above with respect toFIGS.12A-15B. In some implementations, the fill valve3310described with respect toFIGS.16A-17Bmay be similar to the fill valve2210described above with respect toFIGS.12A-15B. In the exemplary arrangement shown inFIG.17A, the inline fuel transfer pump3000is in a first state. In the first state, the fuel transfer pump3000is connected to the supply tank3200, and is fully extended due to the pressure exerted by the fluid contained in the supply tank3200, and flowing out of the supply tank3200and into the inlet portion3120of the pump3000. In the exemplary arrangement shown inFIG.17B, the inline fuel transfer pump3000is in a second state. In the second state, the pump3000has been compressed, pushing fuel contained within the interior of the cylinder3160out through the fuel transfer nozzle3210, and into the fuel canister3300through the fill valve3310. That is, in transitioning from the first state to the second state, the piston3150moves, or reciprocates, within the cylinder3160(i.e., the piston3150is manually pumped, or moved, within the cylinder3160) to eject the fuel contained within the cylinder3160out of the pump3000through the fuel transfer nozzle3210, and into the fuel canister3300through the fill valve3310. A reciprocating action, for example, a manual reciprocating action, or reciprocal may be applied to the pump3000to cause a corresponding reciprocal movement of the piston3150in the cylinder3160to draw fuel from the supply tank3200into the cylinder3160in a first direction, and to draw fuel out of the cylinder3160and into the fuel canister3300in a second direction. This reciprocating action may be repeated, and the fuel transferred out of the pump3000and refilled into the pump3000, in this manner until the fuel canister3300is filled. The check valve3130may prevent the supply tank3200from being pressurized due to this reciprocal action. Rather, only the outlet portion of the pump3000(i.e., at the fuel transfer nozzle3210) is pressurized. In some implementations, the flow of fuel from the supply tank3200to the fuel canister3300may be facilitated by the force of gravity (based on, for example, a relative positioning of the supply tank3200in a somewhat inverted position above the fuel canister3300). The exemplary check valve3130included in the fuel transfer station including the inline pumping system3000shown inFIGS.16A-17Bis just one illustrative example of a check valve that may be incorporated into a fuel transfer station, in accordance with implementations described herein. Other check valves capable of controlling the flow of fluid between a supply tank and a fuel canister to be filled may also be appropriate. The exemplary fuel transfer system shown inFIGS.16A-17Bmay provide a simplified mechanism for fuel transfer, and may simplify the filling of an individual fuel canister, particularly in a usage environment in which power, such as, for example, electrical power, time and/or space and/or equipment availability are limited. A refillable fuel cell, or fuel canister, and a fuel transfer station for filling such a refillable fuel canister, in accordance with implementations described herein, may allow a fuel canister to be refilled with fuel, rather than discarded. The transfer station may accommodate a wide variety of different sizes and/or capacities and/or types of refillable fuel canisters to be refilled, for example, with fuel in a liquid state such as, for example, propane. This may allow for the use of this type of fuel to provide power to a wide variety of combustion powered equipment, and may allow for the operation of this equipment at a wide variety of job sites, including indoor job sites which would otherwise restrict the use of gasoline or traditional combustion powered equipment. The ability to refill fuel canisters may enhance user utility and convenience, and reduce cost and waste associated with the use of combustion powered equipment while improving environmental health and safety risks. Other non-combustion energy generation and/or energy transfer devices, such as, for example, electrochemical cells, refrigerant pumps and the like, may also benefit from a refillable fuel canister. While certain features of the described implementations have been illustrated as described herein, many modifications, substitutions, changes and equivalents will now occur to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the scope of the implementations. It should be understood that they have been presented by way of example only, not limitation, and various changes in form and details may be made. Any portion of the apparatus and/or methods described herein may be combined in any combination, except mutually exclusive combinations. The implementations described herein can include various combinations and/or sub-combinations of the functions, components and/or features of the different implementations described. | 56,255 |
11858802 | DETAILED DESCRIPTION The present invention is directed toward a system and method for effecting a consumer transaction within a retail fueling station environment. Specifically, personalized consumer data including advertising and promotion information for purchasing products and services from a vendor is offered to the consumer during the time the consumer is dispensing fuel. The consumer interacts with the fuel dispenser user interface to complete the transaction such as purchasing products and services from a vendor within the retail fueling environment or may include a remote vendor of goods and/or services. The embodiments set forth below represent the necessary information to enable those skilled in the art to practice the invention and illustrate the best mode of practicing the invention. FIG.1illustrates a block diagram of an exemplary retail fueling station environment in accordance with the present invention. The retail fueling station environment typically includes a central building105one or more fuel dispensers (FD)200and a dispenser network (DN)101. The central building105typically includes a premises controller (PC)106, a point of sale (POS)108system, a convenience store (C-Store)107and may also include a quick serve food outlet or restaurant. The premises controller106controls the fuel dispensers200, processes transactions as well as other related activities and is well understood in the art. The premises controller106may be a standalone component or may be incorporated within the point of sale system108. The premises controller106communicates with a remote payment processing system (PPS)109for authorizing payment transactions as well as other related activities by way of a communication link to a wide area network (WAN)110. As described above, the plurality of fuel dispensers200are operatively connected to the dispenser network101which generally includes a dispenser hub which may be accomplished via additional devices, such as distribution box (DB)102as is understood in the art. The dispenser network101is operatively connected to the premises controller106via a premises local area network103or other intermediate devices such as a network router. FIG.2illustrates a block diagram of an exemplary fuel dispenser in accordance with the present invention. The fuel dispenser200includes a user interface201, one or more controllers and one or more communication modules. The controllers include a fuel dispensing controller (FC)203, one or more transaction processors (TP)205and one or more application processors (AP)207. The communication module(s) includes a wired communication module (WC)206and may also include a wireless communication module (WL)208. The wireless communication module208can include a transceiver communicating via Bluetooth protocol, and/or WIFI protocol. The wired communications communication module206operatively connects the fuel dispenser200to the dispenser network101. The user interface201includes components to facilitate consumer interaction with the fuel dispenser200. The user interface201includes a key pad component for inputting data for purchasing fuel or other products and/or services. The key pad component is also used for inputting an authentication code or a personal identification number. The user interface may also include other input and output components202including a camera, an optical reader, facial recognition and/or other biometric sensors as well as a printer so that a transaction receipt and/or a coupon may be printed and presented to the consumer. The user interface201includes a visual display device to provide personalized information, such an advertisement or one or more redeemable discount coupons for purchasing products and services from a vendor or other data related to loyalty programs, promotions and contests. The visual display device includes a monochrome or color LCD display and may also include a touchscreen allowing the consumer to use soft keys to respond to transaction information requests presented to the consumer via the touchscreen. FIG.3illustrates prior art of a mobile personal communication device (MD)300used with a fuel dispenser200. The fuel dispenser200includes an applications processor207and a wireless communication module208. The wireless communication module208operatively connects the personal communication device300with the applications processor207and includes a transceiver communicating via Bluetooth protocol and/or WIFI protocol. The fuel dispenser application processor207operatively connects to a local application server104located within the retail fueling station environment via the premises local area network103or other intermediate devices. The local application server104manages the payment transaction as well as other related activities and is well understood in the art. The local application server104communicates with a remote payment processing server109for authorization of payment transactions via a communication link to the wide area network110. Alternatively the personal communication device300communicates with a remote application server (RAS)310and/or remote payment processing system for authorization of the payment transaction by way of a wireless network320. FIG.4is a block diagram of a system in accordance with the present invention. In one embodiment the retail fueling station environment includes a central building105having a convenience store (“C-store’)107, one or more fuel dispensers200, a dispenser network101and a premises controller106. The central building may also include a quick serve food outlet or restaurant. The premises controller106controls the authorization of fueling transactions and other related activities and is well understood in the art. The premises controller106may be a standalone component or may be incorporated into a point of sale (POS)108device. The premises controller106communicates with a remote payment processing server109for payment authorization via a communication link to a wide area network110. As described above, the plurality of fuel dispensers200are operatively connected to a dispenser network101which may be accomplished via additional devices, such as distribution box102as is understood in the art. The dispenser network101is operatively connected to the premises controller via a premises local area network103or other intermediate devices, such as a router. The fuel dispenser200includes a wireless communication module208and a wired communication module206. The wireless communication module operatively connects the fuel dispenser with a consumer vehicle (CV)400. The wireless communication module208includes a transceiver communicating via Bluetooth protocol, and/or WIFI protocol or other radio frequency protocol. The wired communications module206operatively connects the fuel dispenser to the dispenser network101. By way of the wireless communication module208, presence of a consumer at a fuel dispenser200is detected and the fuel dispenser can receive consumer vehicle information directly from the consumer vehicle400. Communications between the vehicle and the fuel dispenser can use an On Board Diagnostics (OBD)401device e.g. OBDII technology in which the consumer vehicle400includes an OBDII port. When the wireless communication module208detects that the consumer vehicle is proximate thereto, it initiates a communication session with the consumer vehicle400and retrieves the consumer vehicle information including the vehicle identification number (VIN) and other vehicle related data such as fuel metrics. Once the consumer vehicle information is received directly from the consumer's vehicle the customized fueling experience can be provided as further described. FIG.5illustrates a transaction appliance500located within a retail fuel dispensing environment and a transaction server (TAS)412is located remotely outside the retail fueling station environment. In a preferred embodiment the transaction appliance500is located in the central building105, alternatively the transaction appliance500may be located elsewhere within the retail fueling station environment. The transaction appliance500is operatively connected to the plurality of fuel dispensers via the premises local area network103, dispenser network101or other intermediate devices, such as a router. The transaction appliance is also operatively connected to the wide area network110which may be accomplished via the premises local area network103or other intermediate devices, such as a router. FIG.5further illustrates a block diagram of a transaction appliance500of the present invention. The transaction appliance includes an application processor (TAP)501, a transaction appliance wireless communication module (TWL)503and a transaction appliance wired communication module (TWC)502. The transaction appliance wireless communication module503includes a transceiver communicating via Bluetooth protocol and/or WIFI protocol. The transaction appliance wired communication module502is operatively connected to the plurality of fuel dispensers200via the premises local area network103or other intermediate devices, such as a router. Additionally, the transaction appliance wired communication module502is operatively connected to the remote transaction server412via a communication link to a wide area network110. The transaction server412is located remotely outside the retail fueling station environment. The transaction server412is operatively connected to the transaction appliance via the wide area network110. Additionally, the transaction server412is operatively connected to a remote Consumer Profile Server (CPS)411and a Media Content Server (MCS)410. The Consumer Profile Server411matches the consumer vehicle400data with a with a known consumer identity to access a database(s) including consumer profile data, consumer history and loyalty program data. Consumer profile data includes associated names, payment method, identities, images and other biometric information. Consumer history includes previously visited fuel dispensers and other vendor locations. Loyalty program data includes a loyalty identifier number, rewards, whether to apply loyalty rewards and/or to promote a purchase of products and/or services and the like. Fueling preferences include preferred fuel grade, fuel type, and/or the amount of fuel required to fill the fuel tank as obtained from the consumer vehicle data. In a preferred embodiment the user identity is provided to the Media Content Server410which dynamically provides customized or targeted advertisements and personalized consumer data during the fuel dispensing time. The advertisements can be specified by the vendor and/or a remote vendor. Remote vendors are remote in the sense that they are not located at the retail fueling facility. A remote vendor includes any commercial seller of products and/or services, vehicle parts, food and drink, etc. Hence a vendors and/or remote vendor can proactively market and/or or sell products and services by way of personalized merchandising content, advertisements and pricing data as well as provide coupons regarding products and/or services. In other embodiments when the fuel dispenser200initiates a communication session with the consumer vehicle400, the fuel dispenser200receives other vehicle characteristics or metrics directly from the consumer vehicle400. For example the vehicle can monitor driving performance and diagnostics which can be provided to the fuel dispenser200for display on the user interface201during a fueling session. The fuel dispenser200can further receive vehicle operational metrics including mileage performance, whether the vehicle requires maintenance, the amount of fuel currently in the fuel tank, and the like. The consumer vehicle information is transmitted to the transaction appliance500. The transaction appliance500, responsively transmits the consumer vehicle information to the transaction server412. The transaction server412invokes personalized consumer data including the amount of fuel needed to fill the vehicle's fuel tank based on the amount of fuel currently in the vehicle's fuel tank, and/or whether the vehicle is in need of maintenance as determined from the received consumer vehicle information and/or consumer profile data. A consumer transaction is performed based on the selection made by the consumer interacting with the fuel dispenser user interface201. By using the fuel dispenser user interface201the consumer indicates interest in the personalized consumer data. The user interface provides information regarding the products and services and determines whether the consumer desires to purchase a product and/or service or request additional information regarding products or services. If a consumer desires to purchase a product and/or service, the user interface is used to specify order data (e.g. quantity) and payment data. Alternatively payment data may be pre-determined from the consumer profile. If the purchase is approved, the transaction server412can then generate a message for the vendor or remote vendor regarding the purchase and generate a receipt for the consumer. Alternatively a vendor coupon or receipt can be printed and the consumer can redeem the product and/or service from premises convenience store107, quick serve food outlet or restaurant. An example of a product that can be purchased from a fuel dispenser is a cup of coffee. A fuel dispenser consumer could for instance, pre-order a cup of coffee during the fuel dispensing period by providing input to the fuel dispenser user interface. The customer could then pick the cup of coffee from the premises convenience store107, quick serve food outlet or restaurant by indicating the fuel dispenser number or producing a printed out coupon. FIG.6is a process flow diagram illustrating one embodiment of a method for fuel dispensing. At step601, presence of a consumer vehicle400at a fuel dispenser200is detected. Upon detecting that the consumer vehicle400is proximate thereto; at step602the fuel dispenser400initiates a communication session with the consumer vehicle On Board Diagnostics (OBD)401device. At step603, the fuel dispenser200retrieves the consumer vehicle400information including the vehicle identification number, other vehicle related data such as fuel metrics and the corresponding fuel dispenser identification. The consumer vehicle information and fuel dispenser identification are transmitted to the transaction appliance500via the premises local area network (LAN)103. At step604the transaction appliance500transmits a transaction trigger to the transaction server412located remotely outside the retail fueling station environment. At step605, the transaction server412responsively invokes personalized consumer data associated with the transaction trigger including advertising and promotions for purchasing products and services from a vendor. At step606the personalized consumer data is provided to the transaction appliance500; the transaction appliance500in turn transmits the personalized consumer data to the fuel dispenser200with the corresponding fuel dispenser identification. At step607, personalized consumer data is displayed on the fuel dispenser user interface201. The consumer inputs information purchasing products and/or services such as the amount of fuel, authentication code or a personal identification number (PIN), payment information and the like. Once the payment is authorized the fuel pump is activated and fuel dispensing begins. At step608, personalized consumer data including advertising and promotion information for purchasing products and services from a vendor is offered to the consumer during the time the consumer is dispensing fuel. At step609, the consumer interacts with the fuel dispenser user interface to effect a transaction such as purchasing products and/or services from a vendor within the retail fueling environment or may include a remote vendor of goods and/or services. At step610, the transaction appliance500provides effected transaction data and transmits the effected transaction data to the fuel dispenser200with the corresponding fuel dispenser identification. At step611, the content on the fuel dispenser user interface201visual display device content is updated with the effected transaction data, a printer provides a hard copy receipt of the effected transaction and may also be used for printing and providing promotional information or reward coupons. The foregoing description of one or more embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above teaching. It is intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto. | 16,978 |
11858803 | Corresponding reference characters indicate corresponding parts throughout the several views. The exemplifications set out herein illustrate exemplary embodiments of the invention and such exemplifications are not to be construed as limiting the scope of the invention in any manner. DETAILED DESCRIPTION An exemplary fuel delivery system10is shown inFIG.1. Fuel delivery system10includes a fuel dispenser12for dispensing a liquid fuel product14from a liquid storage tank16to consumers. Each storage tank16is fluidly coupled to one or more dispensers12via a corresponding fuel delivery line18. Storage tank16and delivery line18are illustratively positioned underground, but it is also within the scope of the present disclosure that storage tank16and/or delivery line18may be positioned above ground. Fuel delivery system10ofFIG.1also includes a pump20to draw fuel product14from storage tank16and to convey fuel product14through delivery line18to dispenser12. Pump20is illustratively a submersible turbine pump (“STP”) having a turbine pump head22located above storage tank16and a submersible motor24located inside storage tank16. However, it is within the scope of the present disclosure that other types of pumps may be used to transport fuel product14through fuel delivery system10. Fuel delivery system10ofFIG.1further includes various underground sumps (i.e., pits). A first, dispenser sump30is provided beneath dispenser12to protect and provide access to piping (e.g., delivery line18), connectors, valves, and other equipment located therein, and to contain any materials that may be released beneath dispenser12. A second, turbine sump32, which is also shown inFIG.2, is provided above storage tank16to protect and provide access to pump20, piping (e.g., delivery line18), leak detector34, electrical wiring36, and other equipment located therein. Turbine sump32is illustratively capped with an underground lid38and a ground-level manhole cover39, which protect the equipment inside turbine sump32when installed and allow access to the equipment inside turbine sump32when removed. According to an exemplary embodiment of the present disclosure, fuel delivery system10is an automobile fuel delivery system. In this embodiment, fuel product14may be a gasoline/ethanol blend that is delivered to consumers' automobiles, for example. The concentration of ethanol in the gasoline/ethanol blended fuel product14may vary from 0 vol. % to 15 vol. % or more. For example, fuel product14may contain about 2.5 vol. % ethanol (“E-2.5”), about 5 vol. % ethanol (“E-5”), about 7.5 vol. % ethanol (“E-7.5”), about 10 vol. % ethanol (“E-10”), about 15 vol. % ethanol (“E-15”), or more, in some cases up to about 85 vol. % ethanol (“E-85”). As discussed in U.S. Publication No. 2012/0261437, the disclosure of which is expressly incorporated herein by reference in its entirety, the ethanol may attract water into the gasoline/ethanol blended fuel product14. The water in fuel product14may be present in a dissolved state, an emulsified state, or a free water state. Eventually, the water may also cause phase separation of fuel product14. In addition to being present in storage tank16as part of the gasoline/ethanol blended fuel product14, ethanol may find its way into other locations of fuel delivery system10in a vapor or liquid state, including dispenser sump30and turbine sump32. In the event of a fluid leak from dispenser12, for example, some of the gasoline/ethanol blended fuel product14may drip from dispenser12into dispenser sump30in a liquid state. Also, in the event of a vapor leak from storage tank16, vapor in the ullage of storage tank16may escape from storage tank16and travel into turbine sump32. In certain situations, turbine sump32and/or components contained therein (e.g., metal fittings, metal valves, metal plates) may be sufficiently cool in temperature to condense the ethanol vapor back into a liquid state in turbine sump32. Along with ethanol, water from the surrounding soil, fuel product14, or another source may also find its way into sumps30,32in a vapor or liquid state, such as by dripping into sumps30,32in a liquid state or by evaporating and then condensing in sumps30,32. Ethanol and/or water leaks into sumps30,32may occur through various connection points in sumps30,32, for example. Ethanol and/or water may escape from ventilated sumps30,32but may become trapped in unventilated sumps30,32. In the presence of certain bacteria and water, ethanol that is present in fuel delivery system10may be oxidized to produce acetate, according to Reaction I below. CH3CH2OH+H2O→CH3COO−+H++2H2(I) The acetate may then be protonated to produce acetic acid, according to Reaction II below. CH3COO−H+→CH3COOH (II) The conversion of ethanol to acetic acid may also occur in the presence of oxygen according to Reaction III below. 2CH3CH2OH+O2→2CH3COOH+2H2O (III) Acetic acid producing bacteria or AAB may produce acetate and acetic acid by a metabolic fermentation process, which is used commercially to produce vinegar, for example. Acetic acid producing bacteria generally belong to the Acetobacteraceae family, which includes the generaAcetobacter, Gluconobacter, andGluconacetobacter. Acetic acid producing bacteria are very prevalent in nature and may be present in the soil around fuel delivery system10, for example. Such bacteria may find their way into sumps30,32to drive Reactions I-III above, such as when soil or debris falls into sumps30,32or when rainwater seeps into sumps30,32. The products of Reactions I-III above may reach equilibrium in sumps30,32, with some of the acetate and acetic acid dissolving into liquid water that is present in sumps30,32, and some of the acetate and acetic acid volatilizing into a vapor state. In general, the amount acetate or acetic acid that is present in the vapor state is proportional to the amount of acetate or acetic acid that is present in the liquid state (i.e, the more acetate or acetic acid that is present in the vapor state, the more acetate or acetic acid that is present in the liquid state). Even though acetic acid is classified as a weak acid, it may be corrosive to fuel delivery system10, especially at high concentrations. For example, the acetic acid may react to deposit metal oxides (e.g., rust) or metal acetates on metallic fittings of fuel delivery system10. Because Reactions I-III are microbiologically-influenced reactions, these deposits in fuel delivery system10may be tubular or globular in shape. To limit corrosion in fuel delivery system10, a control system100and a corresponding monitoring method are provided herein. As shown inFIG.3, the illustrative control system100includes controller102, one or more monitors104in communication with controller102, output106in communication with controller102, and remediation system108in communication with controller102, each of which is described further below. Controller102of control system100illustratively includes a microprocessor110(e.g., a central processing unit (CPU)) and an associated memory112. Controller102may be any type of computing device capable of accessing a computer-readable medium having one or more sets of instructions (e.g., software code) stored therein and executing the instructions to perform one or more of the sequences, methodologies, procedures, or functions described herein. In general, controller102may access and execute the instructions to collect, sort, and/or analyze data from monitor104, determine an appropriate response, and communicate the response to output106and/or remediation system108. Controller102is not limited to being a single computing device, but rather may be a collection of computing devices (e.g., a collection of computing devices accessible over a network) which together execute the instructions. The instructions and a suitable operating system for executing the instructions may reside within memory112of controller102, for example. Memory112may also be configured to store real-time and historical data and measurements from monitors104, as well as reference data. Memory112may store information in database arrangements, such as arrays and look-up tables. Controller102of control system100may be part of a larger controller that controls the rest of fuel delivery system10. In this embodiment, controller102may be capable of operating and communicating with other components of fuel delivery system10, such as dispenser12(FIG.1), pump20(FIG.2), and leak detector34(FIG.2), for example. An exemplary controller102is the TS-550 Evo® Fuel Management System available from Franklin Fueling Systems Inc. of Madison, Wis. Monitor104of control system100is configured to automatically and routinely collect data indicative of a corrosive environment in fuel delivery system10. In operation, monitor104may draw in a liquid or vapor sample from fuel delivery system10and directly test the sample or test a target material that has been exposed to the sample, for example. In certain embodiments, monitor104operates continuously, collecting samples and measuring data approximately once every second or minute, for example. Monitor104is also configured to communicate the collected data to controller102. In certain embodiments, monitor104manipulates the data before sending the data to controller102. In other embodiments, monitor104sends the data to controller102in raw form for manipulation by controller102. The illustrative monitor104is wired to controller102, but it is also within the scope of the present disclosure that monitor104may communicate wirelessly (e.g., via an internet network) with controller102. Depending on the type of data being collected by each monitor104, the location of each monitor104in fuel delivery system10may vary. Returning to the illustrated embodiment ofFIG.2, for example, monitor104′ is positioned in the liquid space (e.g, middle or bottom) of storage tank16to collect data regarding the liquid fuel product14in storage tank16, monitor104″ is positioned in the ullage or vapor space (i.e., top) of storage tank16to collect data regarding any vapors present in storage tank16, monitor104′″ is positioned in the liquid space (i.e., bottom) of turbine sump32to collect data regarding any liquids present in turbine sump32, and monitor104″ is positioned in the vapor space (i.e., top) of turbine sump32to collect data regarding any vapors present in turbine sump32. Monitor104may be positioned in other suitable locations of fuel delivery system10, including delivery line18and dispenser sump30(FIG.1), for example. Various monitors104for use in control system100ofFIG.3are discussed further below. Output106of control system100may be capable of communicating an alarm or warning from controller102to an operator. Output106may include a visual indication device (e.g., a gauge, a display screen, lights, a printer), an audio indication device (e.g., a speaker, an audible alarm), a tactile indication device, or another suitable device for communicating information to the operator, as well as combinations thereof. Controller102may transmit information to output106in real-time, or controller102may store information in memory112for subsequent transmission or download to output106. Remediation system108of control system100may be capable of taking at least one corrective action to remediate the corrosive environment in fuel delivery system10. Various embodiments of remediation system108are described below. The illustrative output106and remediation system108are wired to controller102, but it is also within the scope of the present disclosure that output106and/or remediation system108may communicate wirelessly (e.g., via an internet network) with controller102. For example, to facilitate communication between output106and the operator, output106may be located in the operator's control room or office. In operation, and as discussed above, controller102collects, sorts, and/or analyzes data from monitor104, determines an appropriate response, and communicates the response to output106and/or remediation system108. According to an exemplary embodiment of the present disclosure, output106warns the operator of a corrosive environment in fuel delivery system10and/or remediation system108takes corrective action before the occurrence of any corrosion or any significant corrosion in fuel delivery system10. In this embodiment, corrosion may be prevented or minimized. It is also within the scope of the present disclosure that output106may alert the operator to the occurrence of corrosion in fuel delivery system10and/or remediation system108may take corrective action to at least avoid further corrosion. Various factors may influence whether controller102issues an alarm or warning from output106that a corrosive environment is present in fuel delivery system10or becoming more likely to develop. Similar factors may also influence whether controller102instructs remediation system108to take corrective action in response to the corrosive environment. As discussed further below, these factors may be evaluated based on data obtained from one or more monitors104. One factor indicative of a corrosive environment includes the concentration of acidic molecules in fuel delivery system10, with controller102issuing an alarm or warning from output106and/or activating remediation system108when the measured concentration of acidic molecules in fuel delivery system10exceeds an acceptable concentration of acidic molecules in fuel delivery system10. The concentration may be expressed in various units. For example, controller102may activate output106and/or remediation system108when the measured concentration of acidic molecules in fuel delivery system10exceeds 25 ppm, 50 ppm, 100 ppm, 150 ppm, 200 ppm, or more, or when the measured concentration of acidic molecules in fuel delivery system10exceeds 25 mg/L, 50 mg/L, 100 mg/L, 150 mg/L, 200 mg/L, or more. At or beneath the acceptable concentration, corrosion in fuel delivery system10may be limited. Controller102may also issue an alarm or warning from output106and/or activate remediation system108when the concentration of acidic molecules increases at an undesirably high rate. Another factor indicative of a corrosive environment includes the concentration of hydrogen ions in fuel delivery system10, with controller102issuing an alarm or warning from output106and/or activating remediation system108when the measured concentration of hydrogen ions in fuel delivery system10exceeds an acceptable concentration of hydrogen ions in fuel delivery system10. For example, controller102may activate output106and/or remediation system108when the hydrogen ion concentration causes the pH in fuel delivery system10to drop below 5, 4, 3, or 2, for example. Within the acceptable pH range, corrosion in fuel delivery system10may be limited. Controller102may also issue an alarm or warning from output106and/or activate remediation system108when the concentration of hydrogen ions increases at an undesirably high rate. Yet another factor indicative of a corrosive environment includes the concentration of bacteria in fuel delivery system10, with controller102issuing an alarm or warning from output106and/or activating remediation system108when the measured concentration of bacteria in fuel delivery system10exceeds an acceptable concentration of bacteria in fuel delivery system10. At or beneath the acceptable concentration, the production of corrosive materials in fuel delivery system10may be limited. Controller102may also issue an alarm or warning from output106and/or activate remediation system108when the concentration of bacteria increases at an undesirably high rate. Yet another factor indicative of a corrosive environment includes the concentration of water in fuel delivery system10, with controller102issuing an alarm or warning from output106and/or activating remediation system108when the measured concentration of water in fuel delivery system10exceeds an acceptable concentration of water in fuel delivery system10. At or beneath the acceptable concentration, the production of corrosive materials in fuel delivery system10may be limited. Controller102may also issue an alarm or warning from output106and/or activate remediation system108when the concentration of water increases at an undesirably high rate. The water may be present in liquid and/or vapor form. Controller102may be programmed to progressively vary the alarm or warning communication from output106as the risk of corrosion in fuel delivery system10increases. For example, controller102may automatically trigger: a minor alarm (e.g., a blinking light) when monitor104detects a relatively low acid concentration level (e.g., 5 ppm) in fuel delivery system10or a relatively steady acid concentration level over time; a moderate alarm (e.g., an audible alarm) when monitor104detects a moderate acid concentration level (e.g., 10 ppm) in fuel delivery system10or a moderate increase in the acid concentration level over time; and a severe alarm (e.g., a telephone call or an e-mail to the gas station operator) when monitor104detects a relatively high acid concentration level (e.g., 25 ppm) in fuel delivery system10or a relatively high increase in the acid concentration level over time. The alarm or warning communication from output106allows the operator to manually take precautionary or corrective measures to limit corrosion of fuel delivery system10. For example, if an alarm or warning communication is signaled from turbine sump32(FIG.2), the operator may remove manhole cover39and lid38to clean turbine sump32, which may involve removing bacteria and potentially corrosive liquids and vapors from turbine sump32. As another example, the operator may inspect fuel delivery system10for a liquid leak or a vapor leak that allowed ethanol and/or its acidic reaction products to enter turbine sump32in the first place. Even if no immediate action is required, the alarm or warning communication from output106may allow the operator to better plan for and predict when such action may become necessary. For example, the minor alarm from output106may indicate that service should be performed within about 2 months, the moderate alarm from output106may indicate that service should be performed within about 1 month, and the severe alarm from output106may indicate that service should be performed within about 1 week. As discussed above, control system100includes one or more monitors104that collect data indicative of a corrosive environment in fuel delivery system10. Each monitor104may vary in the type of data that is collected, the type of sample that is evaluated for testing, and the location of the sample that is evaluated for testing, as exemplified below. In one embodiment, monitor104collects electrical data indicative of a corrosive environment in fuel delivery system10. An exemplary electrical monitor104ais shown inFIG.4and includes an energy source120, a corrosive target material122that is exposed to a liquid or vapor sample S from fuel delivery system10, and a sensor124. To enhance the longevity of monitor104a, energy source120and/or sensor124may be protected from any corrosive environment in fuel delivery system10, unlike target material122. Target material122may be designed to corrode before the equipment of fuel delivery system10corrodes. Target material122may be constructed of or coated with a material that is susceptible to acidic corrosion, such as copper or low carbon steel. Also, target material122may be relatively thin or small in size compared to the equipment of fuel delivery system10such that even a small amount of corrosion will impact the structural integrity of target material122. For example, target material122may be in the form of a thin film or wire. In use, energy source120directs an electrical current through target material122. When target material122is intact, sensor124senses the electrical current traveling through target material122. However, when exposure to sample S causes target material122to corrode and potentially break, sensor124will sense a decreased electrical current, or no current, traveling through target material122. It is also within the scope of the present disclosure that the corrosion and/or breakage of target material122may be detected visually, such as by using a camera as sensor124. First monitor104amay share the data collected by sensor124with controller102(FIG.3) to signal a corrosive environment in fuel delivery system10when the electrical current reaches an undesirable level or changes at an undesirable rate, for example. After use, the corroded target material122may be discarded and replaced. Another exemplary electrical monitor104bis shown inFIG.5and includes opposing, charged metal plates130. The electrical monitor104boperates by measuring electrical properties (e.g., capacitance, impedence) of a liquid or vapor sample S that has been withdrawn from fuel delivery system10. In the case of a capacitance monitor104b, for example, the sample S is directed between plates130. Knowing the size of plates130and the distance between plates130, the dielectric constant of the sample S may be calculated. As the quantity of acetate, acetic acid, and/or water in the sample S varies, the dielectric constant of the sample S may also vary. The electrical monitor104bmay share the collected data with controller102(FIG.3) to signal a corrosive environment in fuel delivery system10when the dielectric constant reaches an undesirable level or changes at an undesirable rate, for example. One example of electrical monitor104bis a water content monitor that may be used to monitor the water content of fuel product14or another sample S from fuel delivery system10. An exemplary water content monitor is the ICM-W monitor available from MP Filtri, which uses a capacitive sensor to measure the relative humidity (RH) of the tested fluid. As the RH increases toward a saturation point, the water in the fluid may transition from a dissolved state, to an emulsified state, to a free water state. Other exemplary water content monitors are described in the above-incorporated U.S. Publication No. 2012/0261437. Another example of electrical monitor104bis a humidity sensor that may be used to monitor the humidity in the vapor space of storage tank16and/or turbine sump32. In another embodiment, monitor104collects elecrochemical data indicative of a corrosive environment in fuel delivery system10. An exemplary electrochemical monitor (not shown) performs potentiometric titration of a sample that has been withdrawn from fuel delivery system10. A suitable potentiometric titration device includes an electrochemical cell with an indicator electrode and a reference electrode that maintains a consistent electrical potential. As a titrant is added to the sample and the electrodes interact with the sample, the electric potential across the sample is measured. Potentiometric or chronopotentiometric sensors, which may be based on solid-state reversible oxide films, such as that of iridium, may be used to measure potential in the cell. As the concentration of acetate or acetic acid in the sample varies, the potential may also vary. The potentiometric titration device may share the collected data with controller102(FIG.3) to signal a corrosive environment in fuel delivery system10when the potential reaches an undesirable level or changes at an undesirable rate, for example. An electrochemical monitor may also operate by exposing the sample to an electrode, performing a reduction-oxidation with the sample at the electrode, and measuring the resulting current, for example. In yet another embodiment, monitor104collects optical data indicative of a corrosive environment in fuel delivery system10. An exemplary optical monitor104cis shown inFIG.6and includes a light source140(e.g., LED, laser), an optical target material142that is exposed to a liquid or vapor sample S from fuel delivery system10, and an optical detector144(e.g., photosensor, camera). To enhance the safety of monitor104c, light source140may be a low-energy and high-output device, such as a green LED. Target material142may be constructed of or coated with a material (e.g., an acid-sensitive polymer) that changes optical properties (e.g., color, transmitted light intensity) in the presence of the sample S. Optical monitor104cmay enable real-time, continuous monitoring of fuel delivery system10by installing light source140, target material142, and detector144together in fuel delivery system10. To enhance the longevity of this real-time monitor104c, light source140and/or detector144may be protected from any corrosive environment in fuel delivery system10, unlike target material142. For example, light source140and/or detector144may be contained in a sealed housing, whereas target material142may be exposed to the surrounding environment in fuel delivery system10. Alternatively, optical monitor104cmay enable manual, periodic monitoring of fuel delivery system10. During exposure, target material142may be installed alone in fuel delivery system10. During testing, target material142may be periodically removed from fuel delivery system10and positioned between light source140and detector144. In a first embodiment of the manual monitor104c, light source140and detector144may be sold as a stand-alone, hand-held unit that is configured to receive the removed target material142. In a second embodiment of the manual monitor104c, light source140may be sold along with a software application to convert the operator's own smartphone or mobile device into a suitable detecor144. Detector144of monitor104cmay transmit information to controller102(FIG.3) in real-time or store information in memory for subsequent transmission or download. One suitable target material142includes a pH indicator that changes color when target material142is exposed to an acidic pH with H+protons, such as a pH less than about 5, 4, 3, or 2, for example. The optical properties of target material142may be configured to change before the equipment of fuel delivery system10corrodes. Detector144may use optical fibers as the sensing element (i.e., intrinsic sensors) or as a means of relaying signals to a remote sensing element (i.e., extrinsic sensors). In use, light source140directs a beam of light toward target material142. Before target material142changes color, for example, detector144may detect a certain reflection, transmission (i.e., spectrophotometry), absorbtion (i.e., densitometry), and/or refraction of the the light beam from target material142. However, after target material142changes color, detector144will detect a different reflection, transmission, absorbtion, and/or refraction of the the light beam. It is also within the scope of the present disclosure that the changes in target material142may be detected visually, such as by using a camera (e.g., a smartphone camera) as detector144. Third monitor104cmay share the data collected by detector144with controller102(FIG.3) to signal a corrosive environment in fuel delivery system10when the color reaches an undesirable level or changes at an undesirable rate, for example. Another suitable target material142includes a sacrificial, corrosive material that corrodes (e.g., rusts) when exposed to a corrosive environment in fuel delivery system10. For example, the corrosive target material142may include copper or low carbon steel. The corrosive target material142may have a high surface area to volume ratio to provide detector144with a large and reliable sample size. For example, as shown inFIG.6, the corrosive target material142may be in the form of a woven mesh or perforated sheet having a large plurality of pores143. In use, light source140directs a beam of light along an axis A toward the corrosive target material142. Before target material142corrodes, detector144may detect a certain amount of light that passes from the light source140and through the open pores143of the illuminated target material142along the same axis A. However, as target material142corrodes, the material may visibly swell as rust accumulates in and around some or all of the pores143. This accumulating rust may obstruct or prevent light from traveling through pores143, so detector144(e.g., a photodiode) will detect a decreasing amount of light through the corroding target material142. It is also within the scope of the present disclosure that the changes in target material142may be detected visually, such as by using a camera or another suitable imaging device as detector144. Detector144may capture an image of the illuminated target material142and then evaluate the image (e.g., pixels of the image) for transmitted light intensity, specific light patterns, etc. As discussed above, third monitor104cmay share the data collected by detector144with controller102(FIG.3) to signal a corrosive environment in fuel delivery system10when the transmitted light intensity reaches an undesirable level or changes at an undesirable rate, for example. After use, the corroded target material142may be discarded and replaced. Another exemplary optical monitor104c′ is shown inFIGS.16-19. Optical monitor104c′ ofFIGS.16-19is similar to optical monitor104cofFIG.6and includes several components and features in common with optical monitor104cas indicated by the use of common reference numbers between optical monitors104c,104c′, including a light source140′, a corrosive target material142′, and an optical detector144′. Optical monitor104c′ may be mounted in the vapor space of storage tank16and/or turbine sump32of fuel delivery system10(FIG.2). The illustrative optical monitor104c′ is generally cylindrical in shape and has a longitudinal axis L. In the illustrated embodiment ofFIG.19, light source140′ and target material142′ are located on a first side of axis L (illustratively the right side of axis L), and optical detector144′ is located on a second side of axis L (illustratively the left side of axis L). Light source140′ and optical detector144′ are substantially coplanar and are located above target material142′. The illustrative target material142′ is a L-shaped mesh sheet, with a vertical portion145a′ of target material142′ extending parallel to axis L and a horizontal portion145b′ of target material142′ extending perpendicular to axis L. The illustrative optical monitor104c′ includes a reflective surface500′ positioned downstream of light source140′ and upstream of optical detector144′, wherein the reflective surface500′ is configured to reflect incident light from light source140′ toward optical detector144′. In the illustrated embodiment ofFIG.19, the incident light from light source140′ travels downward and inward toward axis L along a first axis A1toward reflective surface500′, and then the reflected light from reflective surface500′ travels upward and outward from axis L along a second axis A2toward optical detector144′. Reflective surface500′ may produce a specular reflection with the reflected light traveling along a single axis A2, as shown inFIG.19, or a diffuse reflection with the reflected light traveling in many different directions. Reflective surface500′ may be a shiny, mirrored, or otherwise reflective surface. Reflective surface500′ may be shaped and oriented to direct the reflected light toward optical detector144′. For example, inFIG.19, the reflective surface500′ is flat and is angled about 10 degrees relative to a horizontal plane to direct the reflected light toward optical detector144′. The angled reflective surface500′ ofFIG.19may also encourage drainage of any condensation (fuel or aqueous) that forms upon reflective surface500′. The illustrative optical monitor104c′ also includes at least one printed circuit board (PCB)502′ that mechanically and electrically supports light source140′ and optical detector144′. PCB502′ may also allow light source140′ and/or optical detector144′ to communicate with controller102(FIG.3). Light source140′ and optical detector144′ are illustratively coupled to the same PCB502′, but it is also within the scope of the present disclosure to use distinct PCBs. The illustrative optical monitor104c′ further includes a cover510′, an upper housing512′, and a lower housing514′. Lower housing514′ may be removably coupled to upper housing512′, such as using a snap connection515′, a threaded connection, or another removable connection. Upper housing512′ contains light source140′, optical detector144′, and circuit board502′. Upper housing512′ may be hermetically sealed to separate and protect its contents from the potentially corrosive environment in fuel delivery system10(FIG.2). However, upper housing512′ may be at least partially or entirely transparent to permit the passage of light, as discussed further below. Lower housing514′ contains target material142′ and reflective surface500′. Reflective surface500′ may be formed directly upon lower housing514′ (e.g., a reflective coating) or may be formed on a separate component (e.g., a reflective panel) that is coupled to lower housing514′. In the illustrated embodiment ofFIG.19, reflective surface500′ is located on bottom wall516′ of lower housing514′. Unlike the contents of upper housing512′, which are separated from the vapors in fuel delivery system10, the contents of lower housing514′, particularly target material142′, are exposed to the vapors in fuel delivery system10. The illustrative lower housing514′ has bottom wall516′ with a plurality of bottom openings517′ and a side wall518′ with a plurality of side openings519′ to encourage the vapors in fuel delivery system10to enter lower housing514′ and interact with target material142′. Openings517′,519′ may vary in shape, size, and location. In general, lower housing514′ should be designed to be sufficiently solid to support and protect its contents while being sufficiently open to expose its contents to the vapors in fuel delivery system10. For example, the bottom openings517′ may be concentrated beneath target material142′. Also, the side openings519′ adjacent to target material142′ may be relatively small, whereas the side openings519′ opposite from target material142′ may be relatively large. In use, and as shown inFIG.19, light source140′ directs a beam of light along the first axis A1, through the transparent upper housing512′, and toward target material142′. The L-shaped configuration of target material142′ may block any direct light pathways between light source140′ and reflective surface500′ to ensure that all of the light from light source140′ encounters target material142′ before reaching reflective surface500′. The light that is able to pass through the pores143′ of target material142′ continues to reflective surface500′, which then reflects the light along the second axis A2, back through the transparent upper housing512′, and to optical detector144′. Optical detector144′ may signal a corrosive environment in fuel delivery system10when the transmitted light intensity through the corroding target material142′ reaches an undesirable level or changes at an undesirable rate, for example. After use, lower housing514′ may be detached (e.g., unsnapped) from upper housing512′ to facilitate removal and replacement of the corroded target material142′ and/or reflective surface500′ without disturbing the contents of upper housing512′. Optical monitor104c′ may be configured to detect one or more errors. If the light intensity detected by detector144′ is too high (e.g., at or near 100%), optical monitor104c′ may issue a “Target Material Error” to inform the operator that target material142′ may be missing or damaged. To avoid false alarms caused by exposure to ambient light, such as when opening turbine sump32(FIG.2), optical monitor104c′ may only issue the “Target Material Error” when the high light intensity is detected for a predetermined period of time (e.g., 1 hour or more). On the other hand, if the light intensity detected by detector144′ is too low (e.g., at or near 0%), optical monitor104c′ may issue a “Light or Reflector Error” to inform the operator that light source140′ and/or reflective surface500′ may be missing or damaged. In this scenario, the entire lower housing514′, including reflective surface500′, may be missing or damaged. Optical monitor104c′ may be combined with one or more other monitors of the present disclosure. For example, in the illustrated embodiment ofFIG.16, PCB502′ of optical monitor104c′ also supports a humidity sensor520′, which passes through upper housing512′ for exposure to the vapors in fuel delivery system10(FIG.2). PCB502′ may also support a temperature sensor (not shown), which may be used to compensate for any temperature-related fluctuations in the performance of light source140′ and/or optical detector144′. In still yet another embodiment, monitor104collects spectroscopic data indicative of a corrosive environment in fuel delivery system10. An exemplary spectrometer (not shown) operates by subjecting a liquid or vapor sample from fuel delivery system10to an energy source and measuring the radiative energy as a function of its wavelength and/or frequency. Suitable spectrometers include, for example, infrared (IR) electromagnetic spectrometers, ultraviolet (UV) electromagnetic spectrometers, gas chromatography-mass spectrometers (GC-MS), and nuclear magnetic resonance (NMR) spectrometers. Suitable spectrometers may detect absorption from a ground state to an excited state, and/or fluorescence from the excited state to the ground state. The spectroscopic data may be represented by a spectrum showing the radiative energy as a function of wavelength and/or frequency. It is within the scope of the present disclosure that the spectrum may be edited to hone in on certain impurites in the sample, such as acetate and acetic acid, which may cause corrosion in fuel delivery system10, as well as sulfuric acid, which may cause odors in fuel delivery system10. As the impurities develop in fuel delivery system10, peaks corresponding to the impurities would form and/or grow on the spectrum. The spectrometer may share the collected data with controller102(FIG.3) to signal a corrosive environment in fuel delivery system10when the impurity level reaches an undesirable level or changes at an undesirable rate, for example. In still yet another embodiment, monitor104collects microbial data indicative of a corrosive environment in fuel delivery system10. An exemplary microbial detector (not shown) operates by exposing a liquid or vapor sample from fuel delivery system10to a fluorogenic enzyme substrate, incubating the sample and allowing any bacteria in the sample to cleave the enzyme substrate, and measuring fluorescence produced by the cleaved enzyme substrate. The concentration of the fluorescent product may be directly related to the concentration of acetic acid producing bacteria (e.g.,Acetobacter, Gluconobacter, Gluconacetobacter) in the sample. Suitable microbial detectors are commercially available from Mycometer, Inc. of Tampa, Fla. The microbial detector may share the collected data with controller102(FIG.3) to signal a corrosive environment in fuel delivery system10when the fluorescent product concentration reaches an undesirable level or changes at an undesirable rate, for example. To minimize the impact of other variables in monitor104, a control sample may be provided in combination with the test sample. For example, monitor104cofFIG.6may include a non-corrosive control material for comparison with the corrosive target material142. This comparison would minimize the impact of other variables in monitor104c, such as decreasing output from light source140over time. As discussed above, control system100ofFIG.3includes a remediation system108capable of taking at least one corrective action to remediate the corrosive environment in fuel delivery system10. Controller102may activate remediation system108periodically (e.g., hourly, daily) in a preventative manner. Alternatively or additionally, controller102may activate remediation system108when the corrosive environment is detected by monitor104. Various embodiments of remediation system108are described below with reference toFIG.2. In a first embodiment, remediation system108is configured to ventilate turbine sump32of fuel delivery system10. In the illustrated embodiment ofFIG.2, remediation system108includes a first ventilation passageway160and a second ventilation or siphon passageway170. The first ventilation passageway160illustratively includes an inlet162in communication with the surrounding atmosphere and an outlet164in communication with the upper vapor space (i.e., top) of turbine sump32. InFIG.2, the first ventilation passageway160is positioned in lid38of turbine sump32, but this position may vary. A control valve166(e.g., bulkhead-style vacuum breaker, check valve) may be provided along the first ventilation passageway160. Control valve166may be biased closed and opened when a sufficient vacuum develops in turbine sump32, which allows air from the surrounding atmosphere to enter turbine sump32through the first ventilation passageway160. The second ventilation or siphon passageway170is illustratively coupled to a siphon port26of pump20and includes an inlet172positioned in the lower vapor space (i.e., middle) of turbine sump32and an outlet174positioned in storage tank16. A control valve176(e.g., automated valve, flow orifice, check valve, or combination thereof) may be provided in communication with controller102(FIG.3) to selectively open and close the second ventilation passageway170. Other features of the second ventilation passageway170not shown inFIG.2may include a restrictor, a filter, and/or one or more pressure sensors. When pump20is active (i.e., turned on) to dispense fuel product14, pump20generates a vacuum at siphon port26. The vacuum from pump20draws vapor (e.g., fuel/air mixture) from turbine sump32, directs the vapor to the manifold of pump20where it mixes with the circulating liquid fuel flow, and then discharges the vapor into storage tank16through the second ventilation passageway170. As the vacuum in turbine sump32increases, control valve166may also open to draw fresh air from the surrounding atmosphere and into turbine sump32through the first ventilation passageway160. When pump20is inactive (i.e., turned off), controller102(FIG.3) may close control valve176to prevent back-flow through the second ventilation passageway170. Additional information regarding the second ventilation passageway170is disclosed in U.S. Pat. No. 7,051,579, the disclosure of which is expressly incorporated herein by reference in its entirety. The vapor pressure in turbine sump32and/or storage tank16may be monitored using the one or more pressure sensors (not shown) and controlled. To prevent over-pressurization of storage tank16, for example, the vapor flow into storage tank16through the second ventilation passageway170may be controlled. More specifically, the amount and flow rate of vapor pulled into storage tank16through the second ventilation passageway170may be limited to be less than the amount and flow rate of fuel product14dispensed from storage tank16. In one embodiment, control valve176may be used to control the vapor flow through the second ventilation passageway170by opening the second ventilation passageway170for limited durations and closing the second ventilation passageway170when the pressure sensor detects an elevated pressure in storage tank16. In another embodiment, the restrictor (not shown) may be used to limit the vapor flow rate through the second ventilation passageway170to a level that will avoid an elevated pressure in storage tank16. Other embodiments of the first ventilation passageway160are also contemplated. In a first example, the first ventilation passageway160may be located in the interstitial space between a primary pipe and a secondary pipe (e.g., XP Flexible Piping available from Franklin Fueling Systems Inc. of Madison, Wis.) using a suitable valve (e.g., APT™ brand test boot valve stems available from Franklin Fueling Systems Inc. of Madison, Wis.). In a second example, the first ventilation passageway160may be a dedicated fresh air line into turbine sump32. In a third example, the first ventilation passageway160may be incorporated into a pressure/vacuum (PV) valve system. Traditional PV valve systems communicate with storage tank16and the surrounding atmosphere to help maintain proper pressure differentials therebetween. One such PV valve system is disclosed in U.S. Pat. No. 8,141,577, the disclosure of which is expressly incorporated herein by reference in its entirety. In one embodiment, the PV valve system may be modified to pull fresh air through turbine sump32on its way into storage tank16when the atmospheric pressure exceeds the ullage pressure by a predetermined pressure differential (i.e., when a sufficient vacuum exists in storage tank16). In another embodiment, the PV valve system may be modified to include a pair of tubes (e.g., coaxial tubes) in communication with the surrounding atmosphere, wherein one of the tubes communicates with storage tank16to serve as a traditional PV vent when the ullage pressure exceeds the atmospheric pressure by a predetermined pressure differential, and another of the tubes communicates with turbine sump32to introduce fresh air into turbine sump32. Other embodiments of the second ventilation passageway170are also contemplated. In a first example, instead of venting the fuel/air mixture from turbine sump32into storage tank16as shown inFIG.2, the mixture may be directed through a filter and then released into the atmosphere. In a second example, instead of using siphon port26as the vacuum source for the second ventilation passageway170as shown inFIG.2, the vacuum source may be an existing vacuum pump in fuel delivery system10(e.g., 9000 Mini-Jet available from Franklin Fueling Systems Inc. of Madison, Wis.), a supplemental and stand-alone vacuum pump, or a vacuum created by displaced fuel in storage tank16and/or fuel delivery line18. In one embodiment, and as discussed above, the second ventilation passageway170may be incorporated into the PV valve system to pull fresh air through turbine sump32and then into storage tank16when fuel is displaced from storage tank16. In another embodiment, the second ventilation passageway170may communicate with an in-line siphon port on fuel delivery line18to pull air from turbine sump32when fuel is displaced along fuel delivery line18. In a second embodiment, remediation system108is configured to irradiate bacteria in turbine sump32of fuel delivery system10. In the illustrated embodiment ofFIG.2, a first radiation source180is positioned on an outer wall of turbine sump32, and a second radiation source180′ is positioned in the ullage of storage tank16. Exemplary radiation sources180,180′ include ultraviolet-C (UV-C) light sources. When activated by controller102(FIG.3), radiation sources180,180′ may irradiate and destroy any bacteria in turbine sump32and/or storage tank16, especially acetic acid producing bacteria (e.g.,Acetobacter, Gluconobacter, Gluconacetobacter). In a third embodiment, remediation system108is configured to filter water from fuel product14. An exemplary water filtration system200is shown inFIG.11and is located together with pump20in turbine sump32above storage tank16(FIG.1). The illustrative water filtration system200includes a fuel inlet passageway202coupled to port27of pump20, a water filter204, a fuel return passageway206from the upper end of water filter204, and a water removal passageway208from the lower end of water filter204. The port27of pump20may be located upstream of leak detector34and its associated check valve (not shown) such that the water filtration system200avoids interfering with leak detector34. Water filter204is configured to separate water, including emulsified water and free water, from fuel product14. Water filter204may also be configured to separate other impurities from fuel product14. Water filter204may operate by coalescing the water into relatively heavy droplets that separate from the relatively light fuel product14and settle at the lower end of water filter204. Incoming fuel pressure drives fuel radially outwardly through the sidewall of filter element207(FIG.15), which is made from a porous filter substrate adapted to allow fuel to pass therethrough while preventing water passage therethrough. Any water that is separated from the fuel is driven downwardly through the bottom of filter element207, which is made from a porous filter substrate that allows the passage of water therethrough. The separated water then falls by gravity to the bottom of the filter housing. Exemplary water filters204including filter element207are available from DieselPure Inc. Such water filters204may reduce the water content of fuel product14to 200 ppm or less, according to the SAE J1488 ver.2010 test method. The illustrative water filtration system200also includes one or more inlet valves203to selectively open and close the fuel inlet passageway202and one or more drain valves209to selectively open and close the water removal passageway208. In certain embodiments, valves203,209are solenoid valves that are controlled through controller102. In other embodiments, valves203,209are manual valves that are manually controlled by a user. In the embodiment ofFIGS.14-15, inlet solenoid valve203is provided downstream of strainer205, which includes a mesh screen to protect valve203from exposure to solid sediment. A further manual ball valve203′ is provided downstream of solenoid valve203for manual on/off control of the illustrated filtration system200′, the details of which are further discussed below. In operation, water filtration system200circulates fuel product14through water filter204. Water filtration system200may operate at a rate of approximately 15 to 20 gallons per minute (GPM), for example. When pump20operates with inlet valve203open, pump20directs some or all of fuel product14from storage tank16, through port27of pump20, through the open fuel inlet passageway202, and through water filter204. If a customer is operating dispenser12(FIG.1) during operation of water filtration system200, pump20may direct a portion of the fuel product14to dispenser12via the delivery line18(FIG.1) and another portion of the fuel product14to water filter204via the fuel inlet passageway202. It is also within the scope of the present disclosure that the operation of water filtration system200may be interrupted during operation of dispenser12by temporarily closing inlet valve(s)203and/or203′ to water filter204. As shown schematically inFIG.14, water filter204may produce a clean or filtered fuel product14near the upper end of water filter204and a separated water product, which may be a water/oil mixture, near the lower end of water filter204. Alternatively, water filter204A shown inFIGS.21and22may utilize water/oil separation to product a clean or filtered fuel product14, as described further below. For purposes of the present disclosure, “water filter204” can interchangeably refer to water filter204shown inFIGS.14and15and described in detail herein, or to water filter204A shown inFIGS.21and22and described in detail herein. As used herein, “oil” may refer to oil and oil-based products including motor fuel, such as gasoline and diesel. The clean or filtered fuel product14that is discharged by water filter204, such as rising to the upper end of water filter204, may be returned continuously to storage tank16via the fuel return passageway206. The filtered fuel product14may be returned to storage tank16in a dispersed and/or forceful manner that promotes circulation in storage tank16, which prevents debris from settling in storage tank16and promotes filtration of such debris. By returning the filtered fuel product14to storage tank16, water filtration system200may reduce the presence of water and avoid formation of a corrosive environment in fuel delivery system10(FIG.1), including storage tank16and/or sump32of fuel delivery system10. Water filtration system200may be distinguished from an in-line system that delivers a filtered fuel product to dispenser12(FIG.1) solely to protect a consumer's vehicle. The separated water product that is discharged by water filter204, such as by settling at the lower end of water filter204, may be drained via the water removal passageway208when drain valve209is open. The separated water product may be directed out of turbine sump32and above grade for continuous removal, as shown inFIG.11. Alternatively, the separated water product may be directed via passageway208to a storage tank210inside turbine sump32for batch removal when necessary, as shown inFIGS.12,14and22. If the separated water product is a water/oil mixture, the separated water product may be subjected to further processing to remove any oil from the remaining water. For example, a selective absorbent, such as the Smart Sponge® available from AbTech Industries Inc., may be used to absorb and remove any oil from the remaining water. Referring toFIG.14, storage tank210further includes a vent line236operable to vent the headspace above the separated water product as the level within tank210increases. In an exemplary embodiment, vent line236may be routed to the headspace above fuel product14within underground storage tank16, such that any treatment or capture of the vapor within tank210may be routed through existing infrastructure used for treatment/capture of fuel vapor within tank16. Alternatively, tank210may be vented to a dedicated space as required or desired for a particular application. The illustrative water filtration systems200,200′ ofFIGS.11,12,14and15include a high-level water sensor220and a low-level water sensor222operably connected to water filter204. The water sensors220and222may be capacitance sensors capable of distinguishing fuel product14from water. The high-level water sensor220may be located beneath the entry into fuel return passageway206to prevent water from entering fuel return passageway206. The illustrative water filtration system200ofFIG.12further includes a high-level water sensor224in storage tank210. The high-level water sensor224may be an optical sensor capable of distinguishing the separated water product from air. Sensors220,222, and224may be low-power devices suitable for operation in turbine sump32. In one exemplary embodiment, filter204may have a water capacity of about 2.75 liters (0.726 gallons) between the levels of sensors220,222. Turning toFIG.14, water filtration system200′ is shown. Water filtration system200′ is similar to filtration system200described above and includes several components and features in common with system200as indicated by the use of common reference numbers between systems200,200′. However, water filtration system200′ further includes eductor230in fuel inlet passageway202which operates to effect continuous fuel filtration during operation of pump20, while also allowing for normal operation of fuel dispenser12served by pump20as further described below. As fuel is withdrawn from tank16by operation of pump20, a portion of the fuel which would otherwise be delivered to dispenser12via delivery line18is instead diverted to fuel inlet passageway202. In an exemplary embodiment, this diverted flow may be less than 15 gallons/minute, such as between 10 and 12 gallons/minute. This diverted flow of pressurized fuel passes through eductor230, as shown inFIGS.14and15, which is a venturi device having a constriction in the cross-sectional area of the eductor flow path. As the flow of fuel passes through this construction, a negative pressure (i.e., a vacuum) is formed at vacuum port232(FIG.15), which may be separate flow tube terminating in an aperture formed in the sidewall of eductor230downstream of the constriction. Filtration uptake line234is connected to vacuum port232and extends downwardly into tank16, such that filtration uptake line234draws fuel from the bottom of tank16. In an exemplary embodiment, gap G2between the inlet of line234and the bottom surface of tank16is zero or near-zero, such that all or substantially all water or sediment which may be settled at the bottom of tank16is accessible to filtration uptake line234. For example, line234may be a rigid or semi-rigid tube with an inlet having an angled surface formed, e.g., by a cut surface forming a 45-degree angle with the longitudinal axis of the tube. This angled surface forms a point at the inlet of line234which can be lowered into abutting contact with the lower surface of tank16, while the open passageway exposed by the angled surface allows the free flow of fuel into line234. Other inlet configuration may also be used for line234, including traditional inlet openings close to, but not abutting, the lower surface of the tank. By contrast to the zero or near-zero gap G2for filtration uptake line234, a larger gap G1is formed between the intake of fuel uptake line19and the bottom surface of tank16. For example, the intake opening to submersible pump24(FIG.1) may be about 4-6 inches above the lower surface of tank16. Where the pump is located above fuel product14, the intake opening into fuel uptake line may instead be about 4-6 inches above the lower surface of tank16. This elevation differential reflected by gaps G1and G2ensures that any water or contaminated fuel settled at the bottom of tank16will be taken up by filtration uptake line234rather than fuel uptake line19. At the same time, the relatively high elevation of the intake opening serving delivery line18ensures that any accumulation of contaminated fuel will be safely within gap G1, such that only clean fuel will be delivered to dispenser12. In this way, filtration system200′ simultaneously remediates contamination and protects against uptake of any contaminated fuel that may exist in tank16, thereby providing “double protection” against delivery of contaminated fuel to dispenser12. The illustrative filtration system200′ also achieves this dual mitigation/prevention functionality with low-maintenance operation, by using eductor230to convert the operation of pump20into the motive force for the operation of system200′. In particular, a single only pump20used in conjunction with system200′ both provides clean fuel to dispenser(s)12via delivery line18, while also ensuring that any accumulation of contaminated fuel at the bottom of tank16is remediated by uptake into filtration line234and subsequent delivery to filter204. The lack of a requirement of extra pumping capacity lowers both initial cost and running costs. Moreover, the additional components of system200′, such as eductor230, filter204, valves203,209and water tank210, all require little to no regular maintenance. Filtration system200′ also achieves its dual mitigation/prevention function in an economically efficient manner by using an existing pump to power the filtration process, while avoiding the need for large-capacity filters. As described in detail above, filtration system200′ is configured to operate in conjunction with the normal use of fuel delivery system10(FIG.1), such that the filtration occurs whenever dispensers12are used to fuel vehicles. This ensures that filtration system200′ will operate with a frequency commensurate with the frequency of use of fuel delivery system10. This high frequency of operation allows filter204to be specified with a relatively small filtration capacity for a given system size, while ensuring that filtration system200′ retains sufficient overall capacity to mitigate even substantial contamination. For example, a throughput of 10-12 gallons/minute through filter204may be sufficient to treat all the fuel contained in a tank16sized to serve 6-8 fuel dispensers12(FIG.1) with each dispenser12capable of delivering 15-20 gallons of clean fuel per minute. In this system sizing example, eductor230may be sized to deliver 0.1-0.3 gallons per minute of fluid via filtration uptake line234with a maximum vertical lift of 15 feet, using a flow through fuel inlet passageway202of 10-12 gallons per minute at an inlet pressure of about 30 PSIG (resulting in a pressure of at least 5 PSIG at the outlet of eductor230). An alternative water filtration system200A is shown inFIGS.21and22. Water filtration system200A is similar to filtration system200′ described above and includes several components and features in common with systems200and200′, as indicated by the use of common reference numbers between systems200,200′ and200A. Moreover, common reference numbers are used for common components of systems200′ and200A, and structures of filtration system200A have reference numbers which correspond to similar or identical structures of filtration system200′, except with “A” appended thereto as further described below. Filtration systems200′ and200A may be used interchangeably in connection with fuel delivery system10and its associated systems. However, filtration system200A includes filter204A utilizing an oil/water separation tank205A to accomplish the primary removal of water from fuel product14, rather than a filter element207as described above with respect to filtration system200′. In addition, the routing of fuel flows and the use of eductor230A in generating the motive force for fuel filtration contrasts with system200′, as described in further detail below. Similar to system200′, filtration system200A uses a diverted flow of fuel from submersible turbine pump20as the primary driver of fluid flows through eductor230, such that pump20provides the primary motive force for filtration. In the illustrated embodiment ofFIG.22, eductor230A receives the motive fuel flow from the outlet of pump20, e.g., along a discharge fluid passageway. However, it is contemplated that eductor230can receive a diverted flow on the suction side of pump20, including from fuel uptake line19, for example. The diverted fuel flow passes through port27of pump20, as shown inFIG.21, and through inlet passageway202, strainer205and inlet valve203in a similar fashion to system200′. However, unlike system200′, filtration system200A positions eductor230downstream of both valve203, and the outlet fuel flow from eductor230A is delivered directly to fuel return passageway206and then to storage tank16. This is in contrast to the flow of fluid discharged from eductor230described above, which directs both the motive fuel flow from inlet passageway202, and the filtration flow from uptake line234, to filter204(FIG.15). As best seen inFIG.22, filter204A is functionally interposed between eductor230A and fuel filtration uptake line234A. As the motive fuel flow passes through eductor230A from inlet passageway202to return passageway206A, the vacuum created by eductor230A is transmitted to the interior of filter204A via filter return passageway216A which extends from the vacuum port of eductor230A to an aperture in the upper portion (e.g., the top wall) of filter204A. This connection creates a vacuum pressure within filter204A, which draws a flow of fluid (e.g., fuel or a fuel/water mixture) from the bottom of tank16via filtration uptake line234A. This filtration flow enters filter204A at its top portion, but is delivered to the bottom portion of filter204A via dip tube214A (FIG.22). In operation, filter204A will operate in a steady state in which tank205A is always filled with fluid drawn from tank16. New fluid received from uptake line234A is deposited at the bottom of filter204A via dip tube214A, and an equal flow of fluid is discharged from the top of filter204A via return passageway216. In an exemplary embodiment, the flow rate through filter204A is slow enough, relative to the internal volume of filter204A, to allow for natural separation and stratification of water and fuel within the volume of filter204A, such that any water contained in the incoming fuel remains at the bottom of filter204A and only clean fuel is present at the top of filter204A. In an exemplary embodiment, the flow rate through filter204A is controlled with a combination of vacuum pressure from eductor230A and the cross-sectional size of the channel defined by dip tube214A. These two variables may be controlled to produce a nominal flow rate (i.e., throughput) through filter204A, as well as a fluid velocity through dip tube214A. In particular, the vacuum level produced by eductor230A is positively correlated with both flow rate and fluid velocity, while the cross-section of dip tube214A is positively correlated with flow rate but negatively correlated with fluid velocity. To preserve the ability for natural fluid stratification and avoid turbulence at the bottom of filter204A, flow rate should be kept low enough to allow incoming fuel to remain coagulated as a volume of fuel separate from any surrounding water, rather than separating out into smaller droplets that would need to re-coagulate before “floating” out of the water layer. For example, an exemplary fluid velocity which produces such favorable fluid mechanics for filter204A may be as high as 1.0, 2.0, 3.0 or 4.0 ft/second, such as about 3.3 ft/second. In one exemplary arrangement, oil/water separation tank205A has a nominal volume of 1.1 gallons, dip tube214A defines a fluid flow cannula with an internal diameter of 0.25 inches, and vacuum level generated by eductor230A is maintained between 12-15 inHg. This configuration produces a flow rate of about 0.50 gallons per minute (gpm) and an incoming fluid velocity (at the exit of dip tube214A into the lower portion of filter204A) of about 3.27 ft/sec. In this arrangement, throughput of filter204A is maximized while preventing unfavorable fluid flow characteristics as described above. Moreover, if vacuum is increased to 18 inHg, aeration of the incoming fuel can create unfavorable effects, such as foaming of diesel fuel. Additional elements may be provided create operator control (or control via controller102, shown inFIG.3) over one or more constituent elements of the fluid velocity. For example, an adjustable or restricting flow orifice, such a ball valve or flow orifice plate, may be provided in the motive flow to eductor230A. In an exemplary embodiment, this restriction may be placed downstream of eductor230A in fuel return passageway206A for example. This adjustable flow orifice may constrict the flow through passageway206A, which establishes a back pressure on eductor230A and thereby limits or defines the nominal vacuum pressure generated by eductor230A. Another control element may be a similar adjustable or restricting flow orifice placed in filtration uptake line234A, which limits the uptake flow rate to ensure the nominal flow volume and speed is achieved. In the above-described example of 0.50 gpm, a flow orifice diameter of 0.0938 inches in uptake line234A has been found to produce the target flow rate of 0.50 gpm and the target flow speed of about 3.3 ft/sec when the vacuum pressure on eductor230A is set to a target range of 12-15 inHg. The size of filter204A may be scaled up or down to accommodate any desired filtration capacity, and the particular configuration of filtration system200A can be modified in keeping with the principles articulated above. For example, increasing the cross-section of dip tube214A decreases fluid velocity, such that the nominal flow rate through filtration uptake line234A may be increased without producing an unfavorable fluid velocity. Similarly, the nominal volume of tank205A may be decreased if no turbulence is experienced in the stratification of the contained fluids, or may be increased in order to accommodate a modest level of turbulence. If water is present in the fluid drawn from the bottom of storage tank16through uptake line234A (FIG.21), the water will naturally separate from the fuel and settle to the bottom of filter204A, where the water is collected and retained for later withdrawal (described below). The clean fuel14, which floats to the top of the stratified fluids within filter204A, will be drawn back through eductor230via filter return passageway216A and allowed to mix with the motive flow of fuel to be discharged to tank16via fuel return passageway206A. In this way, filter return passageway216A combines with fuel return passageway206A to form the fuel return passageway which returns filtered fuel product from filter204A to the storage tank. If sufficient water accumulates within filter204A, the water reaches high-level water sensor220A (FIG.22) exposed to the interior of tank205A and positioned above the lower portion of filter204A. In the illustrated embodiment, high-level water sensor22A is located on the upper portion of the filter204A, at a height that results in a majority of the fluid in the filter204A being below sensor220A. In some embodiments, 60%, 70%, 80% or 90% of the internal volume of filter204A may be below sensor220A. This arrangement allows a significant amount of water to accumulate to avoid frequent draining procedures, while also using the remaining filter volume as a secure buffer of clean fuel above the water level to prevent accidental discharge of water or contaminated fuel from filter204A to storage tank16. When contacted with water, sensor220A activates and sends a signal to controller102(FIG.3), which may then activate an alarm or initial a remediation protocol, or take other corrective action as described herein. For example, activation of water sensor220A may issue a notification to prompt an operator to drain the water accumulated in tank205A, or may initiate a similarly automated water removal process. FIG.22illustrates water removal passageway208A, which is functionally interposed between filtration uptake line234A and dip tube214A. To initiate a water removal procedure either by a human operator or by operation of controller102(FIG.3), uptake valve212A may first be closed to prevent any further uptake of fuel14from tank16. Water outlet valve209A may then be opened, and a pump (not shown) attached to water removal passageway208A may be activated to draw water from the bottom of filter204A via dip tube214A. Where the water withdrawal is done by a human operator, a hand pump or manually operable electric pump may be used. Alternatively, an automated electric pump may be used by the operator, or controlled by controller102(FIG.3) to automatically drain the water as part of a corrective action protocol. In an exemplary embodiment, check valve218A may be provided in uptake line234between tank16and uptake valve212A, in order to provide additional insurance against a backflow of water into tank16during water withdrawal. Check valve218A also guards against any potential siphoning of water from filter204A, which may be located physically above tank16, into tank16via dip tube214A and filtration uptake line234A. The water withdrawal process may be calibrated, either by a human operator or controller102(FIG.3), to withdraw a predetermined quantity of fluid upon initiation of a water removal protocol. The predetermined amount may be the volume of fluid calculated to exist below water sensor220A and within water filter204A, for example. Optionally, inlet valve203may be closed during the water removal process, in order to prevent a competing suction pressure from eductor230. Alternatively, turbine pump20(FIG.21) may be shut down and inlet valve203may be left open. Turning now toFIG.23, filtration system200B includes another separator-type filter204B and is otherwise similarly constructed to filtration system200A described above. Common reference numbers are used for common components of systems200′,200A and200B, and structures of filtration system200B have reference numbers which correspond to similar or identical structures of filtration systems200′ and200A, except with “B” appended thereto as further described below. Filtration system200B has all the same functions and features as filtration system200A described above, except as noted below. Filtration systems200′,200A and200B may be used interchangeably in connection with fuel delivery system10and its associated systems. However, filter204B of filtration system200B includes sensor valve assembly244, shown inFIGS.24B-27, which can be used in lieu of (or in addition to) high-level water sensor220A (FIG.22) to sense the presence of water near the top of tank205B and, in conjunction with sensor242(FIG.24B), issue a signal or alert indicative of this high-water condition. As best seen inFIG.23, the components of filtration system200B are sized and configured to fit within sump32, together with a typical set of existing components including turbine pump22, delivery lines18and associated shutoff valves and ancillary structures. In the illustrative embodiment ofFIGS.24A and24B, mounting bracket240is provided to provide structural support for tank205B and associated structures from the flow lines between inlet passageway202B and return passageway206B. Like filtration systems200,200′ and200A described above, filtration system200B may also be applied to other sumps or parts of fuel delivery system10, such as dispenser sump30(FIG.1). Also similar to systems200′ and200A, system200B uses a diverted flow of fuel from submersible turbine pump20as the primary driver of fluid flows through eductor230, via inlet passageway202B and strainer205(FIG.24A), such that pump20provides the primary motive force for filtration. Fuel flows downstream to fuel return passageway206B to return to the underground storage tank16(FIG.24A), passing eductor230to create vacuum pressure in filter return passageway216B, which in turn transmits the vacuum pressure to the interior of tank205B via valve assembly244(as further described below). This vacuum pressure also within tank205B is sufficient to draw fuel from UST16via filtration uptake line234B, which extends to the bottom of UST16as seen inFIG.24Aand also described in detail herein with respect to other filtration system configurations. The fuel drawn through uptake line234B provides a slow and steady flow into the bottom of tank205B via dip tube214B, also described in greater detail with respect to filtration system200A. During steady-state operation, the vacuum in return passageway216B draws fuel back to the primary return flow through fuel return passageway206B. In the illustrated embodiment ofFIGS.24A and24B, strainer205is provided between valve assembly244and eductor230. Turning now toFIG.25, filter204B is shown partially filled with water W and, during steady-state operation, the remainder of tank205B is filled with fuel floating above water W. In this configuration, float248resides at the bottom of the interior cavity252of sensor valve body246of sensor assembly244, retained by snap ring250. Fuel deposited into tank205B via dip tube214B rises to float on the heavier water W, while any water contained in the deposited fuel stratifies to remain in water W. Because water W is well below float248, pure fuel is continuously cycled through sensor valve assembly via ports249in valve body246. This pure fuel is then drawn into vacuum port254to be returned to UST16via return passageway216B (FIG.24B). During the steady-state, low-water operation depicted byFIG.25, a vacuum is maintained throughout the components of water filtration system200B as described herein. This vacuum maintains a steady flow of fuel through filter return passageway216B via eductor230, as shown inFIG.24B. This flow is measured by flow sensor242, which is in fluid communication with the suction port of eductor230and/or the interior flow path defined by passageway216B. Sensor242detects the presence (and, optionally, the rate) of fluid flow through the suction port of eductor230, and issues a signal (or a lack of a signal) indicative of such fluid flow. This signal may be received by controller102, for example, or may simply be received by an operator via an indicator (light, siren, etc.). InFIG.26, the level of water W has risen such that a portion of sensor valve assembly244is submerged below the level of water W. Float248has a density below that of water W, but above that of the hydrocarbon fuel stratified above water W as described above. Details of an exemplary float248can be found in U.S. Pat. No. 8,878,682, entitled METHOD AND APPARATUS FOR DETECTION OF PHASE SEPARATION IN STORAGE TANKS USING A FLOAT SENSOR and filed Oct. 16, 2009, the entire disclosure of which is hereby expressly incorporated herein by reference. As the level of water W rises to engage float248, float248rises within interior cavity252, eventually approaching the top wall of cavity252and port254. When float248get near enough to port254, the concentration of vacuum pressure at port254draws float248into contact with the top wall of cavity252as illustrated inFIG.26, shutting off (or substantially reducing) the flow of fluid. Because port254becomes blocked as a result of a high water level, shutting off the flow of fluid from filter204B prevents any of water W from reentering UST16. The ceasing of fluid flow through passageway216B also stops fluid flow at the vacuum port of eductor230. In addition, the flow of fluid may reduce before ceasing completely. Sensor242detects the reduction and/or cessation of fluid flow, and issues a signal (or a lack of a signal) indicative of cessation of flow or of a reduction of flow below a predetermined threshold nominal value. Controller102may issue an alert and/or initiate remediation when sensor242indicates the high level of water W shown inFIG.26. As described in detail above with respect to filtration system200A, remediation may include draining of water W. To facilitate such draining, water filtration system200B may be equipped with the same water removal passageway208and associated structures found in filtration system200A, as shown inFIG.22and described in detail above. When water W is removed from tank205B, float248falls away from port254toward its bottom-seated position shown inFIG.25, once again allowing fluid to flow through the vacuum port of eductor230. As noted above, water filter204B may be located within a sump (e.g., sump32shown inFIG.23) and therefore near or above grade. Because water W may be allowed to accumulate within tank205B, below-freezing weather has the potential to create ice within tank205B. To address this potential in cold-weather installations, a temperature probe may be installed within or on the outside wall of tank205B and configured to issue a signal to controller102or a system operator. When the temperature probe indicates temperatures near, at, or below freezing, the operator or controller102may initiate a flow of fuel from UST16through filter204B, as described herein. Because the UST16is located underground and well below grade, the incoming fuel is reliably above freezing and can be used to maintain the internal temperature of tank205B above freezing. This incoming flow may be maintained until the temperature probe reaches a threshold above-freezing temperature, regardless of whether controller102is calling for fuel flow for filtration purposes. Although this temperature-control system and method are described with respect to filtration system200B, the same system may also be applied in the same way to other filtration systems made in accordance with the present disclosure, including systems200,200′ and200A. Controller102(FIG.3), or a human operator, may also use inlet valve203to selectively activate or deactivate the fuel filtration process enabled by filtration systems200A or200B (or, alternatively, systems200or200′, it being understood that systems200,200′,200A and200B may be used interchangeably as noted herein). For example, controller102may be programmed with a pre-determined schedule for fuel filtration, and may open valve203to initiate a filtration cycle. After a predetermined amount of time during which the filtration cycle is active and filtration is occurring as described above, controller102may close valve203to stop the filtration cycle. After a predetermined amount of time during which the filtration cycle is not active, a new cycle may begin. Alternatively, in some embodiments, valve203may be omitted or left open, such that fuel filtration occurs any time pump20is active. The use of the separator-type filters204A,204B allow filtration systems200A,200B to be virtually maintenance free, with the only regular maintenance task being the periodic removal of accumulated water from filter204A,204B. Even this maintenance task may be automated as noted above. In contrast to filtration system200′, which uses a substrate-type filter207as described in detail above, filtration systems200A,200B have no substrate filters which would require replacement or service. The separator-type filters204A,204B may also be sized to fit existing or newly-installed sumps, such as turbine sump32of fuel delivery system10(FIG.1). As noted above, a system designer has flexibility in sizing the volume of filters204A,204B by controlling the flow rate of fluid to be filtered. Therefore, where there is a requirement for a filtration system to accommodate a small space within a sump, filters204A,204B can be sized accordingly and the nominal filtration flow rate per can be set at an appropriate percentage of the filter volume as described in detail above. However, it is contemplated that a filter substrate, such as filter207, or any other coalescing filter element, particulate filter element, or a combination thereof may be used inside filters204A,204B, as required or desired for a particular application. As discussed herein, filtration systems200,200′,200A and200B utilize submersible pump20, already existing as a component of fuel delivery system10, as a motive fuel flow source to power a vacuum generating device, illustrated with respect to the various embodiments as eductor230. Although the illustrative filtration systems200′,200A,200B use eductor230to draw the contaminated fuel from the bottom of tank16, other equipment may be used to perform this operation, such as another type of venturi device or a supplemental pump (in addition to pump20). For example, a flow from the pump20, including a primary and/or diverted flow, may be used to drive an impeller which drives a separate pump for filtration, similar to the operation of a turbocharger system of an internal combustion engine, which uses exhaust gases to power an impeller. The dedicated filtration pump powered by the flow of the primary pump may then be used in place of eductor230to drive filtration flows as described herein. Yet another alternative is to use a dedicated, electrically powered pump for filtration flows. This dedicated pump may be used in place of eductor230or230A as shown inFIGS.15and22, for example. In this configuration of filtration system200,200′,200A or200B, fuel return passageway206,206A or206B is used only for return of filtered fuel flows, with no need for a separate motive flow of fuel as described herein with respect to venturi-based systems. The dedicated filtration pump may have a low-flow configuration sufficient for only the filtration flow desired for the throughput of filter204,204A or204B. In still another alternative arrangement, pump20may be configured as a diaphragm-type pump, in which a primary stroke of the pump is used for delivery of fuel to dispenser12via delivery line18(FIG.1), while the reverse stroke can be used to drive filtration flows as described herein. In this configuration, of filtration system200,200′,200A or200B eductor230is omitted. If the flows resulting from the reverse stroke of the diaphragm pump20are commensurate with the desired filtration flows through filter204,204A or204B, then fuel return passageway206,206A or206B is again used only for filtration flows with no separate excess or motive flow. If the flows from the reverse stroke of diaphragm pump20are higher than the desired flows through filter204,204A or204B, then fuel return passageway206,206A or206B may be also be sized to discharge excess flows back to tank16. Referring next toFIG.13, an exemplary method300is disclosed for operating water filtration systems200,200′,200A,200B. Method300may be performed using controller102(FIG.3). Method300is described below with reference to the illustrative water filtration system200ofFIG.12, though the disclosed method is also applicable to systems200′,200A and200B. In step302of method300, controller102determines whether a predetermined start time has been reached. The start time may occur at a desired time, preferably outside of high-demand fuel dispensing hours (e.g., 4:30 to 7:30 AM), and with a desired frequency. For example, the start time may occur daily at about 8:00 PM. When the start time of step302is reached, method300continues to step304. It is also within the scope of the present disclosure that method300may be initiated based on an input from one or more monitors104(FIG.3). It is further within the scope of the present disclosure that method300may be initiated only when a certain minimum level of fuel product14is present in storage tank16, such as about 20 to 30 inches of fuel product14, more specifically about 24 inches of fuel product14. In step304of method300, controller102operates water filter204to filter fuel product14. As discussed above, this filtering step304may involve opening inlet valve203of fuel inlet passageway202and activating pump20. After passing through water filter204, the filtered fuel product14may be returned continuously to storage tank16via fuel return passageway206. In step306of method300, controller102determines whether a predetermined cycle time has expired. The cycle time may vary. For example, the cycle time may be about 1-10 hours, more specifically about 7-9 hours, and more specifically about 8 hours. If the cycle time has expired, method300continues to step307, in which controller102closes inlet valve203of fuel inlet passageway202to water filter204and resets the cycle time before returning to step302to await a new start time. If the cycle time has not yet expired, method300continues to step308. In step308of method300, controller102determines whether a water level in water filter204is too high. Step308may involve communicating with the high-level water sensor220in water filter204. If the high-level water sensor220detects water (i.e., activates), method300continues to steps310and312. If the high-level water sensor220does not detect water (i.e., deactivates), method300skips steps310and312and continues to step314. In step310of method300, controller102drains the separated water product from water filter204. As discussed above, this draining step310may involve opening drain valve209of water removal passageway208. From step310, method continues to step312. In step312of method300, controller102determines whether a water level in water filter204is sufficiently low. Step312may involve communicating with the low-level water sensor222in water filter204. If the low-level water sensor222still detects water (i.e., activates), method300returns to step310to continue draining water filter204. Once the low-level water sensor222no longer detects water (i.e., deactivates), method300continues to step314. Controller102may initiate an alarm if the draining step310is performed for a predetermined period of time without deactivating the low-level water sensor222. Controller102may also initiate an alarm if a discrepancy exists between the high-level water sensor220and the low-level water sensor222, specifically if the high-level water sensor220detects water (i.e., activates) but the low-level water sensor222does not detect water (i.e., deactivates). In step314of method300, controller102determines whether a water level in storage tank210is too high. Step314may involve communicating with the high-level water sensor224in storage tank210. Step314may also involve calculating the volume of water contained in storage tank210based on prior draining steps310from water filter204. This volume calculation may involve logging the number of draining steps310from water filter204triggered by the high water-level sensor220and determining the known volume of water drained between sensors220and222during each draining step310. If the high-level water sensor224does not detect water (i.e., deactivates) or the calculated water volume inside storage tank210is lower than a predetermined limit, method300returns to step304to continue operating water filter204. If the high-level water sensor224detects water (i.e., activates) or the calculated water volume inside storage tank210reaches the predetermined limit, method300continues to step316. In step316of method300, controller102initiates an alarm or sends another communication requiring storage tank210to be emptied and replaced. Controller102also closes inlet valve203of fuel inlet passageway202and resets the cycle time. After storage tank210is emptied and replaced, controller102returns to step302to await a new start time. In a fourth embodiment, remediation system108is configured to control the humidity in turbine sump32of fuel delivery system10. In the illustrated embodiment ofFIG.2, remediation system108includes a desiccant400(e.g., calcium chloride, silica gel) that is configured to adsorb water from the atmosphere in turbine sump32. Desiccant400may be removably coupled to turbine sump32, such as being detachably suspended from lid38of turbine sump32. In this embodiment, monitor104″″ may be a humidity sensor that is configured to measure the humidity in the vapor space of turbine sump32. Monitor104″″ may also be configured to measure the temperature in the vapor space of turbine sump32. The humidity and/or temperature data may be communicated to controller102(FIG.3). When the humidity level increases above a predetermined level (e.g., 40%), output106may instruct the operator to inspect turbine sump32and/or to replace desiccant400. The above-described embodiments of remediation system108may be provided individually or in combination, as shown inFIG.2. Thus, remediation system108may be configured to ventilate turbine sump32of fuel delivery system10, irradiate bacteria in turbine sump32of fuel delivery system10, operate water filtration system200, and/or control the humidity in turbine sump32of fuel delivery system10. While this invention has been described as having exemplary designs, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims. EXAMPLES 1. Example 1: Degradation of Transmitted Light Intensity in Corrosive Environment Various plain steel samples were prepared as summarized in Table 1 below. Each sample was cut into a 1-inch square. TABLE 1No.DescriptionDimensions1Fine wire mesh60 × 60 mesh, 0.0075″ wire diameter2Thick wire mesh14 × 14 mesh, 0.035″ wire diameter3Perforated sheet0.033″ hole diameter4Fine wire mesh30 × 30 mesh, 0.012″ wire diameter5Perforated sheet0.024″ hole diameter The samples were placed in a sealed glass container together with a 5% acetic acid solution. The samples were suspended on a non-corrosive, stainless steel platform over the acetic acid solution for exposure to the acetic acid vapor in the container. Select samples were removed from the container after about 23, 80, and 130 hours. Other samples were reserved as control samples. Each sample was placed inside a holder and illuminated with a LED light source inside a tube to control light pollution. An ambient light sensor from ams AG was used to measure the intensity of the light passing through each sample. The results are presented inFIGS.7-9.FIG.7includes photographs of the illuminated samples themselves.FIG.8is a graphical representation of the relative light intensity transmitted through each sample over time.FIG.9is a graphical representation of the normalized light intensity transmitted through each sample over time, with an intensity of 1.00 assigned to each control sample. As shown inFIGS.7-9, all of the samples exhibited increased corrosion and decreased light transmission over time. The fine wire mesh samples (Sample Nos. 1 and 4) exhibited the most significant corrosion over time. 2. Example 2: Real-Time Degradation of Transmitted Light Intensity in Corrosive Environment Sample No. 4 of Example 1 was placed inside a sealed plastic bag together with a paper towel that had been saturated with a 5% acetic acid solution. The sample was subjected to illumination testing in the same manner as Example 1, except that the sample remained inside the sealed bag during testing. The results are presented inFIG.10, which is a graphical representation of the actual light intensity transmitted through the sample over time. Like Example 1, the sample exhibited increased corrosion and decreased light transmission over time. 3. Example 3: Humidity Control with Desiccant A turbine sump having a volume of 11.5 cubic feet and a stable temperature between about 65° F. and 70° F. was humidified to about 95% using damp rags. The rags were then removed from the humidified turbine sump. A desiccant bag was placed inside the humidified turbine sump, which was then sealed closed. The desiccant bag contained 125 g of calcium chloride with a gelling agent to prevent formation of aqueous calcium chloride. The relative humidity and temperature in the turbine sump were measured over time, as shown inFIG.20. After 1 day, the desiccant had adsorbed enough moisture to decrease the relative humidity to about 40%. After 3 days, the desiccant had adsorbed enough moisture to decrease the relative humidity beneath about 20%. The relative humidity eventually decreased beneath 10%. | 94,308 |
11858804 | DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION With reference to the figures, number1indicates a system for emptying a container, e.g. a drum, containing a fluid product. The system1comprises a pumping unit2. Such pumping unit2comprises:a pump5;a scraping plate4arranged at a first end of the pump5and having a through hole at it;a motor3arranged at a second end of the pump5. Preferably, the motor3is of the pneumatic activation type. The pumping unit2is moved vertically inside the container100by means of a pneumatic cylinder6. Preferably, the pneumatic cylinder6is operatively active on the pumping unit2for providing at least a first force and a second force of a greater magnitude than the first. The system1further comprises a first and a second sensor suitable to detect the presence of the pumping unit2. There is also a supply circuit for supplying air to the pumping unit2. Preferably, the air supply circuit communicates with the scraping plate4so that it dispenses air below it. The system1further comprises a control unit7configured at least to:activate the pump5in response to the detection by the first sensor of a passage of the pumping unit2at a first level of the container100;stop the descent of the pumping unit2and deactivate the pump5in response to the detection by the second sensor of a passage of the pumping unit2at a second level of the container100;enable the communication between the pumping unit2and the air supply circuit after having deactivated the pump5;interrupt the communication between the pumping unit2and the air supply circuit in response to the detection by the first sensor of a further passage of the pumping unit2at the first level of the container100; The second level is lower than the first level. Preferably, the control unit7is further configured to make the pumping unit2stop at the second level for a predefined period of time so as to complete the emptying of the container100. This happens after stopping the descent of the pumping unit2and before deactivating the pump5. Preferably, the control unit7is further configured to:force the cylinder6to exert the first force on the pumping unit2after having deactivated the pump5;force the cylinder6to exert the second force on the pumping unit2in response to the detection by the first sensor of a further passage of the pumping unit2at the first level of the container100. In the embodiment described and illustrated herein, the sensors are arranged on the pneumatic cylinder6. According to the height of the container100, it is possible to determine a first position and a second position assumed by the cylinder6when the pumping unit2passes at the first level and the second level, respectively. By positioning the first and the second sensor in this way, it is possible to detect when the pumping unit2is at the first and the second level. In the eventuality of a format change for the container100, the position of the sensors is easily and quickly adaptable. Preferably, the sensors are of the magnetic type. It is to be noted that the connection between the pneumatic cylinder6and the pumping unit2is of the rigid type, therefore the motion of the pumping unit2is of the rigid type. Therefore, knowing the position assumed by any point of the pumping unit2with respect to the pneumatic cylinder6, the position of all the points of the pumping unit2is also known. Therefore, it can be envisaged without any significant modification to the system1to implement the sensors described above in a component of the pumping unit2. In an alternative embodiment, the sensors are arranged on the scraping plate4. For example, such sensors are proximity sensors, of the induction or ultrasonic type. Preferably, the system1further comprises a positioning means8for positioning the container below the pumping unit2. In the embodiment described and illustrated herein, such positioning means8comprises at least one adjustable guide element9. Preferably, there are at least three guide elements9suitable for contacting the container100in three distinct points. In an alternative embodiment, the positioning means8comprises a conveyor belt with intermittent operation. Preferably, the system1further comprises a plurality of wheels10. Thus the system1can be moved on a resting plane. The method for emptying a container, e.g. a drum, containing a fluid product, according to the present invention, is described below. Above all, the container100is arranged below a pumping unit2in a predefined position. Preferably, the arrangement in a predefined position takes place by means of the adjustable guide element9. The pumping unit2is moved close to a mouth of the container100. Then, the passage of the pumping unit2at the first level of the container100is preferably detected by means of the first sensor. For example, such first level may be the mouth or a level of the container100below the mouth. For example, such level may identify the level of the product contained inside. Passage of the pumping unit2at the first level means that the passage of at least one of the elements comprising the pumping unit2is detected. Preferably, the passage of the scraping plate4at the first level of the container100is detected. Upon detection of the passage of the pumping unit2at the first level, the pump5is activated. The pumping unit2descends towards a bottom of the container100so that the pump5sucks the product inside the container100during the descent of the pumping unit2. Preferably, the descent of the pumping unit2is activated by the sole weight of the pumping unit2without the intervention of external forces thereto. During the descent, the passage of the scraping plate2at the second level of the container100is detected. For example, the second level may be the bottom of the container100or a level of the container100above the bottom. In any case, as already mentioned, the second level is lower than the first level. The detection preferably takes place through the second sensor. Upon detection of the passage of the pumping unit2at the second level, the descent of the pumping unit2stops and the pump5is deactivated. Passage of the pumping unit2at the second level means that the passage of at least one of the elements comprising the pumping unit2is detected. Preferably, the passage of the scraping plate4at the second level of the container100is detected. The method further comprises a step of dispensing air inside the container100coming from the air supply circuit to the pumping unit2. Then, the pumping unit2is made to return upwards towards the mouth through the combined action of a pneumatic cylinder6which is operatively active on the pumping unit2for providing the first force and of dispensed air. According to one embodiment, the first force exerted by the pneumatic cylinder6in this step is substantially equal and opposite to the weight force of the pumping unit2. During the upwards return, a further passage of the pumping unit2at the first level is detected, preferably by means of the first sensor. Upon detection of the further passage of the pumping unit2at the first level, the dispensing of air is interrupted. Finally, the pumping unit2is extracted from the container100through the action of the pneumatic cylinder6. Preferably, in this step, the pneumatic cylinder6exerts on the pumping unit2the second force of a greater magnitude with respect to the first force. Preferably, the pumping unit2is made to stop at the second level for a predefined period of time so as to complete the emptying of the container100. This step takes place after stopping the descent of the pumping unit2and before deactivating the pump5. The characteristics and the advantages of the method and system for emptying a container, e.g. a drum, containing a fluid product, according to the present invention, prove to be clearly indicated in the description provided, as do the advantages. In particular, the use of sensors for detecting the passage of the pumping unit in determined positions makes it possible to automate, at least in part, the drum emptying operations, reducing the times and increasing the reliability. In fact, it is no longer necessary to have to appoint an operator to establish the end of one operation and the beginning of the next. Furthermore, the descent of the pumping unit only takes place due to the weight force of the pumping unit. The pneumatic cylinder does not push downwards, thus preventing the formation of overturning moments during emptying, which are dangerous to any operators who may be in the vicinity. Furthermore, in this way, bases are not necessary to contrast the thrust of the cylinder in the downwards direction, which would make the machine less hygienic and easy to clean, as well as making the step of positioning drums below the pumping unit more difficult. Furthermore, the change in magnitude of the thrust of the cylinder to the pumping unit when the pumping unit is to be extracted from the container enables the lifting of the container itself to be prevented, as happens in some known solutions. Furthermore, it is no longer necessary to envisage the use of means for locking the container to solve the problem of the container being lifted, therefore the system is more streamlined. | 9,304 |
11858805 | DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS FIG.1shows a top view onto a micromechanical structure1made up of a substrate2and a seismic mass3.FIG.2shows a cross-section through micromechanical structure1ofFIG.1at the intersecting line denoted by A.FIG.3shows a cross-section through micromechanical structure1ofFIG.1at the intersecting line denoted by B. The micromechanical structure is described hereafter based onFIGS.1through3, it being possible that individual elements are not visible in all figures. Micromechanical structure1includes first detection means (i.e., first detector)4and second detection means (i.e., second detector)5. A first direction11and a second direction12define a main extension plane of the substrate, first direction11and second direction12being situated essentially perpendicularly on each other and, in particular, being perpendicular to one another. First detection4means are provided for detecting a translatory deflection of seismic mass3in first direction11. Second detection means5are provided for detecting a rotatory deflection of seismic mass3about a rotation axis, the rotation axis being situated essentially in parallel to second direction12, in particular, in parallel to second direction12. Seismic mass3is connected to substrate2via an anchoring element6and four torsion spring sections7. In the process, anchoring element6is connected to substrate2and torsion spring sections7, and torsion spring sections7are connected to anchoring element6and seismic mass3. First detection means4include an electrode structure made up of first electrodes41and second electrodes42, first electrodes41being attached at seismic mass3and second electrodes42being attached at the substrate. First electrodes41and second electrodes42have an essentially two-dimensional extension in second direction12and a third direction13, third direction13being essentially perpendicular to the main extension plane. In other words, an extension of first electrodes41or second electrodes42in first direction11is small compared to an extension in second direction12or third direction13. Anchoring element6includes a first section61and a second section62. A gap63is situated between first section61and section62. A connecting element8connects two first electrodes41and is guided through the gap. Connecting element8enables an improved mechanical stability of the first electrodes connected by connecting element8. When seismic mass3is deflected in first direction11out of a rest position due to an acceleration in first direction11acting on seismic mass3, first electrodes41connected to seismic mass3are displaced with respect to second electrodes42connected to substrate2. This displacement may be detected as a change of a capacitance of a first capacitor formed by first electrodes41and second electrodes42. A measure of the displacement is dependent on a first spring constant of torsion spring sections7, the first spring constant indicating a measure of a deflection of torsion spring section7in first direction11, based on a force acting on torsion spring sections7. The further features of micromechanical structure1described inFIGS.1through3are optional and represent preferred specific embodiments. Two first electrodes41are situated on a first side64of anchoring element6, and two first electrodes41are also situated on a second side65situated opposite first side64. First electrodes41on first side64are connected to connecting element8with the aid of a first transverse structure81. First electrodes41on second side65are connected to connecting element8with the aid of a second transverse structure82. It may be provided that a number of first electrodes41deviating fromFIGS.1through3is situated on first side64and second side65. Seismic mass3includes a frame31. Torsion spring sections7abut frame31and anchoring element6. First electrodes41abut the frame. Two outer areas34and two inner areas35are formed by frame31, anchoring element6, and torsion spring sections7. Outer areas34are situated between frame31and two torsion spring sections7in each case. Inner areas35are in each case situated between frame31, two torsion spring sections7, and anchoring element6. Connecting element8connects first electrodes41, which are each situated in one of inner areas35, to one another. In particular, connecting element8connects all first electrodes41in one of inner areas35to all first electrodes41in the other inner area35. Frame31includes a first mass32and a second mass33, which are each situated on the outside of seismic mass3, based on first direction11. Since second mass33is greater than first mass32, an acceleration of micromechanical structure3in third direction13results in a rotation of seismic mass3about the rotation axis in parallel to second direction12. As a result of first mass32and second mass33, an asymmetrical mass distribution is given, which is necessary for this effect. Second detection means5include third electrodes53situated at frame31and fourth electrodes54situated at substrate2. When seismic mass3is deflected rotatorily about the rotation axis in parallel to second direction12out of a rest position due to an acceleration in third direction13acting on seismic mass3, third electrodes53connected to seismic mass3or frame31are displaced with respect to fourth electrodes54connected to substrate2. This displacement may be detected as a change of a capacitance of a first capacitor formed by third electrodes53and fourth electrodes54. In the process, a measure of the displacement is dependent on a second spring constant of torsion spring sections7, the second spring constant indicating a measure of a torsional stiffness of torsion spring sections7. Instead of the shown second detection means5, other second detection means5may also be provided, with the aid of which a rotatory deflection about the rotation axis in parallel to second axis12may be detected. Two second electrodes42are assigned to each of first electrodes41, so that always two second electrodes42and one first electrode41form part of a detection means4. During a deflection in first direction11, in each detection means the plate distance of a first capacitor, formed of first electrode41and one of the second electrodes42, is reduced, while the plate distance of a further first capacitor, formed of first electrode41and the other of second electrodes42, is increased. FIG.4shows a top view onto a section of a further micromechanical structure1, which corresponds to micromechanical structure1ofFIGS.1through3, unless differences are described hereafter. In particular, inner areas35are shown inFIG.4. In outer areas34, micromechanical structure1may, in particular, be identical to micromechanical structure1ofFIGS.1through3. In inner areas35, only one first electrode41and two second electrodes42are in each case situated on first side64and second side65. Connecting element8connects first electrodes41. Since only one first electrode41is situated in each of inner areas35, no transverse structures81,82are provided. In the area in which sections61,62of anchoring element6are connected to torsion spring sections7, anchoring element6includes a respective taper66. It may be provided that anchoring elements6, in the area of taper66, are not guided up to substrate2in third direction13, so that the two torsion spring sections7, which abut first section61, and the two torsion spring sections7, which abut second section62, in each case form a continuous torsion spring71. These two embodiments of micromechanical structure1ofFIG.4may also be provided independently of one another in the micromechanical structure ofFIGS.1through3. FIG.5shows a cross-section through micromechanical structure1ofFIG.4at the intersecting line through connecting element8denoted inFIG.4by C. Connecting element8includes a first elevation83. The first elevation is situated between connecting element8and substrate2. As a result of first elevation83, a distance between substrate2and connecting element8is decreased, compared to areas outside first elevation83. First elevation83is used to prevent seismic mass3from striking against substrate2, or at least make it more difficult, if seismic mass3is moved in third direction13toward substrate2due to a force acting on micromechanical structure1. In particular, a planar striking of connecting element8against substrate2is to be prevented or at least made more difficult. In contrast to the representation ofFIG.5, it is also possible for multiple first elevations83to be provided. An embodiment identical to first elevation83ofFIG.5may also be provided in micromechanical structure1ofFIGS.1through3. In this case, it may also be provided to situate one or multiple first elevation(s)83at first transverse structure81or second transverse structure82, in addition or as an alternative to first elevation83shown inFIG.5. In contrast to the representation ofFIG.5, frame31may also be configured in such a way that frame31has the same extension in third direction13as first electrodes41. FIG.6shows a top view onto a section of a further micromechanical structure1, which corresponds to micromechanical structure1ofFIGS.1through3, unless differences are described hereafter.FIG.7shows a cross-section through micromechanical structure1ofFIG.6at the intersecting line denoted inFIG.6by D. In particular, inner areas35are shown inFIG.6. In outer areas34, micromechanical structure1may, in particular, be identical to micromechanical structure1ofFIGS.1through3. Connecting element8includes two second elevations84. As a result of second elevations84, a distance between connecting element8and anchoring element6is decreased, compared to areas outside second elevations84. Second elevations84are used to prevent seismic mass3from striking against substrate2, or at least make it more difficult, if seismic mass3is moved in first direction11due to a force acting on micromechanical structure1. In particular, a planar striking of connecting element8against anchoring element6is to be prevented or at least made more difficult. It is also possible for more than two second elevations84or only one second elevation84to be provided. As an alternative, connecting element8and first electrodes41may also include the features described in connection withFIGS.4and5. In contrast to the representation ofFIG.7, torsion spring sections7may also be configured in such a way that torsion spring sections7have the same extension in third direction13as first electrodes41. Second elevations84shown inFIGS.6and7may be provided as an alternative or in addition to first elevation83described in connection withFIG.5. If only first elevations83or only second elevations84are provided, these may also in general be referred to as elevations83or elevations84. FIG.8shows a top view onto a section of a further micromechanical structure1, which corresponds to micromechanical structure1ofFIGS.1through3, unless differences are described hereafter. Further connecting elements85, which each connect two first electrodes41to one another, are situated between first electrodes41in outer areas34. In this way, a mechanical stability of micromechanical structure1is further increased. The embodiment of connecting element8may be as is described in connection withFIGS.1to7. Further connecting elements85may include first elevations83, as is described in connection withFIG.5. Micromechanical structure1may be made of silicon. In particular, electrodes41,42,53,54may also be made of silicon, in particular, made of doped silicon. For manufacturing the micromechanical structure1, it may be provided to situate silicon and silicon oxide in layers in such a way that, after the silicon oxide has been removed, for example with the aid of an etching process, the described micromechanical structure1made of silicon remains. FIG.9shows a micromechanical sensor9including a micromechanical structure described inFIGS.1through8. Micromechanical sensor9furthermore includes an electrical circuit91, with the aid of which detection means4,5may be read out. In particular, electrical circuit91may be configured to evaluate a first capacitor, formed by first electrodes41and second electrodes42, with respect to a changing capacitance, and to evaluate a second capacitor, formed by third electrodes53and fourth electrodes54, with respect to a changing capacitance. Although the present invention was described in detail by the preferred exemplary embodiments, the present invention is not limited to the described examples, and other variations may be derived therefrom by those skilled in the art without departing from the scope of protection of the present invention. | 12,703 |
11858806 | DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS In this description: (a) the term “portion” can mean an entire portion or a portion that is less than the entire portion; (b) the term “formed on a substrate” can mean being arranged such that the “formed” object is supported by the substrate and extends above a preexisting surface of the substrate; (c) the terms “inwards” and “inner” can refer to a direction towards a cavity formed on a substrate; (d) the terms “outwards” and “outer” can refer to a direction away from a cavity formed on a substrate, such as a direction towards a wafer edge, a die edge, or a saw lane; (e) the terms “downwards” and “lower” can refer to a direction towards a first substrate, such as a silicon substrate; and (f) the terms “upwards” and “upper” can refer to a second substrate, such as a glass wafer. Microelectromechanical system (MEMS) devices such as actuators, switches, motors, sensors, variable capacitors, spatial light modulators (SLMs) and similar microelectronic devices can have movable elements. For example, an SLM device can include an array of movable elements. Each such element can be an individually addressable light modulator element in which an “on” or “off” position is set in response to input data. The input data can be image information to command light modulator elements of the array to either project or block light directed at the array from an illumination source. In an example SLM device of an image projection system, the input data includes bit frames generated in response to pixel hue and intensity information data of an image frame of an image input signal. The bit frames can be projected using a pulse-width modulation. Pulse-width modulation schemes include weighted time intervals for projection of pixels of pixel hue and intensity corresponding to respective pixels in the input data. The weighted time intervals are sufficiently long to permit human eye integration over a given image frame display period. An example of an SLM device is a digital micromirror device (DMD), such as a Texas Instruments DLP® micromirror array device. Such DMD devices have been commercially employed in a wide variety of devices, such as televisions, cinemagraphic projection systems, business-related projectors and pico projectors. DMD devices can be manufactured to include micromirrors to digitally image and project an input digital image onto a display surface (such as a projection screen). For example, a projector system can include a DMD device can be included arranged to modulate an incident beam of light received through a window glass of the DMD device and focused on micromirrors therein. Each such micromirror can be individually and dynamically adjusted in response to input data to project a visual image onto a projection screen. An individual micromirror can be formed as a portion of a torsion spring. When the mirror goes “hard over,” the mirror contacts (e.g., hits) a stopping surface. Occasionally, the contacting mirror encounters environmentally induced adhesion (e.g., stiction) forces sufficient to prevent the mirror from rebounding from the stopping surface. Such stiction can result from environmental contamination and can create defects and reliability problems. Another such problem is excessive dynamic friction, which can result from contact between moving elements in a MEMS device. Both the excessive dynamic friction and the incidence of adhesion can be reduced by coating surfaces of the moving elements of a MEMS device with a passivating agent or lubricant (e.g., “lube”). However, the passivating agents and lubricating coatings can be compromised by other chemical species used to manufacture a MEMS device. Over time, chemical species can migrate and then degrade the performance of moving elements of a MEMS device. Such coatings for MEMS devices are described in U.S. patent application Ser. No. 14/333,829, filed Jul. 17, 2014, entitled “Coatings for Relatively Movable Surfaces,” by W. Morrison, et al., which is incorporated herein by reference in its entirety for all purposes. In the manufacture of semiconductors and MEMS devices, each MEMS device is manufactured using wafer-scale processing techniques. For example, a wafer can include many like MEMS devices arranged in rows and columns (e.g., in an array) on a substrate of a single wafer. Such techniques can decrease costs because many devices can be processed in parallel by simultaneously applying process steps. Various MEMS devices can be formed on a surface of a first substrate (such as a silicon substrate). Bondline structures can be formed (e.g., positioned) on the first substrate or a second substrate. The bondline structures can: define a distance that separates the first and second substrates; structurally bond the first substrate to the second substrate to form a unified substrate assembly; and hermetically seal a cavity enclosed by the first and second substrates and the bondline structures. Various wafer-to-wafer bonding processes for forming a hermetically sealed cavity can include substances or conditions that can compromise delicate components formed within the hermetically sealed cavity and/or extending under a bondline structure of the wafer-to-wafer bond. For example, high temperatures for melting eutectic substances and/or fusing glass frit can melt or accelerate chemical processes that degrade performance of the delicate components. Similarly, the relatively high temperatures can more quickly degrade lubrication systems in the cavity by heat-accelerated reactions of eutectic metallurgical substances (including, for example, selenium, indium and/or other low-temperature materials) with lubrication substances. Further, the lubrication systems and anodic bonding used to form surface-fabricated MEMS structures can contaminate otherwise clean and flat surfaces used to form wafer-to-wafer bonds. Also, pressures encountered in forming the wafer-to-wafer bonds cause thermocompression, which tends to damage CMOS (complementary-metal-oxide semiconductor) circuitry (including gates and related metallization). In described examples, a MEMS device and/or a CMOS device is sealed in such a cavity, such that the sealed device is environmentally protected from an outside environment. Electrical signals can be coupled to and from the sealed device via electrical conductors traversing a hermetically sealed sidewall, for example, without compromising the cavity seal. As described hereinbelow, a bonding structure is formed on a substrate to impede (and/or otherwise restrict) reactant species against migrating into a cavity surrounded by the bonding structure. For example, the bondline structure can be arranged around (e.g., outwards from) the cavity, such that the migration of reactant species is impeded (e.g., prevented) from against entering a headspace of the cavity. The bonding substances can include inert (or relatively inert) metals (e.g., gold and nickel), such that reactive substances (such as indium, selenium and/or other reactant species) need not be intentionally included. Accordingly, outgassing from bonding substances in the sidewall of the bonding structure is minimized, such that contamination of sensitive structures such as micromirrors (as well as the coating of lubricant and/or passivating agents thereof) is reduced. As described hereinbelow, reliability and performance of a sealed device can be improved by processes and structures for sealing devices in cavity formed during wafer-to-wafer bonding. The described processes and sidewall structures expose inert metals to the cavity, and are applied at low temperatures and low bonding pressures. The low temperatures and low bonding pressures used to form the sidewall structures helps protect metallization and/or circuitry formed beneath (or above) the sidewall. In an example, a plating process forms an gold overplated edge. The gold overplated edge can be an overhanging portion of a gold cantilevered structure that is cantilevered subsequent to the plating of the gold layer by partially etching away an underlying resist. The gold overplated edge includes a retrograde profile (e.g., as shown inFIG.4, where a void exists underneath a suspended portion of the overplated gold). Such gold overplated edges are formed on first and second substrates, such that the first and second substrates can be bonded together (e.g., vertically bonded) by compressive forces. The compressive forces form a thermocompressive bond as a first gold overplated edge is compressed against a second gold overplated edge (e.g., which includes a retrograde profile that is inverted and mirrored with respect to the retrograde profile of the first gold overplated edge. The thermocompressive bond can be formed at greatly reduced temperatures and pressure (e.g., as compare against processes involving fusing and/or melting of various eutectic substances). The thermocompressive bond can be formed at room temperature by applying normal (e.g., orthogonal) vertical compressive forces. The compressive forces induce localized vertical shearing of the first (e.g., lower) and second (e.g., upper) gold overplated edges, such that heat is locally generated by the vertical shearing. The vertical shearing welds the first and second gold overplated edges together to form a hermetic seal around a cavity for including a sealed device. The welding can occur at low pressures (e.g., atmospheric pressures) because the overplated structure deforms the gold edge in a localized area (e.g., which reduces net forces and pressure on the substrate and/or intervening structures that would be otherwise applied). In various examples described below (e.g., with respect toFIG.7,FIG.8andFIG.9), the strength of the wafer-to-wafer thermocompressive bonds can be increased by forming multiple concentric rings of shearing-induced sealing welds. FIG.1is a cross-sectional diagram of an example first-substrate assembly for hermetic vertical shear weld wafer bonding. The assembly100includes a first substrate110: the first substrate110can be a semiconductor wafer (or die) formed from a crystalline lattice of silicon or gallium arsenide, for example. As shown inFIG.5, a second substrate110bcan be used to form structures similar to and suitable for bonding to the structures formed on the first substrate110. The second substrate110bcan be of the same material as the first substrate100a, or of a different material (e.g., glass, for transmitting light to the sealed device). The first substrate110(and the second substrate110b) can be formed in accordance with wafer-level processing to achieve an economy of scale in manufacture. (In other examples, die-level bonding processes and structures can replace the wafer-level bonding processes and structures described herein.) The first substrate110can be formed with terminals (e.g., pins, not shown) on a lower or upper surface of the first substrate110to electrically intercouple with other system devices arranged outside of a sealed cavity to be formed on the first substrate110. A seed layer120is deposited on the upper surface of the first substrate110. The seed layer120can be deposited by a chemical vapor deposition process and includes a deposited material suitable for forming a layer of a first metal thereupon. In an example, the first metal layer can be relatively “hard” metal (such as nickel, which is “hard” relative to the hardness of gold). A resist structure130is formed over the seed layer. The resist structure130delimits an edge for limiting a horizontal extent of the first metal to be deposited on the seed layer as described hereinbelow with reference toFIG.2. FIG.2is a cross-sectional diagram of an example first-substrate assembly including a first metal for hermetic vertical shear weld wafer bonding. Assembly200shows a first metal layer240(e.g., of nickel) deposited on the upper surface of the substrate100. The resist130includes a vertical surface adjacent to the first metal layer240, which determines the shape and location of the adjacent vertical surface of the first metal layer240. The intersection of the first metal layer240upper surface and the first metal layer240adjacent vertical surface is a fulcrum against which a hermetic vertical shear weld wafer bond can be formed (e.g., as described hereinbelow with respect toFIG.6). The first metal layer240can be deposited to a depth determined in part by the height of the resist130, such that a flat surface is formed by the upper surfaces of the resist130and the first metal layer240. The upper surfaces of the resist130and the hard metal layer240can optionally be planarized to form the flat surface. The flat surface can be used to deposit a layer of a second metal thereupon as described hereinbelow with reference toFIG.3. FIG.3is a cross-sectional diagram of an example first-substrate assembly including a second metal for hermetic vertical shear weld wafer bonding. Assembly300includes a second metal layer350deposited over the upper surfaces of the resist130and the first metal layer240. In an example, the second metal layer350is a “soft” metal (e.g., gold) relative to the hardness of the metal (e.g., nickel) of the first metal layer240. For example, the first metal layer240retains its shape (e.g., because of the relative hardness to the second metal layer350), including the shape (e.g., edge) of the fulcrum around which the second metal is deformed (e.g., bent and sheared). The second metal layer350is deformed around the fulcrum by compressive forces applied for forming a hermetic vertical shear weld wafer bond (e.g., as described hereinbelow with respect toFIG.6). The second metal layer350can be patterned to cover the first metal layer240, the resist130and the vertical interface between (e.g., adjacent to both) the first metal layer240and the resist130. The second metal layer350includes a chamfered edge (e.g., a radiused edge, as shown in profile inFIG.3), which is formed (e.g., formed at least in part) over the resist130. The chamfered edge includes a sloped profile for “self-centering” a second-substrate assembly during a wafer-to-wafer bonding of the first- and second-substrates as described hereinbelow with respect toFIG.5. The radius of the chamfered edge provides a net horizontal component of force when the second-substrate assembly is misaligned (e.g., slightly misaligned), such that the net horizontal component of force tends to correct (e.g., tends to self-center) for the horizontal misalignment of the first- and second-substrate assemblies by urging the first- and second-substrate assemblies into horizontal alignment. As described herein below with reference toFIG.4, the resist130(e.g., which is below and subjacent to the chamfered edge of the second metal layer350) is evacuated to expose a vertical edge of the fulcrum of the first metal layer240. FIG.4is a cross-sectional diagram of an example first-substrate assembly including an exposed vertical edge of a fulcrum for hermetic vertical shear weld wafer bonding. Assembly400includes an exposed vertical edge452of a fulcrum. The exposed vertical edge of a fulcrum is exposed by evacuating (e.g., etching away) the resist130. Accordingly, the chamfered edge of the second metal layer350overhangs (e.g., is cantilevered) over the substrate110, such that a void exists beneath the cantilevered portion of the second metal layer350. The void beneath the cantilevered portion of the second metal layer350includes a space into which the second metal layer350can be bent and deformed as described hereinbelow. FIG.5is a cross-sectional diagram of example first- and second-substrate assemblies for hermetic vertical shear weld wafer bonding. Assembly500includes assemblies400aand400b. Assembly400ais an assembly such as assembly400, whereas assembly400bis an assembly similar to the assembly400. The assembly400bincludes sidewall structures (such as a first metal layer240band a second metal layer350b) that are positioned (or otherwise offset) on the second substrate to be aligned with respective edges of the first assembly400a. The alignment intersperses prominences of the assemblies400aand400bfor vertical mating, For example, the respective chamfered edges (of the second metal layers350aand350b) are mutually sheared when vertically compressed together (as described hereinbelow with respect toFIG.6andFIG.7). The assembly400aincludes a substrate110a, first metal layer240a, second metal layer350aand vertical edge452aof a lower fulcrum (which respectively correspond to the substrate110, first metal layer240, and second metal layer350and vertical edge452of the first substrate110). Similarly, the assembly400bincludes a substrate110b, first metal layer240b, second metal layer350band vertical edge452aof an upper fulcrum (which respectively correspond to the substrate110, first metal layer240, and second metal layer350and vertical edge452of the first substrate110). The structures of the assembly400bare inverted and mirrored with respect to the corresponding structures of the assembly400a. As described hereinbelow with respect toFIG.6, the vertical edge452aof the upper fulcrum and the vertical edge452bof the lower fulcrum are vertically aligned and offset, such that the chamfered edges of the second metal structures350aand350bare deformed around the edges of the respective fulcrums of the first metal structures240aand240bin response to forces generated while vertically compressing the first assembly400aand the second assembly400btogether. FIG.6is a cross-sectional diagram of example joined first- and second-substrate assemblies for hermetic vertical shear weld wafer bonding. Assembly600includes the assemblies400aand400b(described hereinabove with respect toFIG.4andFIG.5), wherein the assemblies400aand400bare bonded (e.g., fused) together and hermetically sealed by the weld660. The weld660is formed in response to forces generated while compressing the first assembly400aand the second assembly400btogether. For example, the assembly400acan be formed on a first wafer (such as described hereinbelow with respect ofFIG.9) and the assembly400bcan be formed on a second wafer (such as described hereinbelow with respect ofFIG.9), which are compressed together during wafer-level processing (e.g., before singulation for producing individual dies). As the first assembly400aand the second assembly400bare compressed together, the chamfered edges of the second metal layers350aand350bcome into contact. The second metal layers350aand350bcan include an inert, ductile metal such as gold. The area of contact between contacting portions of the second metal layers350aand350bis relatively small, which increases the localized pressures to values substantially higher than pressures mutually exerted between each of the first metal layers240aand240band their respective substrates110aand110b(as well as any intervening components or structures between any adjacent layers and substrates). Accordingly, relatively high forces are applied to the chamfered edges of the second metal layers350aand350b, which are sufficiently high to deform (and optionally melt portions of) the chamfered edges without damaging the first metal layers, the respective substrates and/or any intervening components. As the chamfered edges of the second metal layers350aand350bcome into contact, torque is applied to each cantilevered portion of the second metal layers350aand350b. The torque is applied with respect to (e.g., around) a fulcrum formed by the arrangement (e.g., intersection) of the exposed vertical and adjacent (e.g., contacting a respective second metal layer350aor350b) horizontal faces of a respective first metal layers240aor240b. Accordingly, each fulcrum (which is formed by a first metal layer240aor240b) contacts a respective cantilevered portion of a second metal layer350aor350b. As the first assembly400aand the second assembly400bcontinue to be further compressed together, each cantilevered portion of the second metal layers350aand350bis deformed: the cantilevered portion of the second metal layer350ais bent in a generally downwards direction, whereas the cantilevered portion of the second metal layer350bis bent in a generally upwards direction. The bending (e.g., which includes compressive, tensile and shear forces) of each such cantilevered portion—and friction (e.g., the friction opposing the slippage across the contacting surfaces of the second metal layers350aand350b)—generates localized heat sufficient to melt the interface between second metal layers350aand350b, such that a weld660(e.g., a hermetic vertical shear weld wafer bond) can be formed by fusing contacting portions of the second metal layers350aand350b. After such welding, the hermetic vertical shear weld wafer bond formed by the weld660generates forces for bonding (e.g., fixedly bonding) the first assembly400aand the second assembly400btogether as well as impedes the migration of contaminants such as reactant species across the weld660into a cavity, described hereinbelow with respect toFIG.7. FIG.7is a cross-sectional elevational view of an example two-substrate assembly that includes example hermetic vertical shear weld wafer bonds. For example, the two-substrate assembly700(shown in cross-section) includes a first (e.g., lower) substrate400aand a second (e.g., upper) substrate400b. The first substrate400aincludes multiple instances of the first metal layers740a(shown in cross-section), which are arranged (e.g., as rings820,840and860, as shown inFIG.8andFIG.9) around a perimeter of the cavity770(e.g., which is to be hermetically sealed). The second substrate assembly400bincludes multiple instances of the first metal layers740b(shown in cross-section), which are arranged around a perimeter of the cavity770and are positioned (e.g., interdigitated) between instances of the first metal layers740a, such that multiple instances of a shear weld is formed (e.g., by compressing the substrate assemblies400aand400btogether). A shear weld is formed in the void between each first (e.g., lower) substrate400afirst (e.g., hard) metal layer740aand a second (e.g., upper) substrate400bfirst (e.g., hard) metal layer740a. For example, assemblies600as shown inFIG.7include a shear weld as described hereinabove with respect toFIG.6. The shear welds join adjacent segments of the second (e.g., soft) metal layers740aand740b(e.g., formed as separate segments on each of the first substrate400aand the second substrate400b) into a unified (e.g., continuous) seal750. The seal750extends outwards from the cavity770(e.g., to a saw lane, not shown) and extends around the perimeter the cavity (e.g., as shown in top view inFIG.8andFIG.9), such that the cavity770is a hermetically sealed environment in which the sealed device780is protected from reactant species. The multiple instances of the shear weld, which ring the cavity770on all four sides, helps to increase the impermeability of the seal formed by the seal750. Further, the seal750is an inert material, such that the sealed device780is not exposed to reactive species from bonding agents otherwise present in a sidewall structure. Accordingly, the first and second metal layers form sidewalls for bonding the first substrate400aand the second substrate400band for sealing the cavity770. The sidewalls are positioned to protect sensitive components180of a chip (e.g., singulated die) within cavity peripherally supported by the sidewalls. The included device780can include an array of micromirrors (not shown) coupled to the first substrate400a, where the performance of each micromirror could otherwise be degraded by the presence of reactive species or moisture from bonding agents or operational environments. Accordingly, the first substrate400a, the second substrate400band the seal700help prevent the intrusion of contaminants such as reactant species, gasses and/or moisture into the cavity770. FIG.8is a top-view diagram of an example first-substrate assembly for hermetic vertical shear weld wafer bonding. The assembly800includes a first substrate810that includes an outer ring820, and intermediate ring840and an inner ring860arranged for bonding to similar structures on a second substrate (not shown). For example, the outer ring820, and intermediate ring840and an inner ring860are metal layers, such as the first (e.g., hard) metal layers (e.g.,740aand340adescribed hereinabove). As described hereinabove (e.g., with reference toFIG.7), each of the rings extend upwards from the substrate810, such that an outer valley830is formed between the outer ring820and the intermediate ring840, and such that an inner valley850is formed between the intermediate ring840and the inner ring860. The rings of the second substrate (not shown) are arranged to mate with the rings820,840and860, such that the shear welds (e.g., shear welds660) are formed in the voids adjacent (e.g., closely adjacent) to the outer ring820, the intermediate ring840and the inner ring860. Accordingly, each of the outer valley830and the inner valley850are arranged for including two shear welds and a second (e.g., soft) metal layer initially formed over corresponding first (e.g., hard) metal layers of the second substrate. (FIG.7shows an example configuration of hermetic vertical shear weld wafer bonding of a first substrate and the second substrate in cross-section.) In response to the formation of the vertical shear welds, the cavity770is hermetically sealed, which protects the sealed device780against migration of reactant species, environmental gasses and moisture. The multiple rings enhance the degree of impermeability of the seal and increase the strength of the bonding forces between the upper and lower substrates. FIG.9is a top-view diagram of an example first-substrate wafer for hermetic vertical shear weld wafer bonding. The wafer900includes a substrate910(which is a substrate such as the substrate810, described hereinabove). Multiple instances of the assembly800are formed on the substrate910. A corresponding wafer (e.g., arranged-to-fit wafer, not shown) includes similar structures positioned to mate within the valleys formed by the rings of each of the instances of the assembly800. Accordingly, the wafer900(and the structures formed thereon) is arranged to mate with a corresponding wafer (not shown) in response to compressive forces applied to join and bond the wafer900and the corresponding wafer together. FIG.10is a cross-sectional diagram of dimensioning of components of example first- and second-substrate assemblies for hermetic vertical shear weld wafer bonding. For example, relative sizing and spacing of components in diagram1000can be described by the variables A, B and C: A is the depth of the first (e.g., nickel) metal layer240a(and240b); B is the depth of the second (e.g., gold) metal layer350a(and350b); and C is the width between the vertical projections of the exposed vertical edge452a(of fulcrum1042a) and the exposed vertical edge452b(of fulcrum1042b). An example minimum spacing C for forming a complete vertical shear weld is: Cmin≥πB22(A+B)(Eq.1) An example maximum spacing C for forming a complete vertical shear weld is: Cmax≤2B(Eq. 2) An example optimum spacing C for forming a complete vertical shear weld is: Coptimum=√{square root over (2B)} (Eq. 3) In an example where A is 5 microns, and B is 5 microns: Cmax≤10 microns; Cmin≥3.9 microns; and Coptimum=7.1 microns. Accordingly, hermetic vertical shear weld wafer bonding can be formed in accordance with wafer-level processing to achieve an economy of scale. The first metal layer240acan be formed over a conductor and/or CMOS circuitry1010, such that net forces for forming the hermetic vertical shear weld wafer bonding are not directly applied (and instead are distributed over greater areas), and such that the pressure applied to the underlying conductor and/or CMOS circuitry1010is substantially reduced (e.g., reduced sufficiently such that sufficient bonding pressure for generating vertical shear welds can be applied without damaging the underlying conductor and/or CMOS circuitry1010). FIG.11is another cross-sectional diagram of example first- and second-substrate assemblies for hermetic vertical shear weld wafer bonding. The diagram1100includes a lower element1160having an exposed vertical edge1162and a cantilever1166. The diagram1100includes an upper element1164. A method of forming an apparatus has been introduced. The method includes depositing a resist on a first substrate peripherally around a cavity including a first surface defiled by the first substrate. A first metal layer is deposited over the first substrate, wherein the first metal layer is deposited against a first vertical edge of the resist. A second metal layer is deposited over the first metal layer and the resist. The resist is removed to form a second metal layer cantilever and a void that extends between the second metal layer cantilever and the first substrate. A second substrate is bonded to the first substrate in response to a contacting structure of the second substrate deforming the second metal layer cantilever, wherein the contacting structure of the second substrate is forced against the second metal layer cantilever in response to compressing the first and second substrates together. Modifications are possible in the described examples, and other examples are possible, within the scope of the claims. | 29,557 |
11858807 | DETAILED DESCRIPTION Overview The technology relates to a rectifier for radiofrequency (RF) energy. The rectifier may include a microelectromechanical system (MEMS) resonator configured to vibrate in response to RF modulation frequencies. Using piezoelectric materials, the non-linearity of electrostatic force may be used to rectify captured RF signals. This mechanical capture of energy may be more sensitive than using diodes or other solid-state technologies. As a result, using piezoelectric RF energy harvesting in addition to or instead of using solid-state technologies, lower levels of RF energy in the environment may be captured and stored than using solid-state electronics alone. The rectifier may include a mainboard including one or more RF inputs and a first electrical contact. The one or more RF inputs may be configured to receive an RF signal, such as from an antenna. The RF signal may be in a particular frequency band. For example, the RF signal may include 750, 850, or 1900 MHz cellular bands, 900 MHz, 2.4 or 5 GHz ISM bands, and/or 3.5 or 6 GHz AFC bands. The rectifier may also include a sub-board positioned parallel to the mainboard with a small gap in between. The sub-board may be secured in position using a first anchor at a first end and a second anchor at a second end. The sub-board may include a thin film piezoelectric layer, a second electrical contact, and a ground plane. The thin film piezoelectric layer may include crystalline aluminum nitride (AlN) and/or other materials that have piezoelectric properties. Dimensions of the sub-board may be configured based on the particular frequency band to be captured. In some examples, the sub-board may include a different material than AlN that has piezoelectric properties. The second electrical contact may be positioned opposite the first electrical contact. The small gap between the mainboard and the sub-board may be a vacuum or filled with a finite amount of air. As the RF signal is received by the one or more RF inputs, the sub-board is configured to vibrate at a resonant frequency. In particular, the dimensions, materials, and other features of the sub-board may be configured to allow the sub-board to vibrate at a resonant frequency in the particular frequency band. The vibration of the sub-board can increase in amplitude over time as the RF signal is received. Energy may be generated due to the vibration and the piezoelectric properties of AlN. The generated energy may be stored and accumulated in a mechanical domain, in the form of vibration of the board (e.g., in an amplitude of the vibration). Alternatively, the generated energy may be stored and accumulated in an energy storage device, such as one or more capacitors. Energy may be accumulated until an amplitude for the vibration allows the second electrical contact to contact the first electrical contact. Upon contact between the first and second electrical contacts, electric charge may flow from the second electrical contact to the first electrical contact, generating a current. The first electrical contact may be connected to an electronic device. The generated current may therefore flow from the first electrical contact to the electronic device to power the electronic device. In some cases, the connection between the electrical contact and the electronic device may include an energy storage device, such as one or more capacitors, to accumulate charge before powering the electronic device. Also in some cases, the connection may include a transformer or a filter configured to prepare the current to meet the requirements for powering the electronic device. In some examples, the rectifier may be integrated with the transformer or filter in a single component. The MEMS rectifier described herein is able to capture very low levels of RF energy in an environment. The increased sensitivity provided by the MEMS resonator may allow for capturing more energy at a more efficient rate. When used in connection with a tracking system, this MEMS rectifier allows for more consistent powering of tracking system components in areas that have lower levels of energy in an environment. In addition, as the energy harvesting function may be relegated at least partially to the MEMS rectifier, the form of the components of the tracking system becomes more flexible. The MEMS rectifier may provide access to minute amounts of energy available, which can also be used in parallel with semiconducting rectifiers that only work at higher incident power levels to form an overall system that captures a wider amount of energy at a range of efficiencies. Example Systems FIGS.1A and1Bare functional and pictorial diagrams of a MEMS rectifier100. The rectifier100includes a mainboard102including one or more RF inputs104and a first electrical contact106. The one or more RF inputs104may be configured to receive an RF signal, such as from an antenna. The one or more RF inputs104may be configured to receive the RF signal having a particular frequency band. For example, the particular frequency band may include 750, 800-1000, or 1900, MHz cellular bands, 2.4 or 5 GHz ISM bands, and/or 3.5 or 6 GHz AFC bands. When the RF signal has a frequency in the particular frequency band, the rectifier100may vibrate to generate an electrical current as described herein. The first electrical contact106may be connected to an electronic device150and may be configured to output an electrical current from the rectifier100to the electronic device150. The rectifier100also includes a sub-board112positioned parallel to the mainboard102with a small gap in between. The sub-board112is secured in position using a first anchor10aat a first end and a second anchor10bat a second end. The sub-board112includes thin film crystalline aluminum nitride (AlN)114, which has piezoelectric properties, a second electrical contact116, and a ground plane118. Dimensions of the sub-board112may be configured based on the particular frequency band to be captured. In some examples, the sub-board may include a different material than AlN that has piezoelectric properties. The second electrical contact116is positioned opposite the first electrical contact106. The first electrical contact106and the second electrical contact116may be a raised portion on the mainboard102and sub-board112, respectively. The raised portion may be a sharp contact point. The raised portion may be formed using a combination of self-terminating etch into a small opening in a mask layer, followed by the top layer being deposited. Other known methods of forming a raised electrical contact on a board may be used in addition or in the alternative to this combination. The gap between the second electrical contact116and the first electrical contact106may be minimized such that a lower threshold of RF energy is needed for actuation that results in contact between the electrical contacts. For example, the gap between the contacts or between the sub-board and the mainboard may be 5 nm, 100 nm, or any measurement in between. The size of the gap may be formed or adjusted using thin film technologies such as LPCVD films, or ALD films. The small gap between the mainboard and the sub-board may be a vacuum or air-filled. When the small gap is a vacuum, the rectifier100may be able to achieve a higher quality factor resonance, which increases the efficiency of rectification. The combination of the mainboard102and the sub-board112comprises a resonator portion of the rectifier100. For example, the sub-board112is configured to vibrate at a resonant frequency in response to the RF signal received by the one or more RF inputs. In particular, the sub-board112may have the dimensions, materials, and other features that allow the sub-board112to vibrate at a resonant frequency in the particular frequency band. The vibration of the sub-board112can increase in amplitude over time as the RF signal is received. Due to the piezoelectric properties of the material in the sub-board112, energy may be generated from the vibration of the sub-board112. The generated energy may be stored and accumulated in the mechanical domain, such as in an amplitude of the vibration. Alternatively, the rectifier100may include an energy storage device (seeFIG.1C), such as one or more capacitors, that is configured to receive and store the generated energy from the vibration of the sub-board112. In some implementations, the rectifier100described above may be included in a monolithic chip. In other implementations, a multi-chip module may be created using a plurality of rectifiers. The sub-board112may be configured to accumulate energy in the mechanical domain, increasing in amplitude up to a point in which the second electrical contact116comes into contact with the first electrical contact106. Upon contact between the first and second electrical contacts, electric charge may flow from the second electrical contact116to the first electrical contact106, generating a current. The generated current may therefore flow from the first electrical contact106to an electronic device150connected to the first electrical contact and power the electronic device. In some cases, the connection between the first electrical contact and the electronic device may include an energy storage device (seeFIG.1D), such as one or more capacitors, to accumulate charge before powering the electronic device. Also in some cases, the connection may include a transformer or a filter configured to prepare the current to meet the requirements for powering the electronic device. In some examples, the rectifier may be integrated with the transformer or filter in a single component. The lateral size of the rectifier100may be in the range of 5 μm-50 μm, inclusive, but may vary from this range as needed for different frequencies and situations. The rectifiers having larger widths will have lower spring constants than smaller widths owing to the lower flexural stiffness (or lower rigidity). The wider rectifiers may enable higher motion generated by the piezoelectric forces, but may be more susceptible to vibration-induced contact events between the electrical contacts due to the lower rigidity. Hence, the dimensions of the rectifier may be selected to provide a target flexural stiffness or rigidity that provides a maximum energy output, while also preventing environmental trigger events. In some examples, the electronic device150connected to the rectifier100may be one or more components in a tracking system, such as tracking system200shown inFIG.2. The tracking system may include electronic components such as a plurality of tracking devices, such as identifier tags or sensors, and a reader. As shown inFIGS.2A and2B, the tracking system200may include a plurality of identifier tags204(such as identifier chips), and a reader206. Each identifier tag may be attached to an item to be tracked, like a package. The rectifier100may therefore capture RF energy210in the environments where the tracking system200is implemented and power one or more of the electronic components of the system. After capturing energy210from the environment, a given rectifier100may transmit an electrical current to one or more identifier tags204. As shown inFIG.2, an electrical current is transmitted from the MEMS rectifier100ato identifier tag204a, from the MEMS rectifier100bto identifier tag204b, from MEMS rectifier100cto identifier204c, from MEMS rectifier100dto identifier204d, and from MEMS rectifier100eto identifier204e. When powered, the plurality of passive tags204may emit a signal to indicate a respective location. The reader206may be a computing device configured to detect the signal emitted by the plurality of identifier tags204, then store and/or transmit data related to the locations of the detected tags. In some implementations, the reader206may be connected to a MEMS rectifier to receive power. The reader206may include one or more processors214, memory216and other components typically present in general purpose computing devices. The one or more processors214may be any conventional processors, such as commercially available CPUs. Alternatively, the one or more processors may be a dedicated device such as an ASIC or other hardware-based processor, such as a field programmable gate array (FPGA). AlthoughFIG.2functionally illustrates the processor(s), memory, and other elements of the reader206as being within the same block, it will be understood by those of ordinary skill in the art that the processor, computing device, or memory may actually include multiple processors, computing devices, or memories that may or may not be stored within the same physical housing. For example, memory may be a hard drive or other storage media located in a housing different from that of the reader206. Accordingly, references to a processor or computing device will be understood to include references to a collection of processors or computing devices or memories that may or may not operate in parallel. The memory216stores information accessible by the one or more processors214, including data217and instructions218that may be executed or otherwise used by the processor(s)214. The memory216may be of any type capable of storing information accessible by the processor(s), including a computing device-readable medium, or other medium that stores data that may be read with the aid of an electronic device, such as a hard-drive, memory card, ROM, RAM, DVD or other optical disks, as well as other write-capable and read-only memories. Systems and methods may include different combinations of the foregoing, whereby different portions of the instructions and data are stored on different types of media. The data217may be retrieved, stored or modified by processor(s)214in accordance with the instructions218. For instance, although the claimed subject matter is not limited by any particular data structure, the data may be stored in computing device registers, in a relational database as a table having a plurality of different fields and records, XML documents or flat files. The data may also be formatted in any computing device-readable format. The instructions218may be any set of instructions to be executed directly (such as machine code) or indirectly (such as scripts) by the processor. For example, the instructions may be stored as computing device code on the computing device-readable medium. In that regard, the terms “instructions” and “programs” may be used interchangeably herein. The instructions may be stored in object code format for direct processing by the processor, or in any other computing device language including scripts or collections of independent source code modules that are interpreted on demand or compiled in advance. Functions, methods and routines of the instructions are explained in more detail below. FIGS.3and4are pictorial and functional diagrams, respectively, of an example system300that includes a plurality of computing devices310,320,330,340and a storage system350connected via a network360. System300also includes passive tags204a,204band reader206. Although only a few tags and computing devices are depicted for simplicity, a typical system may include significantly more. Using the client computing devices, users, such as user322,332,342, may view the location data on a display, such as displays324,334,344of computing devices320,330,340. As shown inFIG.4, each client computing device320,330,340may be a personal computing device intended for use by a user322,332,342, and have all of the components normally used in connection with a personal computing device including a one or more processors (e.g., a central processing unit (CPU)), memory (e.g., RAM and internal hard drives) storing data and instructions, a display such as displays324,334,344(e.g., a monitor having a screen, a touch-screen, a projector, a television, or other device that is operable to display information), and user input devices326,336,346(e.g., a mouse, keyboard, touch screen or microphone). The client computing devices may also include speakers, a network interface device, and all of the components used for connecting these elements to one another. Although the client computing devices320,330, and340may each comprise a full-sized personal computing device, they may alternatively comprise mobile computing devices capable of wirelessly exchanging data with a server over a network such as the Internet. By way of example only, client computing device320may be a mobile phone or a device such as a wireless-enabled PDA, a tablet PC, a wearable computing device or system, or a netbook that is capable of obtaining information via the Internet or other networks. In another example, client computing device330may be a wearable computing system, shown as a wristwatch inFIG.3. As an example, the user may input information using a small keyboard, a keypad, microphone, using visual signals with a camera, or a touch screen. Example Methods In addition to the operations described above and illustrated in the figures, various operations will now be described. It should be understood that the following operations do not have to be performed in the precise order described below. FIG.5is an example flow diagram500including a method of operation for a MEMS rectifier in accordance with some of the aspects described above. WhileFIG.5shows blocks in a particular order, the order may be varied and that multiple operations may be performed simultaneously. Also, operations may be added or omitted. At block502, a RF signal is received by one or more RF inputs104of the MEMS rectifier100. At block504, as the RF signal is received by the one or more RF inputs, a sub-board112of the MEMS rectifier100vibrates. In some cases, the RF signal is in a particular frequency band that causes the sub-board112to vibrate at a particular resonant frequency. The vibration of the sub-board112may increase in amplitude over time as the RF signal is received. At block506, energy is generated due to the vibration and the piezoelectric properties of the sub-board112. At block508, the generated energy is stored. The energy may be stored in a mechanical domain, such as in an amplitude of the vibration, or in an energy storage device, such as one or more capacitors. At block510, an electrical contact on the sub-board112comes into contact with an electrical contact on a mainboard102due to the vibration of the sub-board112. The mainboard102is positioned substantially parallel to the sub-board112with a gap between the mainboard102and the sub-board112. The contact between the two electrical contacts may occur when an amplitude of the vibrating sub-board112is able to span the gap between the mainboard102and the sub-board112. At block512, once the contact between the electrical contacts occurs, electric charge may flow from the sub-board to the mainboard, generating a current. At block514, the generated current may flow from the mainboard102to an electronic device150to power the electronic device150. As the generated current flows from the mainboard102to the electronic device150, the current may flow through one or more electronic components to prepare the current to meet the requirements for powering the device. For example, the one or more electronic components may include an energy storage device, such as one or more capacitors, to accumulate charge before powering the electronic device, or a transformer or a filter to modify the current. In some examples, the rectifier may be integrated with the transformer or filter in a single component. Once powered, the electronic device150may perform a function; for example, an identifier tag, when powered, may emit a signal. FIG.6is an example flow diagram600including a method for manufacturing a MEMS rectifier in accordance with some of the aspects described above. The method may be performed by one or more computing devices controlling machinery that is customized for the steps of the method. WhileFIG.6shows blocks in a particular order, the order may be varied and that multiple operations may be performed simultaneously. Also, operations may be added or omitted. At block602, a first electrical contact106and one or more RF inputs104may be mounted onto a mainboard102. At block604, a second electrical contact116may be mounted to a sub-board112. The sub-board112may include a ground plane118. At block606, the sub-board112may be attached to the mainboard102with a gap between the sub-board112and the mainboard102, thereby forming a resonating unit. The position of the attached sub-board may include the second electrical contact116being directly across the gap from the first electrical contact106, such that at least a portion of the second contact is located at the point on the sub-board that is the shortest distance from the first contact106. When attached, the sub-board112may be substantially parallel to the mainboard102. The sub-board112may be attached using one or more anchors110. In some implementations, at least a portion of the mainboard102or the sub-board112is fabricated using the integrated circuit manufacturing portion. Alternatively, the MEMS rectifier described herein, such as MEMS rectifier100, may be manufactured as an integrated circuit or monolithic chip using steps included in the integrated circuit manufacturing process. The monolithic chip may include an integration of the piezoelectric components, electrostatic components, and solid state components. For example, piezoelectric materials, such as AlN, electrostatic circuitry, such as traces or other parts of the MEMS, and CMOS circuitry or electronics, such as semiconductors, may be integrated in a chip to form the rectifier100. The MEMS rectifier described herein is able to capture very low levels of RF energy in an environment. The increased sensitivity provided by the MEMS resonator may allow for capturing more energy at a more efficient rate. When used in connection with a tracking system, this MEMS rectifier allows for more consistent powering of tracking system components in areas that have lower levels of energy in an environment. In addition, as the energy harvesting function may be relegated at least partially to the MEMS rectifier, the form of the components of the tracking system becomes more flexible. Unless otherwise stated, the foregoing alternative examples are not mutually exclusive, but may be implemented in various combinations to achieve unique advantages. As these and other variations and combinations of the features discussed above can be utilized without departing from the subject matter defined by the claims, the foregoing description of the embodiments should be taken by way of illustration rather than by way of limitation of the subject matter defined by the claims. In addition, the provision of the examples described herein, as well as clauses phrased as “such as,” “including” and the like, should not be interpreted as limiting the subject matter of the claims to the specific examples; rather, the examples are intended to illustrate only one of many possible embodiments. Further, the same reference numbers in different drawings can identify the same or similar elements. | 23,273 |
11858808 | DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS The making and using of the presently preferred embodiments are discussed in detail below. It should be appreciated, however, that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed are merely illustrative of specific ways to make and use the invention, and do not limit the scope of the invention. Although presently available digital microphones provide the ability to switch between the higher quality mode and the lower quality mode, subsequent digital microphone generations may require flexibility in switching between the higher quality mode and the lower quality mode, for example through the use of dynamic SNR adjustment or dynamic power saving strategies. Subsequent digital microphone generations may also require that the dynamic adjustment be performed rapidly and seamlessly by minimizing audible switching artefacts. Audible switching artefacts at the output of the digital microphone can be referred to and are designated herein as “cross-talk”, “X-talk”, or “XT”. Embodiments described herein reconstruct and subtract X-talk disturbing noise in a digital microphone for various power profile changes due to operational mode changes. In this manner, audible artefacts in the output of the digital microphone produced by the operational mode changes are significantly reduced below an audible threshold. As described herein, the term “power profile” refers to the power dissipation of a digital microphone over time, especially during a time period in which there is a transition between two or more operational modes of operation of the digital microphone. In some embodiments, the performance of the digital microphone is changed based on a control signal at the left-right (L/R) pin of the digital microphone the power profile. This occurs typically between a lower power/lower performance mode of operation and a higher power/higher performance mode of operation. Various methods are known for changing the mode of operation of a digital microphone. For example, a change can be made to the bias current or clock frequency of the digital microphone, or a change can be made to the value of a sampling capacitor inside of an ADC of the digital microphone. In turn, the change of mode of operation of the digital microphone leads to a change in power, which in some cases causes an audible acoustic artefact. For example, if there is a change of clock frequency from FSto FS/2 there is a typically change in power consumption of ˜300 μW in the digital microphone. In a reconstruction path, according to embodiments, the power profile associated with this change in power consumption is applied as an input to a first reconstruction filter that models the dynamic of the temperature time constant of the MEMS device and a second reconstruction filter models the acoustic high pass frequency response of the MEMS device. In an embodiment, the first reconstruction filter comprises a second order digital filter, and the second reconstruction filter comprises a first order digital filter. The reconstructed thermo-acoustic X-talk is then subtracted from the main signal path in the digital microphone so that audible artefacts in the output of the digital microphone are significantly reduced. In some embodiments, a reduction below an audible threshold is achieved. In other embodiments, only a portion of the reconstructed thermo-acoustic X-talk is subtracted from the main signal path if only a partial compensation mode of operation is desired. InFIG.1a block diagram of a digital microphone100including a dynamic change of the internal clock is depicted. Digital microphone100includes a MEMS device102for converting the environmental sound and pressure waves into an analog signal. The analog signal is received by an Application-Specific Integrated Circuit (ASIC)104. ASIC104comprises an ADC106for converting the analog signal from the MEMS device102into a digital signal for further digital signal processing. In the digital microphone100ofFIG.1a repeater108is coupled to the output of ADC106, a digital filter no is coupled to the output of repeater108, and a digital modulator112is coupled to the output of digital filter110for providing a one-bit digital output signal at output bus114. Digital microphone100receives a clock (clk) signal at node124, which is received by multiplexer118directly at an input, and indirectly at another input through clock divider120. The output of multiplexer118provides the clock signal and a divided version of the clock signal at output116, which is received in turn by ADC106. The multiplexer118, the clock divider120, and the repeater108are all under control of a control signal (ctrl)122. To achieve flexibility in terms of performance (SNR) and/or power consumption, different clock rates generated by the clock divider120from the constant incoming clock rate (clk) can be used. The different clock rates can range from a reduced internal clock rate (clkred=clk/D) to the high clock rate due to the action of the repeater108interpolating at a factor D under control of the ctrl control signal122. Further details of the digital microphone100shown inFIG.1are disclosed in co-pending U.S. patent application Ser. Nos. 16/773,079 and 16/871,546, both of which are entitled “Configurable Microphone using Interval Clock Changing”, and both of which are hereby incorporated by reference in their entireties. Another strategy to achieve the flexibility in terms of performance (SNR) and/or power consumption in one or more operational modes is by changing the sampling capacitor of the ADC in the digital microphone. InFIG.2a timing diagram200of the power profile over time of the internal clock change of the digital microphone100ofFIG.1is depicted. Timing diagram200includes the timing waveform206of a select pin of the digital microphone over time. InFIG.2, digital microphone100transitions from a higher performance operational mode having the full rate clock frequency FS, to a lower performance operational mode having a half-rate clock frequency FS/2, back to the higher performance operational mode having the full rate clock frequency FS. As is shown in the clock timing bar204, the transition of the falling edge of the select pin waveform206are simultaneous with the transition from the FSclock rate to the FS/2 clock rate. However, the transition of the subsequent rising edge of the select pin waveform206with the transition from the FS/2 clock rate to the FSclock rate is not simultaneous. There is a lag in the transition to the FSclock rate due to the ramped change of the internal bias current of digital microphone100as is explained in further detail below. Timing diagram200also shows the power consumption over time. The power profile202is at a maximum between time instances t0and t1, and ramps down to a lower power consumption between time instances t1and t2, and stays at the lower power consumption between time instances t2and t3. The difference between the maximum power consumption and the lower power consumption is shown as “delta μW”208inFIG.2and is about 300 μW in embodiments. The power profile ramps up to the full power consumption between time instances t3and t4, and returns to the full power consumption between time instances t4and t5. As noted in the timing diagram ofFIG.2, the dynamic power change at time instance t1is negative as the clock frequency changes from FSto FS/2, whereas the dynamic power change at time instance t4is positive as the clock frequency changes from FS/2 back to FS. Thus, as the internal clock is changed, a change of the dynamic current (power) occurs immediately, which should be compensated to avoid audible artefacts due to thermo-acoustic cross-talk. To reduce spikes in the dissipated power, in the case of a change of the internal clock frequency from FSto FS/2, the bias current is reduced slowly (ramped) to avoid such audible artefacts. The same ramped strategy can be applied in the case of a change from FS/2 to FSas noted above. In the case of changing the sampling capacitor to achieve the different operational modes in a digital microphone, the same ramped power profile can be followed. While using slow ramps may decrease or even audible artefacts, the corresponding transitions between the desired operational modes of the digital microphone will be slow. For effective reduction of the audible artefacts, the ramping of the internal power consumption can take place over hundreds of milliseconds in some cases. However, in many applications it is desirable that the transitions between operational modes of the digital microphone be effectuated as rapidly as possible, but still without generating audible artefacts. Embodiments of a digital noise compensation system and method are shown and described in further detail below in order to significantly reduce audible artefacts in a digital microphone, while allowing for the rapid transition between operational modes of the digital microphone. FIG.3is a block diagram of a digital microphone300with X-talk compensation inside of the digital microphone package, according to an embodiment. Digital microphone300includes a MEMS device302coupled to an ASIC304. In an embodiment, ASIC304includes an analog front-end circuit306such as a source-follower circuit coupled to an ADC308. In an embodiment, ADC308comprises a voltage-controlled oscillator ADC (VCO ADC) coupled to a digital low pass filter310. MEMS device302and ASIC304, along with modulator314described in further detail below, comprise the core components or circuits of the main signal path of digital microphone300. In embodiments, a source-follower circuit can be used independently if a switch-capacitor sigma-delta ADC or a VCO ADC is used. In the digital microphone300ofFIG.3an external command over the L/R pin or input at node318is used to initialize a dynamic profile change. Based on this command internal information is derived by a “generation of control signal” component32oto adapt the configuration of the digital microphone300(to effectuate either an internal clock change or a change of a sampling capacitor), which in turn leads to a change in the power profile “P” and therefore causes X-talk. A first internal control signal322A is therefore used to control the internal clock change or sampling capacitor change, and is received by ASIC304as shown. To compensate the X-talk, it is estimated digitally by a X-talk compensation component325, which can also be referred to as a “reconstruction path” according to embodiments. The X-talk compensation component receives a copy322B of the first internal control signal in an embodiment. X-talk compensation component325includes power profile reconstruction component324(for reconstructing the power profile “P”, and to generate a reconstructed power profile “P*”) and reconstruction filter326(which reconstructs thermal and acoustic properties of the X-talk originating in digital microphone300). For modelling the thermal/acoustic properties, all of the thermal/acoustic properties of the entire digital microphone assembly are ideally considered. For example, the volume of ASIC304, the thermal contacts of ASIC304to the surroundings, the package size(s) of digital microphone300, the thermal sensitivity of MEMS device302, the amount of encapsulation (e.g. “glob-top”) used to encapsulate ASIC302, as well as many other thermal and acoustic properties can be considered to achieve an accurate X-talk estimate. The output signal of X-talk compensation component325is subtracted from the main digital signal path of digital microphone300. Thus the output digital filter310in ASIC304is received by a first input of subtractor312, and the output of X-talk compensation component325is received by a second input of subtractor312. The output of subtractor312is received by modulator314to generate a one-bit pulse modulation density (PDM) signal at digital output bus316, according to embodiments. The power reconstruction profile324comprises digital or analog components for reconstructing the power profile of the digital microphone through the use of direct power or current measurements, as is explained in further detail below, especially with respect toFIG.5andFIG.6. The reconstruction filter326is described in further detail below, especially with respect toFIG.7. Additional details regarding reconstruction filter326can be found in U.S. Pat. No. 10,491,996 entitled “Micro-Electro-Mechanical System (MEMS) Circuit and Method for Reconstructing an Interference Variable” that is hereby incorporated by reference in its entirety. Additional details regarding reconstruction filter326can also be found in U.S. Pat. No. 10,244,315 entitled “Circuit Arrangement with an Optimized Frequency Response and Method for Calibrating a Circuit Arrangement” that is hereby incorporated by reference in its entirety. InFIG.3, the X-talk compensation component325can be integrated together with ASIC304in a single integrated circuit, in an embodiment. In other embodiments, the X-talk compensation component325can be integrated on a first integrated circuit, and ASIC304can be integrated on a second integrated circuit. Both the first integrated circuit and the second integrated circuit can be packaged together in a single semiconductor package, according to embodiments. Other packaging implementations can be used in embodiments. The various components shown inFIG.3can be implemented as hardware components such as discrete or integrated circuits, or can be software components comprising instructions stored in memory and implemented by a microprocessor (not shown inFIG.3but is best seen inFIG.11, described in further detail below). Any appropriate mixture of hardware and software components can be used, according to embodiments. Hardware components can comprise integrated circuits or discrete circuit components in various embodiments. The reconstruction of the X-talk can be implemented also outside of the package of the digital microphone, as depicted inFIG.4, according to embodiments.FIG.4shows a digital microphone400, wherein the MEMS device302, ASIC304including the front-end circuit306, ADC308, digital filter310, modulator314, and control signal component320are implemented in a first semiconductor package402. The X-talk compensation component325including power profile reconstruction component324and reconstruction filter326, along with subtractor312are implemented in a second semiconductor package404. In embodiments, the first semiconductor package402and the second semiconductor package404can be implemented on a single substrate such as a printed circuit board (PCB). The control signal at node318is received by the first semiconductor package402and the second semiconductor package404in the implementation ofFIG.4. The PDM signal generated by modulator314in the first semiconductor package402is received by an input of subtractor312in the second semiconductor package404. All other signals and components are substantially as described in digital microphone300described inFIG.3. In embodiments the assembled first semiconductor package402can be provided by a digital microphone manufacturer, and the assembled second semiconductor package404can be provided by a digital microphone customer. The reconstruction of the power profile, if a dynamic change of the profile (SNR versus power) is applied, can also be based on measurements (e.g. measurement of bias current that defines the power consumption of the digital microphone) as is shown in digital microphone500ofFIG.5. Digital microphone500includes the MEMS device302, ASIC304including front-end circuit306, ADC308, digital filter310, subtractor312, modulator314, control signal generation component320, X-talk compensation component325including power profile reconstruction component324and reconstruction filter326all previously described and shown in digital microphone300ofFIG.3. However, in addition, digital microphone500includes a power change measurement component502having an input coupled to a power terminal of ASIC304and an output coupled to the input of X-talk compensation component325. In an embodiment, power change measurement component502need not necessarily receive a control signal and can continuously provide the power change measurement. FIG.6is a schematic diagram of a power measuring circuit600for measuring the power dissipation change or bias current change in the digital microphone500ofFIG.5, according to an embodiment. According to an embodiment, power dissipation over time can be measured by using a low-dropout voltage regulator (LDO) in series with the power terminal of the digital microphone, and measuring the current of the LDO with a replica circuit. In embodiments, the design of power measuring circuit can be made relatively simply in order to save integrated circuit size and cost. Power measuring circuit600thus comprises an LDO voltage regulator602coupled to a current sensor604, in an embodiment. LDO602is coupled to the power terminal of ASIC functional building blocks606at node610, which can represent the functional blocks of ASIC304previously shown and described, or include additional or fewer functional blocks. LDO602comprises a reference voltage input coupled to a VREFreference voltage source, and a current input coupled to a power supply node of ASIC functional building blocks606at node610. LDO602comprises an operational amplifier608having a first input for receiving the VREF reference voltage, a second input coupled to node610, and an output. LDO602also comprises an MOS transistor M1, wherein the current flowing through transistor M1is designated ISUPP, which is the supply current through ASIC functional building blocks606. The gate of transistor M1is coupled to the output of operational amplifier, and the current path of transistor M1is coupled between a source of supply voltage VSUPand node610. Power measuring circuit600also includes a current sensor604, wherein the current sensor comprises an MOS transistor M1C and a sense resistor612coupled to a source of MOS transistor M1C at output node614. In an embodiment sense resistor612can also be coupled to ground. The gate of MOS transistor M1C is coupled to the gate of MOS transistor M1. The current path of MOS transistor M1C is coupled between a source of supply voltage ISUPP_COPYand output node614. The voltage at output node614is thus a continuous measure of the power supply dissipation of ASIC functional building blocks606and generates the replica P* power profile. FIG.7is a block diagram of reconstruction filter326that is used in any of the digital microphones ofFIG.3,FIG.4, orFIG.5. Reconstruction filter326receives the replica P* power profile as an input signal702to a gain stage704. An output of gain stage704is coupled to a first digital filter706. An output of first digital filter706is coupled to a second digital filter708. The output of second digital filter708provides a digital X-talk estimate710. The thermal behavior of MEMS device302is modelled by the first digital filter706using a second order digital infinite impulse response (IIR) filter (thermal model). The acoustic high-pass behavior of the MEMS device302is modelled by the second digital filter708using a first order high-pass digital filter. The input signal P* is the estimated power change (replica power profile) due to the dynamic mode change of the digital microphone being used. Gain stage704, first digital filter706, and second digital filter708can be implemented as digital circuits in, for example, an integrated circuit, or can be implemented through software instructions stored in memory in conjunction with a microprocessor. The disturbing noise generated by the digital microphone varies according to different sizes and shapes of the MEMS device302. Subtracting the same compensation signal from the main signal path of the digital microphone will therefore not adequately compensate out the disturbing noise. In order to adapt to the varying disturbing signals, the reconstruction filter326is advantageously implemented as an adaptive filter by adjusting to the changing interfering signal. FIG.8is a timing diagram800of simulated XT voltages with respect to different switching transitions of a digital microphone for a power change of about 300 μW. The power change of the digital microphone is done at different transition speeds including a slow speed ramp (0.3 sec), middle speed ramps (between 0.1 sec and 0.02 sec) and a high speed step. A seamless threshold voltage is also shown inFIG.8, for which voltage XT signals below this threshold are inaudible. FIG.8shows a X-talk response802for a step transition reaching a peak value of the about 0.8 millivolts, a X-talk response808for a 0.2 second ramp transition reaching a peak value of about 0.7 millivolts, and a X-talk response806for a 0.1 second ramp transition reaching a peak value of about 0.3 millivolts, all in excess of the seamless threshold810, which is 0.2 millivolts in an embodiment.FIG.8also shown a X-talk response804for a 0.3 second ramp transition reaching a peak value of about 0.1 millivolts, which is lower than the threshold value of seamless threshold810. InFIG.8it can be observed that the faster the change in the change between the operational modes of the digital microphone, the larger the value of the corresponding X-talk artefact. Typically, slow ramps are used in digital microphones in order to reduce the amplitude of the artefacts in order to make them fall below the audible threshold. FIG.9is a timing diagram900of X-talk voltage for a step switching transition and the remaining error after X-talk compensation is applied, according to an embodiment. In particular, the reconstructed X-talk response902to a step transition is shown, also reaching a value of about 0.8 millivolts, well in excess of the 0.2 millivolt value of the seamless threshold906. The reconstructed X-talk response902is subtracted from the main signal path during the step transition to provide a compensated output signal as previously described. InFIG.9, the remaining X-talk value904(after compensation) for the worst case scenario (a step transition) is depicted. The compensated output signal has very little remaining X-talk, and is reduced even far below the slow ramp case shown inFIG.8, which is assumed to be inaudible. FIG.10is a block diagram of a method1000of operating a digital microphone including X-talk compensation, according to an embodiment. The method1000includes converting an analog input signal from a microelectromechanical (MEMS) device using an analog-to-digital converter (ADC) in the digital microphone, wherein the ADC comprises a power profile while switching between first and second operating modes representing power consumption of the ADC as a function of time at step1002; reconstructing the power profile at step1004; using the reconstructed power profile, determining a cross-talk estimate of the digital microphone at step1006; and subtracting the cross-talk estimate from an output signal of the ADC to generate a digital output signal corresponding to the analog input signal at step1008. FIG.11is a block diagram of a digital microphone system1100, according to an embodiment. Digital microphone system1100includes a MEMS device1102having an analog output1104coupled to digital microphone1106, which is in communication with a microprocessor1110through digital bus1108for the transfer of control signals and output signals. Digital microphone1106can include any of the digital microphone embodiments previously described. Microprocessor1110is in communication with memory1120through digital bus1116for receiving stored commands and storing data. Any suitable microprocessor or other processor, and any suitable type of memory can be used. Digital microphone system1100can also include other components1118such as other analog or digital circuits or components, such as filters, or other analog or digital circuitry specific to various product applications. Digital microphone system1100is only an example of the type of systems that can include the digital microphone described herein, and many other such digital microphone systems are possible while still incorporating embodiment concepts. According to embodiments, a system and method has been described to reconstruct and subtract X-talk disturbing noise from the main signal path of a digital microphone to provide a digital output signal having very low or inaudible X-talk. The disturbing noise can occur because of power profile changes during operational mode changes of the digital microphone. It is an advantage that the power change and corresponding change in operational mode can be performed one order of magnitude faster and any overhead analog circuitry (for example a digital-to-analog converter) can be eliminated, when compared to prior solutions. Example 1. According to an embodiment, a circuit includes a cross-talk compensation component including a power profile reconstruction component configured for reconstructing the power profile of a digital microphone in communication with a microelectromechanical (MEMS) device, wherein the power profile represents power consumption of the digital microphone over time between at least two operational modes of the digital microphone, and a reconstruction filter configured for modeling thermal and/or acoustic properties of the digital microphone; and a subtractor having a first input configured for receiving a signal from the digital microphone, a second input coupled to the cross-talk compensation component, and an output configured for providing a digital output signal. Example 2. The circuit of Example 1, wherein the reconstruction filter includes an input configured for receiving the reconstructed power profile. Example 3. The circuit of any of the above examples, wherein the power profile reconstruction component includes a power change measurement component configured for measuring the power profile of the digital microphone. Example 4. The digital microphone of any of the above examples, wherein the reconstruction filter includes a gain stage, a first digital filter configured for modeling thermal properties of the digital microphone, and a second digital filter configured for modeling acoustic properties of the digital microphone. Example 5. The digital microphone of any of the above examples, wherein the first digital filter includes a second order digital filter. Example 6. The circuit of any of the above examples, wherein the second digital filter includes a first order digital filter. Example 7. The digital microphone of any of the above examples, wherein the digital microphone, the cross-talk compensation component, and the subtractor are packaged together in a semiconductor package. Example 8. The digital microphone of any of the above examples, wherein the cross-talk compensation component and the subtractor are external to a semiconductor package of the digital microphone. Example 9. According to an embodiment, a digital microphone includes a microelectromechanical system (MEMS) device configured for providing an analog input signal; a front-end circuit coupled to the MEMS device; an analog-to-digital converter (ADC) coupled to the front-end circuit; a first digital filter coupled to the ADC, wherein at least one of the front-end circuit, the ADC, and the first digital filter includes a power profile; a power measurement component configured for measuring power or current of the front-end circuit, the ADC, and the first digital filter; a power profile reconstruction component in communication with the power measurement component; a reconstruction filter configured for modeling thermal and/or acoustic properties of the digital microphone, wherein the reconstruction filter is in communication with the power profile reconstruction component; and a subtractor having a first input coupled to the first digital filter, a second input coupled to the reconstruction filter, and an output configured for providing a digital output signal corresponding to the analog input signal. Example 10. The digital microphone of Example 9, wherein the power measurement component includes a voltage regulator coupled to a current sensor. Example 11. The digital microphone of any of the above examples, wherein the voltage regulator includes a low-dropout voltage regulator having a reference voltage input, and a current input coupled to a power supply node of the front-end circuit, the ADC, and the first digital filter. Example 12. The digital microphone of any of the above examples, wherein the current sensor includes a transistor and a sense resistor coupled to a source of the transistor. Example 13. The digital microphone of any of the above examples, wherein the front-end circuit, the ADC, the first digital filter, the power profile reconstruction component, the power measurement component, the reconstruction filter, and the subtractor are packaged together in a semiconductor package. Example 14. The digital microphone of any of the above examples, further including a control signal generation component coupled to a left/right (L/R) input of the digital microphone and to the ADC. Example 15. The digital microphone of any of the above examples, further including a modulator having an input coupled to the output of the subtractor and an output configured for providing a pulse modulation density (PDM) signal. Example 16. According to an embodiment, a method of operating a digital microphone, the method includes converting an analog input signal from a microelectromechanical (MEMS) device using an analog-to-digital converter (ADC) in the digital microphone, wherein the digital microphone includes a power profile while switching between first and second operating modes representing power consumption of the digital microphone as a function of time; reconstructing the power profile; using the reconstructed power profile, determining a cross-talk estimate of the digital microphone; and subtracting the cross-talk estimate from an output signal of the ADC to generate a digital output signal corresponding to the analog input signal. Example 17. The method of Example 16, wherein reconstructing the power profile includes measuring power or current of the digital microphone. Example 18. The method of any of the above examples, wherein determining the cross-talk estimate of the digital microphone includes digitally filtering the reconstructed power profile. Example 19. The method of any of the above examples, wherein digitally filtering the reconstructed power profile includes digitally filtering the reconstructed power profile using a thermal model of the MEMS device. Example 20. The method of any of the above examples, wherein digitally filtering the reconstructed power profile includes digitally filtering the reconstructed power profile using an acoustic model of the MEMS device. While this invention has been described with reference to illustrative embodiments, this description is not intended to be construed in a limiting sense. Various modifications and combinations of the illustrative embodiments, as well as other embodiments of the invention, will be apparent to persons skilled in the art upon reference to the description. It is therefore intended that the appended claims encompass any such modifications or embodiments. | 31,592 |
11858809 | DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The following describes the technical solutions in the embodiments of the present invention clearly and completely with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. EMBODIMENT Referring toFIGS.1-4, a method for inflating a micro-channel, comprising following steps of:Step (1) calculating an equilibrium hydrogen pressure when titanium hydride decomposes by thermodynamic method; analyzing the decomposition behavior of titanium hydride in the actual heating process by differential scanning calorimeter and thermal weight loss analyzer, so as to obtain the heating temperature to decompose and release hydrogen to determine the quantitative relationship between titanium hydride content-temperature-hydrogen pressure; by the method of combining numerical simulation and bond rolling experiment, analyzing the effect of the hydrogen pressure and bond strength of the metal composite ultra-thin strip after bond rolling on the pore size of the micro-channel, and the corresponding relationship between the pore size of the micro-channel and the content of titanium hydride, the heating temperature, and the bond strength of the metal composite ultra-thin strip is obtained.Step (2) engraving micro/nano grooves on a surface of a thin metal strip by a micro/nano scratcher, immersing the ultra-thin strip with micro/nano grooves in the acetone solution, and cleaning the ultra-thin strip by ultrasonic cleaner to remove the scratch residue on its surface;Step (3) determining an amount of titanium hydride according to the quantitative relationship among titanium hydride content-temperature-hydrogen pressure and the relationship between the target pore size of the micro-channel and the amount of hydrogen released from decomposition of titanium hydride and the heating temperature determined in step (1), and the titanium hydride powder is placed in the micro/nano groove of the metal strip after the surface cleaning treatment in step (2);Step (4) covering another ultra-thin metal strip with identical size and identical surface cleaning treatment in step (2) on the ultra-thin metal strip in step (3), welding the edges of the two ultra-thin metal strips together by spot welding technology, and performing bond rolling;Step (5) heating the metal composite ultra-thin strip after bond rolling in step (4) under vacuum conditions, and keeping temperature to decompose the titanium hydride to release hydrogen, and by hydrogen pressure, plastic deformation occurs at the composite interface of the bond-rolled metal composite ultra-thin strip, and a tubular micro-channel structure is formed along the micro/nano groove engraved in step (2);Step (6) cutting the tubular micro-channel structure generated in step (5) at an appropriate position to obtain a tubular micro-channel product. The single-channel structure shown inFIG.1and the multi-channel structure shown inFIG.2in this embodiment are only two special distributions of micro-channels. The number, direction, and distribution of the micro-channels involved in the present invention can be flexibly set according to requirements; all belong to the content protected by the present invention. In the embodiment, the heating temperature in step (5) is at a range of 500-700° C., and the holding time is at a range of 10-30 min; the titanium hydride in step (1) can be replaced by zirconium hydride or other metal hydrides, and in the step (1)-(5), the thickness of the metal ultra-thin strip is at a range of 20-200 μm, such as 20 μm, 50 μm, 100 μm, 150 μm or 200 μm. The ultra-thin metal strip material is stainless steel, and pure metals such as titanium, copper and aluminum or an alloy of titanium, copper, and aluminum. The two ultra-thin metal strips have the same material during bond rolling, or a combination of dissimilar materials. | 4,025 |
11858810 | FIG.1shows an electrode arrangement1of a device for generating ozone with a group of annular shaped electrodes and a central heat2pipe with a circular cross-section made of glass which are installed in a nesting manner. The isolator2(central heat pipe) is surrounded by a stainless steel mesh3, which forms a high voltage electrode4. The high voltage electrode4is concentrically surrounded by a ground electrode5, wherein in between the electrodes4,5a dielectric6is arranged. The ground electrode5is again surrounded by a dielectric7which is covered by a high voltage electrode8. Gaps9are formed both between the high-voltage electrodes4,8and the dielectric6,7and between the dielectric6,7and the ground electrode5. The central heat pipe2is a hollow cylindrical tube filled with a material that will vaporize at operating temperatures of the inner high-voltage electrode. The tube, as shown inFIG.4, can extend into a bonnet10wherein it is provided with some extended surface11. The extended surface11can be realized by helically wound fins, studs, longitudinally organized fins or other known forms of extended surface. In the condensation zone of the heat pipe2the tube2is cooled by air which is circulated through the bonnet10. The vaporizing and condensing material typically may be water, or methyl alcohol or ethyl alcohol or ammonia. Heat pipes are heat transfer devices which provide high heat transport efficiency. Heat pipes have an enclosed cavity (e.g. defined between each of double walls5A,5B and8A,8B) filled with a condensable heat transfer medium15. Heat is put into the heat pipe at an evaporator section where the working fluid is vaporized and the vapour travels to a condenser section of the heat pipe where it condenses, thereby giving up heat which is radiated or conducted to an eternal load or sink. The condensed working fluid is then returned to the evaporator section typically be refluxing or through a wick which conducts the liquid by capillary action. Annular heat pipes12with a double wall structure —5A,5B and8A,8B, respectively—form the ground electrode5and the outer high-voltage electrode8. These heat pipes typically may be made of various grades of steel, aluminum alloys or chromium-nickel-iron alloys. Each heat pipe2,12has preferably its own closed heat exchange system. InFIG.2the inner high-voltage electrode4is formed by the mesh3and the central heat pipe2, which are both made of metal. In the electrode arrangement ofFIG.3, the central heat pipe2solely forms the inner high-voltage electrode4. A mesh is not provided. FIG.4shows the arrangement of the annular central heat pipe2containing heat transfer medium15, surrounded by a discharge gap9. The cooling section10(i.e. heat exchanger) for heat pipe2, is placed outside of the discharge gap. The cooling fins11are cooled with air17blown by fan16. In practical use, the number of the at least one ground electrode, the at least one insulating layer and the at least one high voltage electrode may be determined according to actual needs. The device according to the invention can be used for systems in which one or a plurality of gaps is used for the discharge. The at least one annular heat pipe allows to efficiently cool the at least one discharge gap. Additional cooling with water is not required. The use of an annular heat pipe leads to significant design advantages; the reaction zone does not need to be cooled directly, a cooling medium and pumping systems are not necessary, the cooling section can be placed in proximity to the discharge gap. The systems are therefore much smaller and can be developed as “plug and play” solutions. Preferably, a heat exchanger with a cooling jacket is arranged in the condensation zone of the heat pipe. This allows transfer of the heat generated by the heat pipe to the cooling water of the heat exchanger. For larger systems with multiple high voltage electrodes it is advantageous, if an interlocking connection between the cooling jacket of the heat exchanger and the heat pipe is used. The heat pipe can but does not need to be made of an electrically conductive material. Therefore the components of the electrode arrangement, the high voltage electrodes, the ground electrodes and the even the dielectric can be designed as a heat pipe. The present invention significantly improves the efficiency of ozone generators and the concentration of the ozone output. Heat balancing between areas of high and low temperature is possible, which results in less NOxgeneration because less power input per surface area is required. | 4,584 |
11858811 | DETAILED DESCRIPTION One area of discovery described herein regards the use of reaction chambers, such as reaction chambers with a hearth-like bed floor and reaction chambers found in rotary hearth furnaces (RHFs), rotary kilns, tunnel kilns, etc., for the reduction and recovery of elements from an oxidized state. For example, phosphorus may be recovered from apatite and other phosphate-bearing materials to produce phosphoric acid and/or elemental phosphorus, as well as supplementary cementitious material and/or lightweight aggregate. Also, for example, the reaction chambers may operate at temperatures from 1180° C. to less than 1400° C., such as from 1225 to less than 1400° C., including 1225 to 1380° C., 1250 to 1380° C., and 1250 to 1350° C. The various methods, systems, and compositions described individually herein may be implemented alone or in combination. A reaction chamber provides an enclosed space where process conditions may be controlled and process off gases collected. In reaction chambers within a hearth-like bed floor, the carbo-thermal reduction reaction of phosphate may occur as a continuous process and may allow for increased phosphate yields while reducing negative impacts of dust. The phosphorus collected from the off gas may be oxidized in a thermal oxidizer, as described further below. The processed agglomerates may be a co-product, as described further below, suitable for several construction applications, including use as a lightweight aggregate (whole agglomerate) or supplementary cementitious material (such as when subsequently ground to less than 45 micrometers (μm)). Aside from the silica ratio in the process feed, compositions for feed agglomerates that are generally known may be used in the methods herein in accordance with known considerations for selecting such compositions. The known improved hard process (IHP) is based on maintaining a certain silica ratio to decrease melting in the solids at operating temperatures. The silica ratio (SR) herein refers to the formula weight ratio of silicon dioxide to calcium oxide plus magnesium oxide or (% SiO2/60)/((% CaO/56)+(% MgO/40.3)). According to the IHP, SR should be maintained around 2.0 to avoid the eutectic point at which slag and some calcium silicates liquefy. The known IHP uses a ported rotary kiln as the means to provide the energy and temperature for the reduction reaction that drives off the phosphorus. Melting in this vessel may lead to very difficult operating conditions as cold agglomerates from the feed end run into and stick to melted material in the hot end of the kiln. This forms large lumps, or clinkers, which may be difficult to remove and may further deteriorate the integrity of the kiln bed containing the agglomerates. Usually, no amount of melting can be tolerated in a rotary kiln. Some of the methods herein use a much lower silica ratio mix that is on the other side of the eutectic point on the phase diagram. The eutectic point starts at around 0.67 SR and ends at around 1.5. Ratios below 0.67 and above 1.6 can allow temperatures to be hotter in the system to initiate reduction without melting. A ratio of 1.6 often does not allow temperatures high enough for reduction to occur, which is the reason for the ratio of 2.0 in the IHP. As demonstrated herein, silica ratios of around 0.5, such as 0.3 to 0.7, can be used that produce reduction yields of 90% or higher without significant melting and at temperatures just above 1250° C. There may be a small amount of melting that occurs at the 0.3 to 0.7 ratio. Generally, it is a very viscous melt that is not flowable, though it may stick to the other agglomerates. In nearly all cases, even small amounts of melting and stickiness can be undesirable in a rotary kiln. An RHF offers a bed floor that keeps agglomerates substantially stable, that is, stationary with respect to each other, while continuously moving under a heat source. A “substantially” stable bed permits some settling or incidental shifting in relative position among the agglomerates while the bed floor continuously moves, but does not intentionally tumble, blend, or similarly disturb the bed. A small amount of melting may be acceptable in this system without the deleterious effect observed in rotary kilns. As a precedent, iron ore systems using RHFs allow their agglomerates to melt to increase yield and throughputs. Accordingly, in phosphorus production, operating temperature may be 1250 to 1380° C., including 1250 to 1350° C., and silica ratio may be 0.7 to 0.3, with the lower silica ratio corresponding to the higher temperature and the higher silica ratio corresponding to the lower temperature, for yields of greater than 80%, such as greater than 85%, including greater than 93%. Residence times with less than 60 minutes of heating at the target temperature, such as 30 to less than 60 minutes, including 30-45 minutes, may be sufficient to achieve the stated yields within the ranges of silica ratio and temperature. Test data below describe results in the indicated ranges. Though well-suited to an RHF, such process conditions could be used in other reaction chambers with a hearth-like bed floor or tunnel kilns with a beneficial result. A rotary kiln might even be suitable, assuming the melting can be tolerated or controlled by some means other than a high silica ratio above 1.6. One benefit of using a lower silica ratio includes increased phosphorus throughputs per unit ton of feed material. For example, in one high silica ratio mix with a silica ratio of 2.5, phosphate (as P2O5) levels are 11-13 weight percent (wt %), depending on other impurities. In a comparable, lower silica ratio mix in which only the silica ratio is changed to 0.5, P2O5levels are 17-20 wt %. This increases throughput or P2O5extraction potential from 9% up to 17%, for example, nearly doubling potential P2O5extraction. Often, producing a mix for feed agglomerates with a high silica ratio, such as above 1.6, includes adding supplemental silica to the mix of phosphate ore and carbonaceous material in addition to silica already in the phosphate ore. To produce a lower silica ratio mix, the amount of supplemental silica may be left out or at least decreased. Less supplemental silica then allows more concentrated phosphate to be contained in the agglomerate mix. Summarizing the description above, tradeoffs exist between choosing to operate at SR 0.3 compared to SR 0.7. At the lower SR 0.3, the melting risk is lower and the P2O5levels are higher, but the yield at lower temperatures is lower. At the higher SR 0.7, the yield at low temperatures is higher, but the melting risk is higher and the P2O5levels are lower. Table 1 highlights the tradeoffs. The description above describes the benefits of operating at SR 0.3 to 0.7 compared to a silica ratio on the other side of the eutectic higher than 1.6, such as 2.0. Even so, the methods, systems, and compositions herein may relieve some of the disadvantages of SR higher than 1.6, as demonstrated with pilot-scale testing at SR 2.0 and higher described below. Table 1 also highlights tradeoffs for silica ratios higher than 1.6. TABLE 1ConsiderationSR 0.3SR 0.4 to SR 0.6SR 0.7Yield at lowerLowerHighertemperaturesMelting riskLowerHigherP2O5in feedHigherLowerSR > 1.6SR 1.7 to SR 1.9SR 2.0 and higherYield at lowerLowerHighertemperaturesMelting riskHigherLowerP2O5in feedHigherLower One example of a suitable RHF includes a rotating annular hearth surrounded by a stationary reaction chamber. The reaction chamber may be heated and maintained up to 1380° C. by indirect heaters and/or by the direct combustion of fuel gas, natural gas, or fuel oil, to which may be added port air or oxygen-enriched combustion air, injected through the furnace roof and/or walls. Indirect heaters provide heat transfer without relying on a direct flame or exhaust from combustion. Post-combustion of carbon monoxide gas from a bed of agglomerates may further heat the reaction chamber. Radiation is the main mode of heat transfer in an RHF from the gas and furnace walls to the agglomerate bed. The secondary heat transfer mechanisms are convection from the gas and conduction from the floor. RHFs are used to reduce iron oxide into pig iron or pure iron. Similar to IHP, iron ore solids are ground and mixed with reductant carbon. This mix is agglomerated and layered onto the hearth where radiative heat allows for the carbon to reduce the oxide. However, the iron product is in the solids discharged from the hearth, while the phosphorus product from IHP is in the off gas. The literature describes direct reduced iron (DRI) produced by RHF and both DRI and zinc oxide produced by RHF. An RHF may have reduction temperatures and times similar to a ported rotary kiln. Off gases could be collected with a phosphoric acid scrubbing system in a similar manner to a kiln process off gas, or other known scrubbing systems. The IHP is based on the use of the ported rotary kiln. Operational issues have occurred with ported rotary kilns, including dust generation from the tumbling action of the bed and lower yields due to exposure of the entire bed to oxidizing gases, such as O2and CO2at low bed temperatures during the slow ramp up of bed temperature. Oxidizing gases burn with the carbon required for the reaction and could also change the agglomerate surface chemistry due to the premature loss of carbon, which would not allow gaseous phosphorus to escape the agglomerate. The gaseous phosphorus can react with calcium remaining on the ball surface to form calcium phosphates. As a result, benefits A-D of the RHF over known rotary kilns and/or known tunnel kilns are listed below. Though listed as benefits of an RHF as an example, the additional descriptions below explain how these benefits may be extended to other systems, including systems using reaction chambers with a hearth-like bed floor.A. No tumbling of the agglomerates while they rest on the hearth-like bed floor, which can generate dust and produce solid precipitates due to subsequent back reactions, as with agglomerates that tumble through a rotary kiln. These precipitates can shorten the life of the rotary kiln.B. Increased phosphorus recovery and increased phosphate yield resulting from decreased exposure of feed agglomerate surface area to harmful oxidation reactions from freeboard gas. This may be achieved through one or more methods including indirect heating, use of a stable bed, fast ramp up to reduction temperature (i.e., decreased heating times), and the use of protective layering in the agglomerate bed. The setup, operation, feed, discharge, and materials of construction of an RHF are better suited for these methods than both a known rotary kiln and a known tunnel kiln.C. Potential to allow feed agglomerates to melt without harmful effects on hearth.D. Downstream phosphoric acid recovery plant for an indirectly-heated RHF can be smaller than a direct fired known rotary kiln or known tunnel kiln for the same amount of materials processed and the same amount of acid production. As explained below, limitations on indirect heating exist in rotary kilns such that an indirectly-heated kiln cannot attain the level of heat transfer found in a directly-heated kiln. Similar benefits may potentially be obtained from use of, or be designed into, systems other than RHFs that include reaction chambers with a hearth-like bed floor. Benefit A: Dusting A rotary kiln operates at an incline with a component of vertical rotation by which it constantly tumbles the feed bed as the means to transport the material from feed end to discharge. The tumbling action creates dust due to attrition of the agglomerate surface. Some of this dust is swept into the feed bed and the freeboard of the kiln, where it can then react with other components and precipitate on colder sections of the kiln, mainly near the solid feed end where the gas is discharged. Some calcium phosphates produced on the agglomerate surface can also dust-off, start to melt in the hot area of the kiln, and then re-precipitate in the cooler sections. These precipitates eventually start to block the air flow, resulting in a need to shut the kiln down and clean out the solids. It has been demonstrated (see, U.S. Pat. No. 9,783,419) that a separate induration kiln (preceding the reduction kiln) effectively heat hardens the feed agglomerates to significantly decrease agglomerate dusting and breakage. But, the rotary tumbling action may still result in dust due to attrition in the reduction kiln. In addition, dust generated in the induration kiln may carry over on the surface of the heat hardened agglomerates fed to the reduction kiln. A dust loss of 0.1% from the feed agglomerates that is discharged to the freeboard can be enough to result in kiln rings and solids buildup. Also, combustion and/or port air can react with gaseous phosphorus, such as P, P2, or P4(referred to herein as “gaseous P”), to create more P4O10in the freeboard, which readily reacts with the incoming dust to create calcium phosphates responsible for buildups and rings in the kiln. An RHF may be the means to impart sufficient energy for the carbo-thermal reduction reaction. The RHF does not tumble the bed as a means of continuous feed and transport to a hot zone, where exposure to temperatures sufficient for reduction occurs, as in a rotary kiln. In an RHF, the bed is established on the hearth table via continuous feed and remains stable while it is transported mechanically via rotation in a horizontal plane under stationary heating sources, whether direct fired, indirect fired, or electric. As a result, dust formation may greatly decrease. The residual dust carried over from previous operational steps (dryer, conveyor, etc.) will likely stay in the bed as the bed is not turning over into an air-swept freeboard like in the kiln. In addition, it is possible for port air not to be added into the reaction chamber itself, but to the RHF exhaust gases by way of an afterburner in a secondary processing step. Thus, P4O10formation diminishes within the reaction chamber, beneficially decreasing dust and free board component reactions that contribute to build-up. Adding port air to a rotary kiln's off gas by way of an afterburner is not as effective due to excess dust in the off gas and the likelihood of buildups and rings in the afterburner. The RHF may also be designed with more uniform temperature zones, which impede formation of cooler spots, regions, and other potential areas for solids precipitation to occur. An RHF is one type of reaction chamber with a hearth-like bed floor. Other reaction chambers with hearth-like bed floors might be used successfully in the methods and systems herein. A hearth-like bed floor does not intentionally tumble the bed. A reaction chamber with a hearth-like bed floor may provide continuous transport of agglomerates through the hot zone, where exposure to temperatures sufficient for reduction occurs. In contrast to continuous transport of agglomerates through the hot zone, batch transport would involve loading agglomerates onto a hearth-like bed floor in a reaction chamber and holding the bed floor stationary in the hot zone for carbo-thermal reduction. There would also be a loss of heat on the bed floor while loading and unloading the bed between batches. Benefit B: Decreasing Oxidizing Freeboard Gases to Increase Phosphorus Recovery and Phosphate Yield Phosphate yield indicates the amount of phosphate initially in feed agglomerates that does not remain in the residue containing processed agglomerates. Phosphorus recovery indicates the amount of phosphorous initially in feed agglomerates that is collected, usually as phosphoric acid, but possibly as elemental phosphorous. Phosphate yields and phosphorous recovery can be negatively impacted by insufficient available energy or temperature to start the carbo-thermal reduction reaction or by insufficient carbon to complete the reaction. Reducing conditions in the kiln atmosphere or kiln freeboard insufficient to suppress the formation of calcium phosphates on the agglomerate surface can also negatively impact yield. Overall, under known ported rotary kiln conditions, actual phosphate yields are approximately 60%, often with a maximum of 70%. Under oxidative conditions, some of the gaseous P released from the carbo-thermal reduction of apatite reacts with calcium on the outer layer of the agglomerates to create a “white shell” that not only continues to build, but also restricts complete evolution of gaseous P, thus limiting overall phosphate extraction and yields. Depending on the oxidative conditions, the P2O5concentration in the white shell may be higher than that of the original feed. Also, the mass of the shell may be up to 50% of the total mass of the reduced agglomerate due to its higher density as compared to the inner core. In some agglomerates, the outer, white shell is quite differentiated from the core and from a transition layer between the core and the white shell and is about 0.5-1.0 millimeter thick. Recent testing and analysis identified the main components of the white shell, its mechanism of formation, and the atmospheric reducing conditions that diminish the white shell formation. Spent agglomerates from a pilot-scale, ported rotary kiln process underwent SEM/EDS and XRD laboratory analysis, revealing that the white shell contained a calcium phosphate mineral, Whitlockite [(Ca9(Mg,Fe)(PO4)6PO3OH)] along with a hydrated alumino-calcium silicate (Levyne) and Fluorapatite [(Ca5(PO4)3F)]. The concentration of phosphorus is higher in these compounds than in the original apatite, indicating that a secondary, calcium-based reaction produced the white shell, rather than unreacted apatite. Besides the white shell, the discharged kiln pellet had an inner dark core comprised of predominantly quartz (natural) and silicon oxide (artificial due to heating) and a calcium alumino-silicate (Anorthite family) (Ca0.5((Al0.1Si1.9)O4). There was less than 1% phosphate in the inner core of the reduced pellet that was discharged from the kiln. The low phosphate content in the inner core confirmed there was sufficient time, temperature, and carbon content available for near complete reactions with 90% or higher yields. The loss of yield was believed due to the formation of calcium phosphates on the surface of the agglomerate, which was a function of the oxidative conditions in the freeboard of the kiln. A thermodynamic analysis of the operating conditions reveals the conditions that might lead to forming this white shell. A predominance diagram (modified for simplicity) can help clarify the conditions for stability of different phases. From the diagram inFIG.5, one can see that conditions to keep phosphorus from back reacting to form calcium phosphate are quite reducing. The lines for P2gas at 1 atm and 0.1 atm are given. These show that for the 0.1 atm P2line, CO concentrations need to be above about 1% (−2 on the log axis), but that CO2concentrations must be less than ˜0.1%. This indicates the degree of reduction that is required in a carbo-thermal reduction process for the production of phosphorus. A second approach to the predominance diagram is only to look at calcium bearing phases to see when CaO is predominate and when calcium phosphate exists. This is shown inFIG.6where hydrogen has been removed from the conditions and the P in the gas is fixed. Changing the partial pressures of P2can impact the diagram slightly, but the purpose is to show where CaO can no longer form phosphates. It can be seen inFIG.6that a CO/CO2ratio of about 10,000 is needed to suppress CaO's ability to combine with phosphorus. This ratio is clearly much higher than the freeboard conditions in a direct fuel fired kiln due to air injection and subsequent formation of high concentrations of CO2. Based upon recent test work using various fixed CO/CO2atmospheres, there is strong evidence that the phosphorus is released from the pellet and recaptured from the bulk gas. It appears that once phosphorus has reacted on the surface, it remains there. This would indicate that the phosphorus transitions from a relatively reactive phase (apatite) to one that is more stable (Whitlockite). The mechanism of phosphorus retention appears to be due to the bulk gas phase being too oxidizing. To control the negative yield impacts of the oxidative atmosphere in a rotary kiln, measures 1-4 could be attempted:1. Use of indirect heating and no port air addition to diminish formation of CO2;2. Decrease bed surface area of the agglomerates exposed to the atmosphere;3. Quicker ramp up times to reaction temperatures to evolve the gaseous P faster than the calcium phosphate formation; and/or4. Addition of protective layer of carbon to keep localized CO/CO2levels high. However, as discussed, ported rotary kilns are designed to use a single fuel-fired burner with a well-mixed bed that exposes surface area of the bed as it rotates under a slow ramp up of temperature. The rotation of the kiln also decreases effectiveness of a protective carbon layer. In comparison, an RHF may be designed to implement one or more of the four favorable measures listed above. Measure 1: Indirect Heating Using Electric Heating Elements and/or Radiant Tube Burners. This diminishes the high CO2content from the direct combustion of natural gas, coal, or fuel oil that occurs in a rotary kiln. This is more easily accomplished in an RHF as multiple heating elements can be added along the perimeter of the hearth above a bed to create the desired heat. Radiant tube burners are indirect-fired heat sources using combustion to generate heat, but containing and venting exhaust. Combustion products do not come in contact with material to be heated. However, a rotating kiln bed limits the number of heating elements/indirect burners in a kiln since the installation is limited to the feed end of the kiln, which may also move the kiln hot spot away from the discharge end of the kiln and upset the counter-current flow of gas compared to solids. The elements/burners cannot be installed along the kiln shell and in the discharge hood (near the kiln hot spot) since the kiln's rotating bed is lifted and may fall damaging the elements/burners. The limited number of elements/burners in a rotary kiln cannot create the desired heat. Measure 2: Bed Surface Area. Unlike the bed in a rotary kiln, the bed in an RHF is stable and mechanically rotated under the heat from the reaction chamber, thus, generally only exposing the top layer of the RHF bed to harmful oxidative atmospheres and not the entire bed, as in a ported rotary kiln. Measure 3: Fast Ramp Up to Reduction Temperatures. In known rotary kilns or known tunnel kilns, feed material slowly moves down the length of the kiln, gradually heating up from the counter flow of hot freeboard gases as it approaches the one main hot spot closer to the burner flame tip near the bed discharge. This is fairly energy efficient, but the slower ramp up time while exposed to oxidative gases promotes premature burn of carbon in the bed and increases “white shell” formation before the reduction temperature is reached. An RHF has the ability to expose the bed to reaction temperatures directly, heating the bed up to reaction temperatures much faster. The entire RHF reaction chamber or a selected portion thereof may be controlled at reduction temperatures with multiple heating elements and/or burners located around the perimeter. The bed floor remains hot after the processed agglomerates are removed, which allows for the immediate heating of fresh agglomerates fed to the RHF. A number of lab furnace tests demonstrated the potential positive benefits of direct exposure to high temperatures versus a slower ramp up. For both test cases, cold (ambient temperature) pellets were used. The temperatures shown in Table 2 below are lab furnace temperatures. The slow ramp test involved placing cold pellets in the lab furnace heated to 900° C. and increasing the furnace temperature from 900 to 1290° C. over 30 minutes to mimic heating of the pellets as they move down the length of a rotary kiln. For the direct exposure test, the lab furnace was already at 1290° C., the furnace door was opened, the cold pellets were placed in the lab furnace, and the door was closed to mimic the RHF. The temperature in the lab furnace returned to 1290° C. in 5 minutes. Both tests had a controlled atmosphere of approximately 12% CO2to simulate direct fired burner conditions and were held at the 1290° C. reaction temp for 15 minutes. TABLE 2Test Results for Fast Ramp Up to ReductionTemperatures—Direct Heat vs. Slow Ramp UpSlow ramp upDirect exposure toNon-protected green(900° C. to 1290° C.)1290° C., fast rampball test 12% CO2in 30 minutesup in 5 minutesPhosphate Yield55%88% The rotary kiln has a wider temperature profile from feed to discharge and takes about 30 minutes for the feed balls to get full exposure to the reduction temperature. An RHF can have even temperatures throughout, thus, the fresh feed is exposed to the reduction temperature quickly, for example, in less than 10 minutes. The 30 minute ramp up time in the rotary kiln is one of the root causes of carbon losses. It was also noted that the slow ramp up material, after reduction, had significantly higher amounts of the white shell, as discussed previously. Measure 4: Layering or Coating to Protect Bed to Keep Oxidative Gases Away from the Feed Reactants. The RHF allows for the use of a protective layer, such as coke or a similar carbon source, to keep oxidative gases away from the feed reactants. Since the bed is stable in an RHF, a layer of coke can be added on top of the bed without disruption. In a rotary kiln, the bed constantly rotates, thus inhibiting carbon protection. Lab furnace tests were conducted under similar ramp up profile and reaction temperatures, with the difference being one set of feed pellets had a protective layer of petroleum coke to consume oxidative gases and one did not have a protective layer of petroleum coke. Even under unfavorable slow ramp up conditions, the protective coke layer provided significant yield benefits (more than 40% increase). TABLE 3Test Results for a Protective Layer of Pet Coke toProvide Atmospheric ProtectionNon-protected,Pet Coke layer on top,Green ball testslow ramp upslow ramp upPhosphate Yield25%67% If warranted, then additional carbon may be added to the feed to provide a protective coating on the agglomerates. A protective coating of carbon may include fine carbon particles added to the agglomerates prior to the RHF, but after the initial agglomerates are made. The carbon coating may be 1-3 wt % extra carbon and can provide protection from the oxidizing atmosphere. The coating thickness may be 0.5 to 0.7 mm. The RHF uniquely enables the effectiveness of this protective coating since the rotary kiln would tend to attrit off the protective coating as it tumbles. Benefit C: Melting Capability An RHF can operate with feed chemistries and furnace temperatures such that the bed starts to melt. Feed agglomerates with silica ratios less than 2.0 often melt at temperatures above 1250° C. If melting were allowed, then feed grades could be increased up to 80% (10% P2O5to 18% P2O5, for instance), as more apatite and less dilutive silica is used, while operating 50-80° C. higher than expected furnace temperatures of 1250 to 1300° C. Known commercial systems allow iron ore feed agglomerates to melt in an RHF for reaction benefits. Comparatively, a rotary kiln does not handle feed stock melting well since viscous melts roll and combine with cooler bed material and continue to grow into difficult to handle lumps or “clinkers.” Several “melt” tests were conducted to determine the feed mix chemistries that can increase overall phosphate extraction yields at temperatures an RHF can sustain without the formation of damaging stickiness from the melting of the feed pellets. The experiments evaluated various furnace conditions that would allow melting of feed stock at operating temperatures from about 1250° C. to about 1350° C., with few operating issues with the molten slag. A number of tests were run at various chemistries, as measured by silica ratios (SR), to determine yields at various time and temperature profiles. During these tests, observations were made to the state of the cooled ball after melting in relation to the ability for continuous discharging and minimal sticking to refractory. Generally, at lower silica ratios, the melt is less viscous and more freely flowing. FIGS.7and8show phosphate yield and phosphate extraction, respectively, versus silica ratios. Based on the assays used to calculate phosphate yield, phosphate extraction indicates the mass of the initial feed material extracted as P2O5. Higher extraction percentage indicates higher throughput potential. Silica ratios between 0.8 and 2.0 melted at 1250° C. and above. Yields above 90% were shown with silica ratios as low as 0.5. The data also implied that, with an increase of 50-80° C. above expected reaction temperatures, extraction rates or P2O5throughputs can increase by 80% using the same total overall solid feed rates containing a higher P2O5content. Benefit D: Smaller Phosphoric Acid Recovery Plants In a rotary kiln, direct combustion of natural gas and air is used to provide the reaction heat and temperature. This produces large quantities of combustion gases, including nitrogen. The acid scrubbing plant size is designed based on the amount of combustion gases it has to handle. In an RHF using indirect electrical heating elements, gases from the reduction reaction (CO and gaseous P) are produced with no off gases from direct combustion of natural gas and air, thus reducing the required size of the acid scrubbing plant. Numerous electrical heating elements can be placed around the circumference of an RHF, whereas in a rotary kiln only one large burner or a few small burners are used at one end of the kiln. As an example, a direct fired system may produce higher gas flows by weight as compared to the indirectly heated systems. In an estimate for an RHF case, about 100,000 tons per year of P2O5with 85% availability are input to an RHF with only indirect heating and the produced gaseous P and CO are fully oxidized in an afterburner with 2% residual oxygen. In a comparable kiln case, about 100,000 tons per year of P2O5with 85% availability are input to a ported rotary kiln with port air sufficient to oxidize all the produced gaseous P and 50% of the produced CO and the remaining CO is oxidized in an afterburner with 2% residual oxygen. Such a kiln was estimated to produce over 4 times higher gas flows by weight to the acid scrubbing plant compared to the RHF. Because the acid scrubbing plant may be made from exotic metals and liners to decrease corrosion, reduction of system size can have a material impact to capital and operating costs. Example 1 A series of trials were completed in a lab furnace using agglomerates with various silica ratios (SR) and containing phosphate ore from various sources at various temperatures maintained for 30 min in a carbon crucible.FIG.11shows the yields obtained with respect to silica ratio for one of the ore sources at 1325° C. maintained for 30 min. Generally, the higher silica ratios showed higher yield, though melting observed at SR 0.55 might be hard to handle. Most SR 0.4 to 0.5 produced yields in excess of 80% without major melting. Even though the lowest silica ratios did not achieve 80% yield, the 1325° C. was only maintained for 30 min. The lowest silica ratios could tolerate a higher temperature without melting and/or longer process time to increase yield. Table 4 summarizes data similar to that ofFIG.11for various ore sources and various temperatures maintained for 30 min. Again, a general trend is apparent at each temperature that higher silica ratios showed higher yield. Though, even at SR 0.39, yield for the highest temperature exceeded 80%.FIG.12graphs data for Mix 1 at SR 0.39 of ore source 3, indicating that temperatures above about 1305° C. would be expected to produce 80% yield in 30 min. Table 4 likewise shows a general trend for other silica ratios that higher temperatures produced higher yield. Though, even at 1275° C., yield for the higher silica ratios exceeded 80%. The melting observed in several of the mixes occurred at 1325° C. TABLE 4YieldYieldYieldYieldYieldMixOreSR1350° C.1325° C.1300° C.1275° C.1250° C.ObservationJ10.2641%30.4%No meltingK20.3471%63.6%No meltingF20.3265.8%55%46%No meltingH10.4184.6%77%No melting130.3987.5%79%69%Minor melting at1325° C.I10.4281.6%76%Minor melting at1325° C.G20.4989.6%82%69%Some melting at1325° C.A30.5091.5%86%84%Some melting at1325° C.B/C30.5593.4%92%87%70%Low viscous meltat 1325° C.E30.6893.6%93%91%81%Low viscous meltat 1325° C. Example 2 Trials were conducted in a pilot-scale RHF at various silica ratios. The 6 feet diameter open (no segmentation) RHF previously used for batch annealing metal pieces was converted to allow for the continuous feed and discharge of ⅜ inch diameter agglomerates to maintain a bed of agglomerates in the furnace hot zone for 25 to 45 minutes depending on the rotational speed of the hearth floor. Heat was provided via electric heating elements suspended vertically from the furnace roof. Furnace and bed temperature were monitored continuously via thermocouples placed horizontally 3 inches above the agglomerate bed and optical pyrometers mounted on the roof for measuring the brightness of the heated agglomerate bed. While operating at 1320° C. with a residence time of 27 min the following results were obtained: 1) SR=0.40, Yield=59%; 2) SR=0.50, Yield=68%; 3) SR=0.60, Yield=85%. Silica ratios in the feed were selected close to 0.5 due to variability in the ores to decrease the likelihood of overshooting SR 0.5 and potentially melting in the RHF, as occurred with the SR 0.60. However, the pilot data correlates well with the lab data in Example 1 and yields similar to the lab data are expect at other silica ratios and other temperatures. Even though the lowest silica ratios did not achieve 80% yield, the 1320° C. was only maintained for 27 min. The lowest silica ratios could tolerate a higher temperature without melting and/or longer process time to increase yield. The pilot plant was also used to test a SR of 2.0 and achieved yields of greater than 80% over a 34 hour period of run time. These yields were more consistent and exceeded those obtained in a ported rotary kiln demonstration plant described in US App. Pub. No. 2019/0292055. Operating temperatures for the pilot plant with the yields >80% ranged from 1300 to 1330° C. for high silica (SR 2.0) and 1340 to 1380° C. for low silica (SR 0.7). These yields also matched with the yields obtained in lab furnace tests. System Design A reaction chamber with a hearth-like bed floor, such as in an RHF, may be designed in segments where selected zones can be physically separated from one another. This could allow controlled air and/or oxygen addition in a reduction zone, where carbo-thermal reduction occurs and the reaction products off gas. From 9 to 10 tons of air may be delivered per ton of phosphate as P2O5input to the chamber. Gaseous P and CO can ignite, consuming oxygen and providing a large heat source to maintain reaction temperatures and to decrease demand for external heat sources. A preheating zone may preheat agglomerates to reduction temperatures in a controlled atmosphere. Thus, the reduction zone and the preheating zone could together form the hot zone, where exposure to temperatures sufficient for reduction occurs. FIGS.1-4show one example of an RHF with segmented zones. The methods herein may be implemented in an RHF10, as shown, as well as in the reaction chambers of other systems. Likewise, the concept of segmented zones in a reaction chamber may be implemented in a manner other than shown for RHF10. InFIGS.1-4, RHF10includes an annular reaction chamber12bounded by a roof14, an inner sidewall16, an outer sidewall18, and a floor20, though shapes other than annular are conceivable. During operation, reaction chamber12contains a bed of feed agglomerates and a freeboard above the bed where off gases collect. Roof14, inner sidewall16, and outer sidewall18include several layers (not shown), such as both structural and insulation layers, used in known RHFs. Floor20also includes several layers shown as a hearth table30supporting a hearth22. In turn, hearth22includes a lower refractory28and an upper refractory26thereon. Upper refractory26provides a bed floor whereon agglomerates may be placed for subsequently forming a reducing bed. As the term is used herein, a “reducing bed” refers to the portion of the bed of feed agglomerates where reduction is occurring. A support frame38holds roof14, inner sidewall16, and outer sidewall18stationary while hearth22, with its annular shape, rotates in clockwise bed direction98along reaction chamber12. Known RHF drive mechanisms may be used to rotate hearth22.FIGS.1-4show a sprocket32positioned at the periphery of hearth table30and engaged with a gear box42powered by a motor44. As motor44activates gear box42, the engaged gear box42advances sprocket32and rotates floor20. Hearth table30rests on four wheels46secured to hearth table30with wheel brackets38. Support frame38provides a circular track40on which wheels46travel as hearth table30rotates. To limit gas entry and exit, outer sidewall18includes a seal wall36that extends downward into a seal trough34(shown only inFIG.3). Likewise, inner sidewall16includes a seal wall37that extends downward into a seal trough35. Seal troughs34and35may be filled with a liquid, such as high temperature oil, to contain the atmosphere inside reaction chamber12even when floor20rotates. Even though RHFs are known, RHF10is configured differently for use as a phosphorus production system. For example, reaction chamber12is segmented into a reduction zone differentiated from a preheat zone by a barrier wall52. InFIGS.1and4, positions around the radius of RHF10are designated with degree markings at 0°, 90°, 180°, and 270°. For the configuration shown inFIGS.1-4, barrier wall52is placed at 60° where it differentiates a reduction zone past 60° from a preheat zone before 60°. Hearth22is configured to move continuously from the preheat zone to the reduction zone during operation. As may be appreciated fromFIGS.1-4, the rotation of hearth22occurs in a horizontal plane such that agglomerates placed thereon may be substantially stable at least while in the reduction zone. RHF10additionally includes a barrier wall54further segmenting reaction chamber12into a cooling zone differentiated from the reduction zone. Barrier wall54is placed at 270° in the configuration shown. Hearth22is configured to move continuously from the reduction zone to the cooling zone during operation. The cooling zone of reaction chamber12is not heated by an external source, but the reduction reaction may continue into the cooling zone until the agglomerates cool sufficiently or the phosphate or carbon reactant is consumed. The reducing bed may cease to exist in the reduction zone if the phosphate or carbon reactant is consumed. Consequently, the hot zone spans 270° and includes the preheat zone spanning 60° and the reduction zone spanning 210°. A reducing bed may begin to form in the preheat zone and may continue to exist into the cooling zone. RHF10further includes a barrier wall50segmenting reaction chamber12and differentiating the cooling zone from the preheat zone. Barrier wall50is placed at 0° in the configuration shown. Hearth22is configured to move continuously from the cooling zone to the preheat zone during operation. Barrier walls50,52, and54decrease gas transfer between the zones and extend downward from roof14to just above agglomerates placed on upper refractory26with a gap sufficient for agglomerates to pass underneath. Consequently, a continuous agglomerate feed mechanism (not shown) may place feed agglomerates on upper refractory26upstream from barrier wall50such that the agglomerates settle into a bed as they enter the preheat zone. A continuous carbon feed mechanism (not shown) may place a carbonaceous material as a protective layer among the agglomerates. Agglomerates then move continuously through the preheat zone between barrier walls50and52where they may reach reduction temperatures before entering the reduction zone. Agglomerates continue around reaction chamber12, entering the cooling zone past barrier wall54. A screw conveyor80(or a scraper, not shown) removes agglomerates from the cooling zone and routes them through a discharge82to a cooler (not shown). RHF10includes burners60,62,64, and66positioned respectively at 70°, 125°, 185°, and 240° as direct-fired fuel burners to maintain reduction temperatures in the reduction zone. Burners60,62,64, and66include inputs for fuel as well as inputs for combustion air. RHF10additionally includes ports70,72,74, and76positioned respectively at 65°, 115°, 175°, and 230° as air and/or oxygen ports to facilitate combusting gaseous P and CO off gasses, thereby to heat the reduction zone additionally. Although not shown inFIGS.1-4, RHF10further includes one or more indirect heating sources in the preheat zone, such as electric heating elements and/or radiant tube burners. Notably, RHF10includes one or more direct-fired burners in the reduction zone, but not in the preheat zone. Also, RHF10includes one or more over-bed air and/or oxygen ports above hearth22in the reduction zone, but not in the preheat zone. In this manner, the preheat zone is configured to maintain a reducing freeboard during a carbo-thermal reduction reaction among feed agglomerates on hearth22. Likewise, RHF10provides a cooling zone that lacks any direct-fired burners, over-bed air and/or oxygen ports, and indirect heating sources. In this manner, the reducing bed cools to below reduction temperatures, halting the reduction reaction without heat addition from external sources or off gas combustion. RHF10includes a vent90through roof14at 260° for removing off gas upstream from barrier wall54for subsequent processing. Off gas flows clockwise in off gas direction96along reaction chamber12, co-current with bed direction98, to allow for heating the bed by the hot off gas as it moves through reaction chamber12. A vent92at 30° collects off gases from the preheat zone and transfers them to the reducing zone via a vent94at 90°. Vent94is shown inFIGS.2and4and vent90is shown inFIG.4. Vents90,92, and94cannot literally be seen in the sectional view shown inFIG.1, but their locations are superimposed with crosshatched spaces inFIG.1, showing their position relative to the other components inFIG.1. While the description ofFIGS.1-4specifies certain numbers and locations of burners, ports, vents, wheels, and barrier walls, it will be appreciated that more or fewer may be provided or located in other positions, depending on the diameter, throughput, and other design criteria of an RHF or other system. Likewise, the positions of burner, ports, vents, wheels, and barrier walls may be different. Also, the numbers and locations of measurement devices to monitor temperature in reaction chamber12are not shown.FIGS.1-4are one example of a design for a demonstration plant RHF with a smaller diameter and less throughput than a commercial-scale RHF. A larger RHF may include additional burners, ports, measurement devices, wheels, and vents to accommodate maintaining reduction temperature along a longer reducing bed and collecting a greater off gas volume. Similar considerations may be made in adapting the segmentation concepts described herein into systems other than RHFs. Example 3 During an additional trial conducted along with the trials of Example 2, energy use of 76 kiloWatts (kW) was measured without port air introduced into the pilot scale RHF. Then, energy use of 45 kW was measured after port air introduction under otherwise the same conditions. The difference represents a 40% reduction in energy. An engineering model for operation with port air at 90% yield estimated a 60% reduction in energy by adding port air to combust gaseous P and CO in the reaction chamber. Elemental Phosphorus Production Off gas from a reducing bed of phosphatic agglomerates initially contains CO and elemental phosphorus in the form of gaseous P. The reaction may be performed under reducing conditions to decrease oxidation of gaseous P so that collected off gas still contains elemental phosphorus.FIG.9shows incorporation of an elemental phosphorus condenser into the RHF system, as one example, when desired, as represented with dashed lines. The elemental phosphorus condenser may be incorporated into other systems that produce gaseous P. Instead of oxidizing the phosphorus for phosphoric acid recovery, as shown inFIG.9, the collected off gas may be directed through a phosphorus condenser, as shown inFIG.10, in which chilled water sprays are used to condense elemental phosphorus. This water is drained to a condensate recirculation tank, passes through a chiller unit, and is returned to the condenser. Solid phosphorus precipitates in the condensate liquid stream and settles in a condensate drain tank (not shown) of the phosphorous condenser and/or the condensate recirculation tank. Precipitates are periodically removed to a phosphorus decant tank from which they are removed and stored as elemental phosphorus product. The solid elemental phosphorus can be further purified or converted to phosphoric acid. Condensate water that collects in the decant tank is pumped to a condensate water treatment system. The liquid level in the condensate drain tank or condensate recirculation tank is maintained by adding fresh water as needed. The exhaust gas from the condenser contains some remaining phosphorus along with carbon monoxide. This exhaust gas from the condenser may be further oxidized for heat and/or phosphoric acid recovery. The residual phosphorus gas and carbon monoxide from the phosphorus condenser may be oxidized in an oxidizer by the introduction of oxygen to form phosphorus pentoxide and carbon dioxide gases. Elemental phosphorus gas auto ignites in presence of oxygen, providing the ignition source and heat for combustion of the carbon monoxide. A small quantity of natural gas may be introduced along with oxygen in the oxidizer to compensate for heat losses occurring in the elemental phosphorus condenser. The oxidized phosphorus is then scrubbed in a secondary scrubbing system (not shown) to form phosphoric acid while carbon dioxide gas is released to the atmosphere through the exhaust stack. Example 4 During additional trials conducted along with Example 2, elemental phosphorus was kept in the off gas of the pilot scale RHF by not introducing port air into the RHF or the thermal oxidizer. The resulting elemental phosphorus was recovered using an existing acid plant as a cooler and condenser. Red phosphorus was obtained and ignited once filtered and dried. Co-Product Production The processed agglomerates may provide a companion product to the elemental phosphorus and/or phosphoric acid. This co-product may be in the form of a lightweight aggregate. It is estimated that for every ton of phosphoric acid produced, about 4 to 7 tons of this companion product will be produced. Preliminary tests of this co-product showed substantial benefits, including:1. Lighter weight compared to known aggregate, which decreases the overall weight of concrete products for easier handling, and lower transportation and construction costs.2. High moisture absorption capacity, which can be a source of internal curing for concrete, thus contributing to better quality and enhanced durability.3. Possible pozzolanic characteristics of the finely ground form of this co-product (˜45 μm) can enhance cement hydration in concrete to yield higher strength and greater durability at a lower cost compared to other pozzolanic/cementitious additives such as coal combustion fly ash and blast furnace slag. With limited and dwindling sources of fly ash and slag in the United States, the availability of this co-product in finely ground form has the potential to meet some demands of the concrete industry.4. Lower overall carbon footprint of 0.73 tons CO2/ton co-product versus 1.25 tons CO2/ton cement. Preliminary analysis of the chemical composition and physical properties of this material indicates that they are similar to the specifications for Portland cement, and granulated blast furnace slag and coal combustion fly ash used in concrete and mortars. Example 5 A variety of mortar mixtures were prepared with 100% ordinary Portland cement (OPC) as a control, coal combustion fly ash in OPC as a second control, and ground processed pellets in OPC. The ground pellets were from the high silica (SR≥2.0) and low silica (SR≤0.7) pellets in Example 2 above. Coarsely ground (approximately 67-70% less than 45 μm) and finely ground (approximately 72-80% less than 45 μm) particles of the high silica and low silica pellets were evaluated. Water and ASTM C33 natural silica sand were combined with OPC and fly ash or OPC and ground pellets to form a mortar, which was cured and subjected to compression testing. Table 5 demonstrates the strength potential for co-product processed agglomerates in cement. The high silica pellets generally performed similarly to or better than the 20% fly ash. TABLE 5Average Compressive Strength (psi)Sample3-day7-day28-day90-day100% cement268930704057470420% fly ash230129563393428515% high-silica, fine-grind239535633852494115% high-silica, coarse-grind284332393957495025% high-silica, fine-grind242230773947531925% high-silica, coarse-grind250930033679589915% low-silica, fine-grind15252785370115% low-silica, coarse-grind12392094247725% low-silica, fine-grind15252431342025% low-silica, coarse-grind133124773258 Method, Systems, and Compositions The discoveries described herein identify a number of solutions that may be implemented in methods, systems, and compositions also described herein. Multiple solutions may be combined for implementation, enabling still further methods, systems, and compositions. The inventors expressly contemplate that the various options described herein for individual methods, systems, and compositions are not intended to be so limited except where incompatible. The features and benefits of individual methods herein may also be used in combination with systems, compositions, and other methods described herein even though not specifically indicated elsewhere. Similarly, the features and benefits of individual systems herein may also be used in combination with methods, compositions, and other systems described herein even though not specifically indicated elsewhere. Further, the features and benefits of individual compositions herein may also be used in combination with methods, systems, and other compositions described herein even though not specifically indicated elsewhere. Phosphorus Production Method A includes forming a reducing bed containing feed agglomerates in a reaction chamber by heating the feed agglomerates. The feed agglomerates include a core initially containing phosphate ore and carbonaceous material, the core initially providing a formula weight ratio of silicon dioxide to calcium oxide plus magnesium oxide ranging from 0.3 to 0.7. Method A includes maintaining a temperature in the reaction chamber from 1250 to 1380° C., such as from 1250 to 1350° C., along at least a portion of the reducing bed. Off gas is generated from the reaction chamber, the off gas containing phosphorus in the form of elemental phosphorus and/or phosphorus pentoxide. Method A includes collecting phosphorus from the off gas and removing from the reaction chamber a residue containing processed agglomerates. Less than 20% of the phosphate initially in the feed agglomerates remains in the residue. Additional features may be implemented in Method A. By way of example, Method A may include continuously moving the reducing bed through the reaction chamber with the feed agglomerates substantially stable while in the reducing bed. The reducing bed may be formed on a rotating bed floor in the reaction chamber, such as in an RHF, including on an annular, rotating hearth of the RHF. The heating of the feed agglomerates may include heating the feed agglomerates at the reaction chamber temperature of 1250 to 1380° C., such as 1250 to 1350° C. The heating may occur under a reducing freeboard at least until after a carbo-thermal reduction reaction begins, which forms the reducing bed. The heating of the feed agglomerates may occur together with the maintaining of the temperature of 1250 to 1380° C. One example includes placing ambient temperature feed agglomerates in the reaction chamber maintained at the temperature of 1250 to 1380° C. Alternatively, at least part of the heating could occur separate from the maintaining of the temperature, such as in a part of the reaction chamber not at 1250 to 1380° C. or perhaps even outside the reaction chamber. Accordingly, feed agglomerates preheated elsewhere to above ambient temperature could be placed in the reaction chamber. For any reaction chamber temperatures exceeding 1180° C., the reducing bed may be exposed for less than 60 minutes, such as 45 minutes or less. The feed agglomerates may be heated for 30 minutes to less than 60 minutes, such as 30 to 45 minutes, at the reaction chamber temperature of 1250 to 1380° C. Method A may further include melting at least a portion of the core in at least some of the agglomerates heated at the 1250 to 1380° C. reaction chamber temperature. Method A may further include delivering over-bed air and/or oxygen through a plurality of ports above the reducing bed. From 9 to 10 tons of air may be delivered per ton of phosphate as P2O5input to the chamber. The reaction chamber used in Method A may include a barrier wall segmenting the reaction chamber into a reduction zone differentiated from a preheat zone and one or more over-bed air and/or oxygen ports above the reducing bed in the reduction zone, but not in the preheat zone. Method A may further include delivering over-bed air and/or oxygen to the reduction zone through the one or more ports, but not delivering over-bed air and not delivering over-bed oxygen to the preheat zone. The phosphate ore used in Method A may contain silicon dioxide and the core initially might not contain supplemental silicon dioxide in addition to the silicon dioxide in the phosphate ore. Alternatively, supplemental silicon dioxide may be included in the initial core. The core may initially provide a phosphate content of greater than 13 weight % as P2O5, such as at least 17 wt %, including 17 to 20 wt %. The feed agglomerates may further include a protective coating on the core, the coating containing carbonaceous material particles. The coating may have a thickness from 0.5 to 0.7 millimeters or provide about 1-3 wt % extra carbon to the initial core. In Method A, less than 15% of the phosphate initially in the feed agglomerates might remain in the residue, such as less than 10%, including less than about 7%. Method A may further include exothermically oxidizing elemental phosphorus and carbon monoxide in the off gas while still in the reaction chamber, thereby adding heat to the reducing bed. The processed agglomerates produced in Method A may contain phosphate ore residue and calcium silicate and exhibit pozzolanic properties suitable for supplementary cementitious material at least when ground to a particle size of approximately 45 micrometers. In Method A, the feed agglomerates in the reducing bed may be below a reducing freeboard and the phosphorus in the off gas may be in the form of elemental phosphorus. Then, Method A may further include oxidizing elemental phosphorus outside of the reaction chamber to phosphorus pentoxide, the collecting of the phosphorus from the off gas including collecting the phosphorus pentoxide as phosphoric acid. Instead, or in addition, Method A may further include collecting elemental phosphorus from the off gas as elemental phosphorus. The described additional features of Method A may also be implemented in Methods B and E below. System C and Composition D below may be used in Method A and Composition F below may be produced by Method A. Phosphorus Production Method B includes forming a reducing bed containing feed agglomerates in a reaction chamber by heating the feed agglomerates. The feed agglomerates include a core initially containing phosphate ore and carbonaceous material. Method B includes continuously moving the reducing bed through the reaction chamber with the feed agglomerates substantially stable while in the reducing bed. A temperature is maintained in the reaction chamber from 1250 to 1380° C., such as from 1250 to 1350° C., along at least a portion of the reducing bed. Off gas is generated from the reaction chamber, the off gas containing phosphorus in the form of elemental phosphorus and/or phosphorus pentoxide. Method B includes collecting phosphorus from the off gas and removing from the reaction chamber a residue containing processed agglomerates. Additional features may be implemented in Method B. By way of example, the core may initially provide a formula weight ratio of silicon dioxide to calcium oxide plus magnesium oxide ranging from 0.3 to 0.7. Instead, the core may initially provide a formula weight ratio of silicon dioxide to calcium oxide plus magnesium oxide higher than 1.6, such as 2.0 and higher, including from 2.0 to 2.5. Less than 20% of the phosphate initially in the feed agglomerates might remain in the residue, such as less than 15%, including less than 10%, for example, less than about 7%. The described additional features of Method A above may also be implemented in Method B. The described additional features of Method B may also be implemented in Method E below. System C and Composition D below may be used in Method B and Composition F below may be produced by Method B. Phosphorus Production System C includes a reaction chamber, a barrier wall segmenting the reaction chamber into a reduction zone differentiated from a preheat zone, and a bed floor at a bottom of the reaction chamber. The bed floor is configured to move continuously from the preheat zone to the reduction zone during operation while keeping feed agglomerates thereon substantially stable at least while in the reduction zone. System C includes one or more direct-fired burners in the reduction zone, but not in the preheat zone, and one or more over-bed air and/or oxygen ports above the bed floor in the reduction zone, but not in the preheat zone. One or more indirect heating sources are in the preheat zone. Additional features may be implemented in System C. By way of example, the preheat zone may be configured to maintain a reducing freeboard during a carbo-thermal reduction reaction among feed agglomerates on the bed floor. The bed floor may be a rotating bed floor, such as in an RHF, for example, an annular, rotating hearth of the RHF. The one or more indirect heating sources may include electric heating elements and/or radiant tube burners. System C may further include a second barrier wall further segmenting the reaction chamber into a cooling zone differentiated from the reduction zone. The bed floor may be configured to move continuously from the reduction zone to the cooling zone during operation. The cooling zone may lack the direct-fired burners, the over-bed air and oxygen ports, and the indirect heating sources. The bed floor may be a rotating bed floor and System C may further include a third barrier wall further segmenting the reaction chamber and differentiating the cooling zone from the preheat zone. The bed floor may be configured to move continuously from the cooling zone to the preheat zone during operation. The described additional features of System C may also be used in Methods A and B above and in Method E below. System C may process Composition D below. Composition F below may result from methods carried out in System C. Composition D, a phosphate ore feed agglomerate, includes a core containing phosphate ore and carbonaceous material. The core provides a formula weight ratio of silicon dioxide to calcium oxide plus magnesium oxide ranging from 0.3 to 0.7 and a phosphate content of greater than 13 weight % as P2O5. Additional features may be implemented in Composition D. By way of example, the phosphate ore in Composition D may contain silicon dioxide and the core does not contain supplemental silicon dioxide in addition to the silicon dioxide in the phosphate ore. Alternatively, supplemental silicon dioxide may be included in the initial core. The core may provide a phosphate content of at least 17 wt %, including 17 to 20 wt %. The feed agglomerates may further include a protective coating on the core, the coating containing carbonaceous material particles. The coating may have a thickness from 0.5 to 0.7 millimeters or provide about 1-3 wt % extra carbon to the initial core. The core may contain from 8 to 10 wt % green petroleum coke as the carbonaceous material. The phosphate ore and carbonaceous material may be approximately homogeneously distributed phosphate ore particles and carbonaceous material particles. The supplemental silicon dioxide may be approximately homogeneously distributed silica particles. The described additional features of Composition D may also be used in Methods A and B above and in Method E below. System C above may process Composition D. Composition F below may result from methods that process Composition D. A Method E for producing a reduction product includes forming a reducing bed containing feed agglomerates in a reaction chamber by heating the feed agglomerates. The feed agglomerates include a core initially containing an oxidizing agent and a reducing agent. Method E includes continuously moving the reducing bed through the reaction chamber with the feed agglomerates substantially stable while in the reducing bed. A temperature is maintained in the reaction chamber along at least a portion of the reducing bed partly by adding heat from a first heat source. Gaseous products are generated that enter a freeboard over the reducing bed from a reduction-oxidation reaction occurring in the reducing bed, the gaseous products containing a reduction product from reduction of the oxidizing agent and an incompletely oxidized oxidation product from oxidation of the reducing agent. Method E includes exothermically oxidizing the reduction product in the freeboard while still in the reaction chamber and exothermically further oxidizing the incompletely oxidized oxidation product in the freeboard while still in the reaction chamber, thereby adding heat to the reducing bed from the freeboard as a second heat source to reach the temperature in the reaction chamber. Method E includes collecting oxidized reduction product and/or remaining, unoxidized reduction product, if any, from the off gas and removing from the reaction chamber a residue containing processed agglomerates. Additional features may be implemented in Method E. By way of example, the reducing agent may be carbon, the reduction-oxidation reaction may be a carbo-thermal reduction reaction, the incompletely oxidized oxidation product may be carbon monoxide, and the carbon monoxide may be exothermically further oxidized to form carbon dioxide. The oxidizing agent may be phosphate, the reduction product may be phosphorus, and the phosphorus in the off gas may be exothermically oxidized to form phosphorus pentoxide. The phosphate may be comprised by phosphate ore containing silicon dioxide and the core initially might not contain supplemental silicon dioxide in addition to the silicon dioxide in the phosphate ore. Alternatively, supplemental silicon dioxide may be included in the initial core. The temperature in the reaction chamber may range from 1250 to 1380° C., including from 1250 to 1350° C. The core may initially provide a formula weight ratio of silicon dioxide to calcium oxide plus magnesium oxide ranging from 0.3 to 0.7. Instead, the core may initially provide a formula weight ratio of silicon dioxide to calcium oxide plus magnesium oxide higher than 1.6, such as 2.0 and higher, including from 2.0 to 2.5. Less than 20% of the phosphate initially in the feed agglomerates might remain in the residue, such as less than 15%, including less than 10%, for example, less than about 7%. The heating of the feed agglomerates may include heating the feed agglomerates at the reaction chamber temperature. The heating may occur under a reducing freeboard at least until after a carbo-thermal reduction reaction begins, which forms the reducing bed. The heating of the feed agglomerates may occur together with the maintaining of the temperature. One example includes placing ambient temperature feed agglomerates in the reaction chamber maintained at the temperature. Alternatively, at least part of the heating could occur separate from the maintaining of the temperature, such as in a part of the reaction chamber not at the temperature or perhaps even outside the reaction chamber. Accordingly, feed agglomerates preheated elsewhere to above ambient temperature could be placed in the reaction chamber. For any reaction chamber temperatures exceeding 1180° C., the reducing bed may be exposed for less than 60 minutes, such as 45 minutes or less. The feed agglomerates may be heated for 30 minutes to less than 60 minutes, such as 30 to 45 minutes, at the reaction chamber temperature. Method E may further include melting at least a portion of the core in at least some of the agglomerates heated at the reaction chamber temperature. The described additional features of Methods A and B above may also be implemented in Method E. System C and Composition D above may be used in Method E and Composition F below may be produced by Method E. Composition F, a supplementary cementitious material (SCM), includes a flowable particulate material containing phosphate ore residue and calcium silicate and exhibiting pozzolanic properties suitable for SCM. Additional features may be implemented in Composition F. By way of example, 60% or more, such as 60 to 80%, of the flowable particulate material has a particle size less than 45 μm. The flowable particulate material may contain about 20-40% CaO and about 32-66% SiO2. A method for making a cement-containing product may include supplementing the addition of Portland cement with the SCM. The described additional features of Composition F may also be used in Methods A, B, and E above. System C above may produce processed agglomerates suitable for forming Composition F. Composition F may result from methods that process Composition D above. Although minima and maxima are listed for the above described ranges and other ranges designated herein, it should be understood that more narrow included ranges may also be desirable and may be distinguishable from prior art. Also, processing principles discussed herein may provide an additional basis for the lesser included ranges. In compliance with the statute, the embodiments have been described in language more or less specific as to structural and methodical features. It is to be understood, however, that the embodiments are not limited to the specific features shown and described. The embodiments are, therefore, claimed in any of their forms or modifications within the proper scope of the appended claims appropriately interpreted in accordance with the doctrine of equivalents. TABLE OF REFERENCE NUMERALS FOR FIGURES 10rotary hearth furnace12reaction chamber14roof16inner sidewall18outer sidewall20floor22hearth26upper refractory28lower refractory30hearth table32sprocket34seal trough35seal trough36seal wall37seal wall38support frame40track42gear box44motor46wheel48wheel bracket50barrier wall52barrier wall54barrier wall60burner62burner64burner66burner70port72port74port76port80screw conveyor82discharge90vent92vent94vent96off gas direction98bed direction | 68,594 |
11858812 | DETAILED DESCRIPTION OF THE INVENTION Described in detail below are the monolithic carbon foam, the fractal carbon foam, the methods of preparing them, and the supercapacitors constructed from them as set forth in the SUMMARY section above. For purposes of the present disclosure, the term “onion-like carbon nanoparticles” or “OLC nanoparticles” refers to quasi-spherical nanoparticles consisting of fullerene-like carbon layers enclosed by concentric graphitic shells. They exhibit unique zero-dimensional spherical or concentric shell structures with small (e.g., <200 nm, <50 nm, and 1 nm to 100 nm) diameters. They are also commonly referred to as nano-onions. These nanoparticles have properties different from other carbon nanostructures such as graphite, nanodiamonds, and nanotubes. Furthermore, the term “spark plasma sintering” or “SPS” refers to a pressure-assisted pulsed-current or direct current process in which powder samples are loaded in an electrically conducting die and sintered under a uniaxial pressure. Spark plasma sintering is a technique that uses pressure-driven powder consolidation in which a pulsed direct electric current passes through a sample compressed in a mold. It is also known as field-assisted sintering or pulse electric current sintering. The term “hot-press” refers to a process that supplies thermal energy from an external heating source to a sample with applied pressure. SPS as used in this invention reduces processing time (e.g., 2 seconds to 30 minutes) as compared to conventional hot-press processes (e.g., at least an hour). The term “monolithic carbon foam” (“MCF”) refers to a material prepared by SPS using onion-like carbon nanoparticles, the term “monolithic carbon foam powder” refers to the powder formed by crushing monolithic carbon foam by any known means, and the term “fractal carbon foam” refers to a carbon foam formed from monolithic carbon foam powder. The term “volumetric micropore surface area” is the resultant difference of BET area and external surface area, obtained by multiplying the specific micropore surface area (m2/g) by the material density (g/cc). Its measurement is described in detail in Galarneau et al., Langmuir 34 (47), 14134-42 (2018). To reiterate, a monolithic carbon foam of this invention (i) is formed of a plurality of OLC nanoparticles fused together and having interconnected pores, (ii) has a volumetric micropore surface area of 200 m2/cc-600 m2/cc, and (iii) has an electrical conductivity of 20 s/cm-140 s/cm. The foam can be prepared by first compacting OLC nanoparticles and then subjecting the compacted OLC nanoparticles in a vacuum or inert gas environment or in a space filled with an inert gas to a SPS process at a pressure of 30 MPa-1000 MPa and a temperature of 300° C.-800° C. for 2 seconds-30 minutes. In one embodiment, the monolithic carbon foam thus prepared contains micropores, mesopores, and, optionally, macropores, which, respectively, have diameters of 0.723 nm-2 nm, 2 nm-50 nm, and >50 nm. In another embodiment, the monolithic carbon foam has a volumetric micropore surface area higher (e.g., 500%-1435%) than that of the OLC nanoparticles and its material density increases (e.g., 0.1 g/cc to 1.2 g/cc, 0.4 g/cc to 1.2 g/cc, 0.1 g/cc to 1 g/cc, 0.5 g/cc to 1 g/cc, and 0.55 g/c to 1 g/cc) with respect to the OLC nanoparticles, whereas its gravimetric total surface area decreases minimally (e.g., from 1200 m2/g to 857 m2/g) also with respect to the OLC nanoparticles. The void fraction of the monolithic carbon foam can range from 30% to 80%, preferably 40% to 70%, and more preferably 45% to 60%. The term “void fraction” refers to the percentage of the volume of voids over the total volume. OLC nanoparticles are used as a starting material. Preferred OLC nanoparticles are amorphous onion-like carbon (“a-OLC”) nanoparticles having a void fraction of 50% or greater (e.g., 50% to 90% and 60% to 80%) and an average diameter of 2 nm to 50 nm (e.g., 5 nm to 40 nm, 20 nm to 40 nm, and 34 nm). The a-OLC nanoparticles each have a hollow sphere structure containing turbostratic graphene layers that are loosely bonded with each other in a disordered manner. Turbostratic graphene layers contain multiple graphene layers (e.g., 2 layers to 100 layers) which are electronically decoupled to allow interlayer rotation and exfoliation. Commercially available a-OLC nanoparticles include those sold under the trade names of Ketjenblack® EC300J (Lion Specialty Chemicals Co., Tokyo, Japan) and Super Conductive Carbon Black Ketjenblack® EC-600JD (Shanghai Tengmin Industry Co., Shanghai, China). Ketjenblack® EC300J has a dibutyl phthalate absorption number (“DBP”) absorption of 360 cm3/100 g, a BET surface area of 800 m2/g, an average diameter of 80 nm, a void fraction of 60%, and a volume resistivity of 3.9 Ω·cm. On the other hand, Ketjenblack® EC-600JD has a DBP absorption of 495 cm3/100 g, a BET surface area of 1270 m2/g, an average diameter of 78 nm, a void fraction of 80%, and a volume resistivity of 1×108Ω·cm. When subjected to the spark plasma sintering (SPS) of this invention, a-OLC nanoparticles are readily deformed into monolithic carbon foam having OLC nanoparticles fused together and interconnected pores. Not to be bound by theory, SPS exerts a gradient pressure and current-induced Joule heating on a-OLC nanoparticles, which are transformed into fused OLC nanoparticles. The monolithic carbon foam thus prepared has a diamond-like core, a crumpled graphene layer, a conductive graphite layer, or any combination thereof. Preferably, it has a diamond-like core and one or two outer layers: e.g., a crumpled graphene layer and a conductive graphite layer. In one example, the monolithic carbon foam has a crumpled graphene layer covering a diamond-like core. In another example, it has a conductive graphite layer covering a diamond-like core. In a preferred structure, the monolithic carbon foam has a diamond-like core, a crumpled graphene outer layer, and a conductive graphite middle layer, the conductive graphite middle layer is in contact with the crumpled graphene outer layer and the diamond-like core. Under the SPS gradient pressure and Joule heating, a-OLC nanoparticles are compacted and undergo rolling, sliding, and partial exfoliation to form monolithic carbon foam having a superior conductivity and a great hardness. On the surface of fused a-OLC nanoparticles, a graphene layer is partially exfoliated and crumpled via friction with neighboring nanoparticles to form the crumpled graphene outer layer containing a single layer of sp2carbon atoms arranged in a two-dimensional nanostructure. At the same time, interconnected pores are generated, thus increasing volumetric surface area. The SPS gradient pressure increases greatly in inner parts of the fused a-OLC nanoparticles. The pressure is strong enough to compress the middle graphene layers to form a conductive graphite middle layer, which contributes to the superior electrical conductivity of the monolithic carbon foam. Both the graphene layer and the graphite layer contain sp2carbon atoms connecting to each other covalently within a graphene plane. The SPS gradient pressure is the greatest in the core of the fused a-OLC nanoparticles. In combination with current induced Joule heating, it compresses the core into a diamond-like core having a sp3rich backbone (e.g., containing sp3carbon atoms at a level of at least 5%, at least 10%, 5-95%, or 10-90%). Indeed, SPS has been used to synthesize diamond from carbon nanomaterials. See Luo et al., Sci Rep 5, 13879 (2015); Shen et al., Nanotechnology 17, 2187-91 (2006); and Zhang et al., Chemical Physics Letter 510, 109-114 (2011). The relative abundance of sp2and spacarbon atoms can be determined by known methods such as X-ray photoelectron spectroscopy. See, e.g., Speranza et al., Diamond and Related Materials 13, 445-450 (2004). The diamond-like core gives rise to an exceptional Vickers hardness Hv of the monolithic carbon foam as high as 950 MPa (e.g., 18 MPa to 935 MPa, 50 MPa to 800 MPa, and 100 MPa to 400 MPa). The monolithic carbon foam can be a hybrid monolithic carbon foam, namely, a doped monolithic carbon foam that includes a carbon-based material (e.g., activated carbon), an oxide material (e.g., molybdenum oxide), a metal, and a semiconductor material (e.g., silicon and molybdenum disulfide). The material can be in the form of fibers, tubes, hollow spheres, 2D materials, or powders. In a preferred embodiment, the material is 2D molybdenum disulfide (MoS2). In another preferred embodiment, the material is silicon nanoparticles. Other materials can be used in the SPS process in place of OLC nanoparticles. Examples include carbon nanotubes (single walled or multiwalled), carbon nanofibers, activated carbons, graphene oxide, reduced graphene oxide, graphite flake, amorphous carbon. Further covered by this invention is a fractal carbon foam prepared from the above-described monolithic carbon foam by crushing the monolithic carbon foam to form a monolithic carbon foam powder; compacting the monolithic carbon foam powder, placing the compacted monolithic carbon foam powder in a vacuum or inert gas environment or in a space filled with an inert gas, and subjecting the monolithic carbon foam powder to a SPS process at a pressure of 30 MPa-1000 MPa and a temperature of 300° C.-800° C. for 2 seconds-30 minutes. Typically, the fractal carbon foam of this invention has a hierarchical pore structure, i.e., including interconnected micropores, mesopores, and macropores. The micropores, the mesopores, and the macropores, respectively, have diameters of 0.723 nm-2 nm, 2 nm-50 nm, and >50 nm. A hybrid fractal carbon foam, another contemplated invention, can be formed from the hybrid monolithic carbon foam described above. Preferably, the monolithic carbon foam, the hybrid monolithic carbon foam, the fractal carbon foam, and the hybrid fractal carbon foam described above are free-standing and free of a binder. The term “free-standing” refers to non-attachment of the above materials to any additional components, e.g., a substrate or any other support. One or more binders can be used to provide stronger binding among nanoparticles, monolithic carbon foams, fractal carbon foams, and hybrid fractal carbon foams. The term “binder” covers materials that assist in the adhesion of nanoparticles such as a-OLC nanoparticles and fused OLC nanoparticles. Suitable binders include carboxymethyl cellulose (“CMC”, styrene butadiene rubber (“SBR”), polyvinylidene fluoride (“PVDF”), polytetrafluoroethylene (PTFE), polyimide, sodium silicate, and ammonium polyphosphate. The monolithic carbon foam and the fractal carbon foam described above are useful in many applications (such as water purification, filtration, catalysts, pseudocapacitors, batteries, carbon capture products, and electrolysis), which require stable materials with high volumetric active surface areas. They are also suitable for energy storage devices due to their high conductivity and great ion accessibility, properties attributable to their unique interconnected pores. Energy storage devices include supercapacitors, pseudocapacitors, and batteries. Also within the scope of this invention is an electrode for use in an energy storage device, the electrode containing an active material made of the monolithic or fractal carbon foam described above. Slurry-based electrodes are also contemplated. These electrodes can be fabricated by coating of slurry that contains 70-95% of MCF powder, 5-20% of a binder, and 0-10% of conducting agent on a current collector. The binders are described above. An energy storage device includes such a negative electrode and such a positive electrode, a separator disposed between the negative and positive electrodes to prevent a short circuit by direct contact thereof, and an electrolyte ionically connecting the electrodes, in which the inner surface of each electrode contacts with the electrolyte and the outer surface of each electrode is covered by a current collector. A suitable material, such as an Al laminated file, can be used to package the energy storage device. A traditional electrode can also be used as a negative or positive electrode as long as one of the negative and positive electrodes is the electrode of this invention. A pseudocapacitor contains a composite material prepared from a MCF or FCF together with a pseudocapacitive material including metal oxides, transition metal carbides (MXenes), transition metal carbonitrides, and conducting polymers, e.g., MnO2, RuO2, MoO3, V2O5, T-Nb2O5, Ti3C2Tx, Ti3C2, Nb2O5, LiTiNb2O7, Li3VO4, polypyrrole, and poly(3,4-ethylenedioxy-thiophene). The composite material typically contains 50-80% of the pseudocapacitive material and 20-50% of a MCF or FCF of this invention. Useful electrolytes include organic solvents such as acetonitrile, propylene carbonate, sulfolane, tetrahydrofuran, diethyl carbonate, γ-butyrolactone, and solutions with quaternary ammonium salts or alkyl ammonium salts, e.g., tetraethylammonium tetrafluoroborate (N(Et)4BF4), triethyl (methyl) tetrafluoroborate (NMe(Et)3BF4), 5-azoniaspiro[4.4]nonane, and tetrafluoroborate(1-) (SBPBF4). Aqueous electrolytes are also useful, e.g., water solutions of acids such as sulfuric acid (H2SO4), alkalis such as potassium hydroxide (KOH), and salts such as quaternary phosphonium salts, sodium perchlorate (NaClO4), lithium perchlorate (LiClO4), and lithium hexafluoride arsenate (LiAsF6). Additional electrolytes include ionic liquids such as 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF4) and 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4). Without further elaboration, it is believed that one skilled in the art can, based on the above description, utilize the present invention to its fullest extent. The following specific examples are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. All publications, including patent documents, cited herein are incorporated by reference in their entirety. Example 1 Preparation and Characterization of Non-doped Monolithic Carbon Foams Preparation of Monolithic Carbon Foams Non-doped monolithic carbon foams were prepared according to the process shown inFIG.1A(100) and described below. Briefly, OLC nanoparticles (Ketjenblack® EC-600JD, LION Specialty Chemicals Co., Ltd.) of a desired weight (102) were compacted in a mold (104). Subsequently, the compacted OLC nanoparticles were loaded into a SPS chamber, which was then evacuated to subject these nanoparticles to a vacuum (106). Thereafter, the OLC nanoparticles were spark plasma sintered under desired conditions (e.g., a pressure of 110 MPa and a temperature of 600° C. for 30 minutes) (108and110) to generate a monolithic carbon foam. A conventional paste-based coating process was optionally used to form a thin film (<100 μm) before the SPS process. The pressure in the SPS chamber was then reestablished at atmospheric pressure, after which the monolithic carbon foam was removed from the SPS chamber (112). As illustrated inFIG.1B, during the SPS process, the OLC nanoparticles were crushed and restructured through fusing neighboring nanoparticles, thereby resulting in a monolithic carbon foam that was free-standing and was free of a binder. More specifically, the uniaxial pressure applied to the OLC nanoparticles during this process induced particle sliding and frictional force between the nanoparticles, which in turn, led to the crushing and exfoliating of these nanoparticles, thus generating the microporous surface of the monolithic carbon foam. It was unexpected that the localized energy generated by the SPS process induced strong and conductive interparticle bonding in the resulting carbon foam. Material Density and Volumetric Micropore Surface Area In general, conventional sintering processes lower the surface area of a sample while increasing its material density. By contrast, as shown in Table 1 below, while the above-described process resulted in monolithic carbon foams having increased densities as compared to OLC nanoparticles, the gravimetric micropore surface and volumetric micropore surface areas of micropore of these foams were unexpectedly higher than those of the nanoparticles. For example, the OLC nanoparticles had a density of 0.1 g/cc and volumetric micropore surface area of 34.6 m2/g, whereas a monolithic carbon foam, having a density of 1 g/cc, had a volumetric micropore surface area of 497.47 m2/g. In other words, the process of this invention increased the volumetric micropore surface area of the OLC nanoparticles from 34.6 m2/cc to 497.47 m2/cc, i.e., a 1435% enhancement. By contrast, carbon black and graphite flakes, two materials commonly used for energy storage, lost their volumetric micropore surface areas after a similar SPS treatment by 100% and 37%, respectively. More importantly, the material density could be tuned to fall in the range of 0.4 g/cc to 1.2 g/cc when SPS was operated at a predetermined temperature and a predetermined pressure. TABLE 1Gravimetric and volumetric surface areas of SPS-processedmonolithic carbon foamsMonolithicMonolithicMonolithicOLCcarboncarboncarbonnano-foamfoamfoamparticlesMCF1MCF2MCF3(0.1 g/cc)(0.55 g/cc)(0.75 g/cc)(1 g/cc)Gravimetric346.57453.72479.25497.47microporesurface area<2 nm (m2/g)Gravimetric total11741083945857surface area(m2/g)Volumetric34.6249.546359.4375497.47microporesurface area<2 nm (m2/cc)Volumetric total117.4595.65708.75857.00surface area(m2/cc) Interconnected Pores The above-described process provides monolithic carbon foams having micropores and mesopores at various ratios, which are preferred for different applications. For example, a higher percentage of micropores is preferred for energy storage applications, e.g., supercapacitors and batteries, as it maximizes energy density. On the other hand, a greater percentage of mesopores is preferred for applications requiring higher power density, as it permits faster charging and discharging. A suitable combination of micropores and mesopores is crucial for optimizing both the energy density and the power density of a supercapacitor or a battery. Through the SPS process, the ratio of micropores and mesopores can be controlled by adjusting the temperature and pressure at which the process is performed. For example, as shown inFIG.1C, both the gravimetric and volumetric surface areas of a monolithic carbon foam were enhanced by increasing the temperature, e.g., from 300° C. to 700° C., at which the SPS process was performed, while keeping the pressure at 80 MPa. The micropores and mesopores were interconnected and distributed within the monolithic carbon foam containing fused OLC nanoparticles as shown in an SEM image. SeeFIG.1D. Unlike the starting material a-OLC nanoparticles, fused OLC nanoparticles formed in the SPS process each had a crumpled surface and graphene-like flakes. SeeFIG.1E. Interconnected pores were further studied using quenched solid density functional theory analysis for pores having a size of 10 nm or smaller and using TEM tomography for pores larger than 10 nm. 3D tomographic reconstructions were segmented into carbonaceous and porous regions using MCF1, which had a density of 0.55 g/cc. The 3D pore structure showed a 100% accessibility with the aid of small branching pore connections. The same analyses were performed on MCF3 having a density as high as 1 g/cc. MCF3 had a 97% accessibility, showing only 3% of inaccessible (i.e., isolated) pores. Interestingly, in MCF1 and MCF3, the average distance from a carbonaceous region to its nearest porous region was 7.2 nm and 9.2 nm, respectively. The results suggest that, independent of material density, the extensive mesoporous network in both MCF1 and MCF3 contained a large volume of highly accessible, micropore-rich surface regions. The unique mesoporous network made monolithic carbon foam a suitable material for building a supercapacitor having a high volumetric capacitance. Pore size distribution was obtained through analysis of nitrogen adsorption-desorption isotherms. As a starting material, a-OLC nanoparticles were provided in an agglomerated state, having mesopores sized in the range of 2 nm to 20 nm. The size distribution represents pores having random packing structure. During an SPS treatment, the mesopore sizes of a-OLC nanoparticles decreased in responding to the pressure and the heat applied on the a-OLC agglomerated nanoparticles. A new pore structure was formed having a new size distribution. The results indicate that the new pore structure was a random close packing (“s-RCP”) structure, very different from HCP and BCC structures.FIG.1Fillustrates the pore size distribution of six MCF examples, i.e., MCF4 to MCF9, as compared to the a-OLC agglomerated nanoparticles. MCF4 was prepared following the SPS procedure described above at a temperature of 300° C. and a pressure of 120 MPa. MCF5, MCF6, MCF7, MCF8, and MCF9 each were prepared in a similar way except at a temperature of 400° C., 500° C., 600° C., 700° C., and 800° C., respectively. In these examples, pores of 5 nm to 20 nm decreased in size at a higher SPS temperature. Pores of 2 nm to 5 nm increased in number. In another study, MCF examples were prepared under different pressures and at a constant temperature. It was found that pore sizes were smaller at higher pressures. As such, the SPS method of this invention allows controlling the pore size and its distribution by adjusting SPS temperature and pressure. Chemical Purity Impurities can be introduced to monolithic carbon foam by surface oxidization to form C—O bonds. Chemical purity typically suffers when surface areas increase. XPS analysis shows that monolithic carbon foam of this invention had an intensive carbon peak at 284 eV and an insignificant oxygen peak, indicating that monolithic carbon foam, unlike a-OLC nanoparticles, had a very small amount of C—O bonds. Furthermore, thermogravimetric analysis shows chemical stability of monolithic carbon foam as it had more than 99% weight retention after heating to 1,000° C. in an argon environment. As a comparison, rGO had a weight loss of more than 20% after heating to 800° C. Mechanical Stability A study was performed to compare the mechanical stability of the monolithic carbon foam prepared by the SPS method described above and the carbon foams prepared by three conventional methods, i.e., (1) hot-pressing at 800° C. and 40 MPa, (2) cold-pressing at 1 GPa followed by annealing at 800° C., and (3) cold-pressing at 1 GPa. More specifically, the SPS-processed monolithic carbon foam and the hot-pressed/cold-pressed monolithic carbon foams were sonicated in isopropyl alcohol (IPA) for 5 minutes (sonication power of 600 W). All three samples containing carbon foams prepared by the conventional methods disintegrated and dispersed, as evidenced by tinting of IPA. By contrast, the sample containing SPS-processed monolithic carbon foam remained clear, indicating that this monolithic carbon foam, mechanically stable, was intact after sonication. To quantify the differences in mechanical stability between monolithic carbon foams prepared by the above-described SPS process and carbon foams prepared by the conventional hot-pressing process, a second study was conducted to measure the Young's moduli of monolithic carbon foams prepared by the six processes: (1) MCF10, SPS-processed at 600° C. and 40 MPa, (2) MCF11, SPS-processed at 600° C. and 120 MPa, (3) MCF12, SPS-processed at 800° C. and 40 MPa, (4) MCF13, SPS-processed at 800° C. and 120 MPa, (5) Comparative 1, hot-pressed at 600° C. and 40 MPa, and (6) Comparative 2, hot-pressed at 800° C. and 40 MPa. The results of this study, shown inFIG.2A, demonstrate that the SPS-processed monolithic carbon foams unexpectedly had Young's moduli greater than the hot-pressed carbon foams. The results of these two studies demonstrate the unexpected mechanical stability of SPS-processed monolithic carbon foam of this invention, as compared to carbon foams prepared by prior art methods. Vickers Hardness The Vickers Hv method, well known in the field, was used to test the hardness of the monolithic carbon foam. For a description of this method, see Hintsala et al., JOM 70, 494-503 (2018). Six MCF examples of this invention were prepared, i.e., MCF14-MCF19. The SPS conditions and the results are shown in Table 2 below. MCF19 had a Vickers Hv hardness as high as 935 MPa. Each of MCF14-18 had a high Vickers Hv hardness of 51 MPa to 935 MPa. By contrast, a commercial activated carbon electrode had a Vickers Hv hardness of 71 MPa, only 10% that of MCF19. Nuclear graphite, a material known for its great hardness, had a Vickers Hv hardness of 190 MPa. Of note, nuclear graphite does not contain pores. TABLE 2Vickers hardnessMonolithicSPSSPSVickerscarbonTemperaturePressurehardness Hvfoam° C.MPaMPaMCF1430012051MCF15400120135MCF16500120309MCF17600120325MCF18700120405MCF19800120935AC electrode——71Nuclear graphite——190 Conductivity A different study was conducted to compare the conductivities and densities of the SPS-processed monolithic carbon foams prepared under three conditions, i.e., 800° C. and 20 MPa (i.e., MCF20), 500° C. and 40 MPa (i.e., MCF21), and 600° C. and 40 MPa (i.e., MCF10), with two conventional hot-pressed carbon foams, i.e., hot-pressed at 800° C. and 20 MPa and at 800° C. and 40 MPa. The results of this study, shown in Table 3 below and inFIG.2B, indicate that the SPS-processed monolithic carbon foams, regardless of preparation conditions, unexpectedly had higher conductivities than the hot-pressed carbon foams. Under the same condition, i.e., 800° C. and 20 MPa, the SPS-processed monolithic carbon foams unexpectedly had higher density than the hot-pressed carbon foams. Ten more MCF examples (i.e., MCF22-MCF31) were prepared each using a temperature and a pressure shown in Table 4 below. Their conductivities were measured. See Table 4. Monolithic carbon foam prepared at a higher temperature had a greater conductivity than monolithic carbon foam prepared at a lower temperature. Similarly, monolithic carbon foam prepared at a higher pressure had a greater conductivity as compared to monolithic carbon foam prepared at a lower pressure. TABLE 3Conductivities and densities of SPS-processedmonolithic carbon foams and hot-pressed monolithic carbon foamsSPS-SPS-SPS-Hot-Hot-processedprocessedprocessedpressedpressedMCF20MCF21MCF10(800° C.,(800° C.,(800° C.,(500° C.,(600° C.,20 MPa)40 MPa)20 MPa)40 MPa)40 MPa)Density0.4290.580.50.550.58(g/cc)Conductivity23.9432.1239.314042(S/cm) TABLE 4Conductivities of certain monolithic carbon foamsMonolithicTemperaturePressureConductivitycarbon foam° C.MPaS/cmMCF224008046MCF 235008061MCF246008074MCF257008080MCF2680080112MCF2740012060MCF2850012070MCF2960012088MCF30700120115MCF31800120124 Mesopore Structure The local atomic structure of a fused OLC nanoparticle of MCF26 was studied using electron energy loss spectroscopy (EELS). EELS mapping analysis shows that the fused OLC nanoparticle of MCF had a three-layered structure, namely, a crumpled graphene outer layer, a graphite middle layer, and a diamond-like core. The crumpled graphene outer layer formed the surface of the MCF nanoparticle facing mesopores. It had the lowest density among the three layers. Further, sp2orbitals dominated this layer as shown inFIG.1G, which was obtained using low-loss EELS and core-loss EELS of carbon K edge, respectively. The graphene layer, crumpled and exfoliated, was observed without stacking order. The crumpled graphene outer layer gave rise to MCF's high micropore surface area and chemical stability. Covered by the crumpled graphene outer layer was the graphite middle layer, which was highly conductive and had a density greater than the crumpled graphene outer layer. The EELS spectrum shows blueshift in the peak positions in comparison to those of the crumpled graphene outer layer, indicating the start of graphitic ordering due to the onset of interlayer interactions as described in Nelson et al., Nano Lett 14, 3827-31 (2014). As graphite is highly conductive, this graphite middle layer contributed to the high conductivity. Further, EELS mapping analysis shows a linear increase of an absolute intensity, confirming the increase of material density as compared to the crumpled graphene layer. Underneath the conductive graphite middle layer was the diamond-like core, where the intensity of π→σ* increased and that of π→π* decreased, indicating that, unlike the outer and middle layers, the core had an spaorbitals-rich structure. Indeed, the EELS spectrum of the diamond-like core is similar to that of the neutron-irradiated graphite used in nuclear reactors as described in Brown, Carbon (New York) 6, 27-30 (1968). It is well known that neutron irradiation deforms the graphite structure into a diamond-like structure, thereby increasing its hardness and compressive strengths. See Neighbour, Journal of Physics D, Applied Physics 33, 2966-72 (2000), and Mason et al., Carbon (New York) 5, 493-506 (1967). Capacitance retention The monolithic carbon foam can be used as an electrode for supercapacitors that do not contain conductive additives and binders. OLC nanoparticles were compacted in a mold. Subsequently, the compacted OLC nanoparticles were loaded into a SPS chamber, which was then evacuated to subject these nanoparticles to a vacuum. Thereafter, the OLC nanoparticles were spark plasma sintered under a pressure of 30 MPa and a temperature of 600° C. for 10 minutes Eliminating conductive additives and binders from an electrode is desirable, as they reduce energy density and hinder performance severely.FIG.3shows an exemplary pouch-cell type supercapacitor containing a monolithic carbon foam electrode (or a fractal carbon foam, preparation of which is described in Example 2 below). The supercapacitor was constructed based on a commercial laboratory test setup for supercapacitor analysis. The capacitance retention of an exemplary supercapacitor, indicative of its lifetime, was compared to a commercial supercapacitor having a binder-based paste coated activated carbon electrode (3.0 V, 70° C., SBPBF4/PC electrolyte). The results are shown in Table 5 below. Of note, capacitance retention was calculated by: Capacitanceafterreliabilitytest(Fg)CapacitanceofAsprepareddevice(Fg)×100 TABLE 5Capacitance retention for supercapacitors containing SPS-processedmonolithic carbon foam or activated carbonLoad time (hrs.)Supercapacitor0150300500SPS-processed100102100100monolithic carbonfoam (%)Activated carbon (%)100858280 As shown in Table 5 above, after a 500-hour reliability test conducted at 3.0 V and 70° C., the supercapacitor containing the monolithic carbon foam unexpectedly had a capacity retention of 100%, whereas the activated carbon device had a capacity retention of only 80%. These results indicate that, unlike the commercial supercapacitor, the monolithic carbon foam-containing supercapacitor is suitable for use at a rated voltage of 3.0 V. Example 2 Preparation and Characterization of a Fractal Carbon Foam A fractal carbon foam was prepared by a procedure adapted from that used to prepare monolithic carbon foams set forth in Example 1 above. More specifically, a monolithic carbon foam was crushed into a powder having a grain size of a few hundred nanometers to a few microns. The monolithic carbon foam powder was then subjected to the SPS process described in Example 1. The fractal carbon foam thus prepared had an interconnected hierarchical pore structure, in which macropores were connected to the mesopores and micropores contained in the monolithic carbon foam powder. Compared to the pore structure of the monolithic carbon foam shown inFIG.4A, which did not contain a macropore-network, the pore structure of the fractal carbon foam shown inFIG.4Bincluded macropore-network that provided a greater pore accessibility. The greater pore accessibility of the fractal carbon foam facilitated diffusion of ions and molecules. Indeed, Nyquist plots of a 100 μm monolithic carbon foam (“MCF”) electrode and a 100 μm fractal carbon foam (“FCF”) electrode (seeFIG.5A, inset) show that the diffusion speed of ions was faster in the FCF electrode, as evidenced by the steeper slope of its Nyquist plot. A study was conducted to compare the device performance of supercapacitors containing different electrode materials, i.e., MCF, FCF, activated carbon, edge free carbon, and reduced carbon oxide (“rGO”). The results are shown inFIG.5B, a Ragone plot. It was found that the fractal graphene foam, while having lower energy density as compared to the monolithic graphene foam, had a higher power density due to its greater pore accessibility. Importantly, both the fractal graphene foam and the monolithic graphene foam had higher energy and power densities as compared to activated carbon, edge free carbon, and rGO. In other words, the carbon foams of this invention, both monolithic and fractal, are unexpectedly superior to the other carbon materials in supercapacitor applications. Example 3 Preparation and Characterization of Hybrid Monolithic Carbon Foams Two hybrid monolithic carbon foams, i.e., a MoS2/carbon hybrid monolithic carbon foam and a Si/carbon hybrid monolithic carbon foam were prepared via procedures described below. For the MoS2/carbon hybrid monolithic carbon foam, a MoS2/carbon precursor material containing Ketjenblack (AkzoNobel; EC600grade) and MoS2was first prepared. Briefly, 10 mg of Ketjenblack and 20 mg of ammonium tetrathiomolybdate (Sigma-Aldrich) were respectively dispersed in 10 mL and 2 mL of N,N-dimethylformamide (“DMF”). Both dispersions were sonicated for 30 minutes, mixed together, and then sonicated for 2 hours to allow for the Ketjenblack to be thoroughly impregnated with ammonium tetrathiomolybdate. The resulting solution was transferred into a 25 mL Teflon-lined stainless steel autoclave and tightly sealed. The autoclave was heated at 200° C. for 15 hours and allowed to cool to room temperature. The resulting MoS2/carbon precursor material was collected by centrifugation and washed with several aliquots of ethanol and deionized water. The washed precursor material was dried overnight in an oven at 60° C. To obtain the MoS2/carbon hybrid monolithic carbon foam, a spray-gun was connected with a nitrogen gas supply and mounted at 10 cm from the tip of the nozzle above a hotplate, where Mo circular foils (Alfa Aesar; 14 mm diameter, effective area ˜1.4 cm2) were secured with heat resistance tape. The Mo foils were used as current collectors. The MoS2/carbon precursor material was dispersed in DMF and used as the feedstock for spraying. The hotplate was heated at 190° C. to dry the Mo foils. Mass loading of up to 1 mg/cm2was obtained by varying the duration of spraying. To perform the SPS process, the electrodes were sandwiched between graphite foils then loaded into a tungsten carbide mold. SPS was conducted at 500° C. and 600° C. with a uniaxial pressure of 2-30 MPa for 30 minutes under vacuum. The mold was cooled rapidly afterwards with the cooling water system in the furnace, after which the hybrid monolithic carbon foam thus formed was removed from it. The resulting MoS2/carbon hybrid monolithic carbon foam was characterized by Raman spectroscopy, which confirmed the presence of both MoS2and carbon in the foam. SeeFIG.6. For the Si/carbon monolithic carbon foam, a precursor solution containing Si nanoparticles (“SiNP”), trimethoxymethylsilane (“TMMS”), and Ketjenblack was first prepared prior to the SPS process. More specifically, 20 mg Si nanopowder (US Research Nanomaterials, Inc.; diameter=30 nm-50 nm) was dispersed in 40 ml ethanol by batch sonication for 2 hours, after which 1 mL of TMMS (Sigma Aldrich; 98%) was added to the solution and sonicated for 1 hour. Subsequently, 6.6 mg of Ketjenblack (AkzoNobel; EC600grade) was dispersed in 40 ml of isopropyl alcohol (“IPA”) for 2 hours to obtain a homogeneous solution. The two solutions were then mixed together and sonicated for 1 hour to obtain a well-dispersed SiNP/TMMS/Ketjenblack precursor solution. To obtain the Si/carbon hybrid monolithic carbon foam, Mo circular foils (Alfa Aesar; 14 mm diameter, effective area ˜1.4 cm2) were placed on a hotplate heated set to 50° C. A spray-gun was then connected with a nitrogen gas supply and mounted at 10 cm (from the tip of the nozzle) above the hotplate. The SiNP/TMMS/Ketjenblack precursor solution was slowly sprayed on the Mo foil to drive out ethanol and IPA, thereby obtaining a Si/Ketjenblack films on the foil. The Si/Ketjenblack films were then subjected to the SPS process, which was performed at 800° C. and a uniaxial pressure of 2-30 MPa for 30 minutes under vacuum. The cycling performance of the two hybrid monolithic carbon foams as electrodes in Li-ion batteries were tested. It was found that these two hybrid foams unexpectedly retained high capacity after as many as 800 cycles, indicating that these materials are excellent electrode materials for Li-ion battery applications. Example 4 Preparation of Supercapacitors Supercapacitors of this invention were fabricated using both the MCF1 as prepared above and commercially available SBPBF4/PC electrolyte. They were compared with commercially available supercapacitors that were activated carbon (“AC”)-based having a density of 0.5 g/cc and containing the same electrolyte. According to the International Electrotechnical Commission standards 62391-1 and -2, the supercapacitor performance (e.g., device lifetime) was evaluated at a high temperature and the maximum working voltage. See Kotz et al., Journal of Power Sources 195, 923-928 (2010), and Weingarth et al., Journal of Power Sources 225, 84-88 (2013). Device lifetime is defined as the maximum time period during which a supercapacitor retains at least 70% of its initial capacitance as a function of the maximum working voltage and the maximum temperature allowable for its use. At 2.5V, 70° C., and 1 A/g discharge rate, the MCF supercapacitor of this invention retained 82% of its initial capacitance after 4,000 hours of testing. By contrast, the AC supercapacitor dropped below 70% after 1,500 hours. SeeFIG.7. By extrapolating, the MCF supercapacitor lifetime was estimated to be 10,000 hours, almost 10 folds that of the AC supercapacitor. Tested under harsh conditions, e.g., at 3V/70° C. and at 2.5V/100° C., the MCF supercapacitor retained 92.5% and 78%, respectively, of its capacitance after 1,000 hours. By contrast, the AC supercapacitor failed at 140 hours and 55 hours, under the same two conditions. The MCF supercapacitor also had a superior performance in the electrochemical impedance spectroscopy (“EIS”) measurement. It preserved the typical Nyquist plots of a supercapacitor with an equivalent series resistance (“ESR”) change of 100% at 1 kHz and up to 2.5V/100° C. As a comparison, the AC supercapacitor had a 300% increase at 3V/70° C. and completely lost its shape at 2.5V/100° C. The results indicate that MCF supercapacitor of this invention has a better power performance than the AC supercapacitor. Two supercapacitors of this invention were prepared, one using a fractal MCF (“FCF”, density 0.9 g/cc), and another using a he-MCF (1 g/cc). They were then tested to establish their performance limits, namely, maximum device working voltages for high volumetric device performance at room temperature. Both supercapacitors retained 100% capacitance at room temperature for 400 hours during the voltage up to 3.5V. As expected, the scan rate performance depended on material density. At low scan rates (e.g., 0.1 A/g), capacitances are similar for both supercapacitors. At high scan rates (e.g., higher than 1 A/g), FCF shows higher capacitances than the he-MCF, indicating higher ion diffusion rate. The same phenomenon was also observed. See the inset ofFIG.5Afor the Nyquist plots of the electrodes prepared from 100 um of MCF and FCF.FIG.5Ashows a comparison of ion diffusion speeds between the high-density MCF supercapacitor and the FCF supercapacitor, where faster diffusion was associated with a steeper characteristic slope. As the FCF had a lower material density, it had more sub-micron sized, well-connected macropores as compared to the high-density MCF. Volumetric Ragone plots were obtained for both the high-density MCF supercapacitor and the FCP supercapacitor, as well as commercially available AC supercapacitors and graphene based supercapacitors. SeeFIG.5B. The high-density MCF supercapacitor had a maximum volumetric device energy density of 34 Wh·L−1at 3.5 v and room temperature. The FCF supercapacitor had a maximum device power density of 30 kW-L−1, also at 3.5 v and room temperature. It is possible to increase these numbers depending on specific uses. In particular, the energy density can be greatly improved by designing MCF using a predetermined temperature and a predetermined pressure in the SPS preparation method. OTHER EMBODIMENTS All of the features disclosed in this specification may be combined in any combination. Each feature disclosed in this specification may be replaced by an alternative feature serving the same, equivalent, or similar purpose. Thus, unless expressly stated otherwise, each feature disclosed is only an example of a generic series of equivalent or similar features. Further, from the above description, one skilled in the art can easily ascertain the essential characteristics of the present invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. Thus, other embodiments are also within the claims. | 42,046 |
11858813 | DETAILED DESCRIPTION In the following description numerous specific details are set forth to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced without limitation to some or all these specific details. By way of example, advantages of high throughput and high yield offered by the present arrangements and present teachings are realized in a batchwise approach to graphene formation and are not limited to the different embodiments of the continuous approach described herein. As another example, certain embodiments are described in terms of processing gases, but the present teachings recognize that reservoirs, gas nozzles, gas dispensing apertures or flow paths may have stored therein and/or convey non-gaseous processing materials that transform into a gaseous state during processing. In other instances, well known process steps have not been described in detail to not unnecessarily obscure the invention. As explained above, a conventional approach of graphene formation that relies upon multiple isolated treatment units suffers from several drawbacks. The present teachings recognize that one such drawback is that the entire substrate surface undergoing processing inside a single treatment unit is subjected to a single set of operating conditions. Under this approach, even if a conveyor displaces the substrate surface from one treatment unit to another, the outcome is undesirable, i.e., the entire substrate surface is subjected to a single set of operating conditions. The present teachings recognize that another conventional approach that changes operating conditions, inside a single treatment unit, one condition at a time also suffers from the same drawback as the substrate surface is subjected to a single set of operating conditions. Against this backdrop, the present arrangements and present teachings are not so limited as they offer numerous embodiments that provide structural provisions for implementing and/or implement multiple sets of operating conditions inside the same treatment unit and/or simultaneously inside different treatment units. Accordingly, the present systems and methods offer high yields and high throughputs for graphene formation that are not realized by conventional approaches of graphene formation. FIG.1shows a continuous graphene formation system100, according to one embodiment of the present arrangements, including an infeed portion200, a furnace300, and an outfeed portion400. Each of infeed portion200, furnace300and outfeed portion400extends a certain lateral distance, i.e., a certain distance along the X-axis as shown inFIG.1. In this embodiment, continuous graphene formation system100, accordingly, extends a total lateral distance, which is a sum of the lateral distances that its component subsystems extend. As explained below, as a substrate, upon which graphene is produced, travels this total lateral distance it undergoes different types of processing at different lateral locations, e.g., different distance values on the X-axis. Stated another way, certain structural provisions and/or processing features provided by the present arrangements and teachings are a function of (or depend upon) the lateral location, e.g., distance value on the X-axis. In one embodiment, a substrate is fed through infeed portion200. As the substrate travels a lateral distance of infeed portion200, it encounters certain localized processing conditions, e.g., scavenging conditions. The present arrangements and teachings provide certain structural provisions and processing features, along the lateral distance of infeed portion200, to effectively prepare the substrate, prior to downstream processing, by removing or scavenging contaminants (e.g., gas contaminants present in or around the substrate). Upon the substrate's arrival inside or after a small amount of lateral distance inside one end of furnace300, it is subjected to high temperatures (e.g., about 500° C. and above) for additional processing to create a substantially clean substrate surface, i.e., a contaminant-depleted substrate surface. The present teachings recognize that creating a contaminant-depleted substrate surface, prior to producing graphene on the substrate surface, provides a high yield graphene producing systems and methods. Building on this recognition, the present arrangements and the present methods of graphene formation continue to provide certain laterally disposed structural provisions and processing features inside furnace300and outfeed portion400to realize-significantly high yields and high throughput of graphene formation. Conventional graphene producing systems and methods fail to recognize these advantages of the present teachings, much less offer such structural provisions and processing features. By way of example, as the contaminant-depleted substrate surface displaces another lateral distance inside the same furnace300, it undergoes, at certain lateral locations, certain novel processing steps, according to the present teachings, associated with annealing to produce an annealed surface. Further, the annealed surface is laterally conveyed yet another lateral distance inside the same furnace, for production, thereon, of graphene having the desired characteristics for its intended commercial application. Again, structural provisions and processing features of the present arrangements and the present teachings implement, at certain lateral locations, certain novel processing steps associated with production of the requisite quality of graphene. After production of graphene has concluded, cooling of the substrate surface begins. Preferably, cooling of the substrate surface, with graphene deposited thereon, commences when the substrate is still present inside the same furnace and near outfeed400and concludes near or at the end of outfeed400. Thus, the substrate surface with graphene deposited thereon is conveyed yet another lateral distance that starts from inside furnace300and extends to the end of outfeed400. Novel structural provisions and processing features, at certain lateral locations within this lateral distance from furnace300to outfeed400, provided by the present arrangements and the present teachings implement cooling of the substrate surface immediately, e.g., on the order of a few seconds, after graphene is deposited thereon. Rapid cooling, after production, of graphene allows for effective downstream recovery of the adhering graphene from the adjacent substrate surface to realize a high yield and high throughput for graphene formation. Further, structural provisions and processing features of the present arrangements and the present teachings do more than offer high yield and high throughput for graphene formation. In the absence of a gas or a mechanical barrier within and between the different component subsystems, the present arrangements and the present teachings prevent or minimize both cross-contamination and cross-interference between the different types of processing of the substrate being carried out inside continuous graphene formation system100. To facilitate a detailed description,FIGS.2,3A,3B,4A,4B,5,6A,6B,7,8A,8B,9,10A,10B and11show the salient structural provisions offered by the present arrangements andFIGS.12-20describe the major steps involved in the processing features of the present teachings. FIG.2shows certain salient components inside infeed portion200including rollers202, a belt drive system204, a substrate roll206, a flexible bellows joint208, tunnels210, multiple pallets212, a chiller plate214, gas curtains216, and a chiller block218. During an operational state of graphene formation system100, rollers202, operating under a gravitational force, advance a substrate holder comprising multiple pallets212towards a location underneath a substrate roll206. In certain embodiments, a continuous drive system of the present arrangements, e.g., belt drive system204, direct push drive system, rack and pinion system or chain drive system, preferably, drives or rotates a subassembly of multiple rollers, e.g., rollers202, to advance pallets212towards a location underneath a substrate roll206. In one embodiment, rollers202of the present arrangements are cogs that fit into a complementary structure on pallets212, which are preferably made from graphite to withstand high levels of heat present inside an enclosure within furnace300. In this operational state, substrate roll206, that may be controlled by a servo motor and an ultrasonic sensor detecting slack loop, dispenses an appropriate length of a substrate sheet that is disposed on and laterally extends (i.e., extends in the X-direction) upon pallets212. In one embodiment, the substrate holder in the present arrangements is a single continuous belt that preferably laterally extends the total lateral distance of continuous graphene formation system100. Regardless of whether pallets212or a continuous belt are/is used as a substrate holder, the present teachings recognize that the roll out motion of substrate roll206is not always dictated by a continuous motion of the advancing pallets212but that the forward movement of the laterally extending substrate sheet is dictated by the supporting, advancing pallets. In an alternative design of infeed portion200of the present arrangements, a speed matching system is employed for matching forward substrate holder speed with a linear amount of the substrate sheet unrolled per unit time. In certain embodiments of the present arrangements, the pallets (e.g., substantially similar in form to pallets212ofFIG.2) are stationary and are not in motion as mentioned above in connection withFIG.2. In these “stationary” embodiments of the substrate holder of the present arrangements, the supported substrate sheet is unrolled from substrate roll206and displaced above the stationary pallets. In preferred implementations of these arrangements, substrate roll206may rely on at least one of the above-described components, e.g., servo motor, sensor for slack loop detection and speed matching, for an effective roll out of the substrate sheet. Inside infeed portion200, the advancing substrate sheet is protected from ambient conditions and contaminants by tunnels210positioned above and around a linear rail system. Approximate a location of a first tunnel, i.e., the tunnel closest to substrate roll206and furthest from furnace300, flexible bellows joint208is provided to allow for expansion of tunnel210when high levels of heat escapes, as explained below, from furnace300ofFIG.2towards tunnels210. On the last tunnel, i.e., the tunnel furthest from substrate roll206and closest to furnace300, preferably, chiller plate214is disposed to remove the heat escaping in the negative lateral direction, i.e., in the negative X-direction, from furnace300and thereby prevent melting or degrading of upstream components, e.g., substrate holder, linear track, tunnels, and the substrate. In the present arrangements of an infeed portion200, multiple tunnels210are arranged in series on and around a supporting linear rail system to create an enclosed environment. Pallets212are arranged adjacent to the linear rail system, which allows for expansion of the tunnel withstand the high levels of heat escaping from furnace300ofFIG.1. Further, each tunnel210is flanked by a gas curtain216. In this configuration, multiple repeating structural units, each including tunnel210and gas curtain216, are contiguously arranged to form infeed portion200. Each such repeating structural unit is referred herein to as a “scavenging sub-enclosure” because of the gas scavenging conditions present therein. Specifically, the surface of substrate sheet (hereinafter referred to as the “substrate surface”) includes or has disposed around it “substrate gas” and the scavenging sub-enclosure has conditions to scavenge the substrate gas. The present teachings recognize that, to those skilled in the art, certain present arrangements of the scavenging sub-enclosure may be seen as a degassing subsystem that creates a degassing environment for the substrate. To this end, gas curtain216is disposed on scavenging sub-enclosures and specifically, between two infeed tunnels210, disposed in series and that isolate contents inside infeed tunnels210from the ambient environment. One or more gas curtains216may be part of one or more scavenging gas distribution systems that provide a substrate gas scavenging composition, from one or more reservoirs containing the substrate gas scavenging composition, to locations inside one or more tunnels210. In this configuration, gas curtain216includes one or more directional scavenging gas outlets that are oriented to direct at least some portion of the stream of substrate gas scavenging composition to flow inside infeed tunnels210in one or more different directions. By way of example, directional scavenging gas outlets may be one or more laterally-oriented gas outlets and one or more angularly-oriented gas outlets. The multiple laterally-oriented gas outlets are oriented in a direction that is parallel to the substrate holder and the multiple angularly-oriented gas outlets are oriented in a direction that is at an angle to an axis perpendicular to the substrate holder. The laterally-oriented gas outlet, in an operational state, protects the substrate sheet from contaminants present around the substrate sheet by generating a laterally flowing stream of the substrate gas scavenging composition. The angularly-oriented gas outlet, in an operational state, generates and directs an angularly flowing stream of the substrate gas scavenging composition to contact the substrate sheet. Further, one or more of the directional curtain outlets generate one or more streams of substrate gas scavenging composition to direct the substrate gas scavenging composition and the annealing gas composition, flowing from furnace300into the infeed tunnels, towards an exit of infeed portion200, i.e., an opening in infeed portion that is away from furnace300. The gas streams and the outflowing gases prevent or minimize flow of ambient gases inside infeed tunnels210. As a result, not only do scavenging sub-enclosures scavenge the substrate gas composition, but also prevent contaminants from settling on or reacting with the substrate surface. In preferred embodiments, infeed portion200of the present arrangements includes one or more scavenging gas stream generating subsystems, each of which provides a substrate gas scavenging composition at appropriate flow rates (which dictates the scavenging composition's pressure inside) to multiple scavenging gas outlets. In this configuration, at least one scavenging gas outlet is arranged at a first corresponding location inside the different scavenging sub-enclosures. A collection of the scavenging gas outlets arranged at the first corresponding location inside each of the different scavenging sub-enclosures comprise a first set of scavenging gas outlets. The substrate gas scavenging composition streams produced from the first set of scavenging gas outlets are combined to form a first continuously flowing substrate gas scavenging composition stream that spans across multiple scavenging sub-enclosures. The present teachings recognize that inside each of the different scavenging sub-enclosures, there are present multiple sets of such corresponding locations (e.g., a top left corner location inside multiple tunnels210, or a top right corner location inside multiple tunnels210) where scavenging gas outlets may be arranged to form multiple sets of correspondingly located scavenging gas outlets. In preferred embodiments of the present teachings, multiple sets of correspondingly located scavenging gas outlets, accordingly, produce multiple continuously flowing substrate gas scavenging composition streams across multiple scavenging sub-enclosures. Multiple continuously flowing scavenging gas streams of the present teachings effectively strip the substrate gas from the substrate surface and evacuate contents, such as argon gas and degassed material from the substrate surface, present inside infeed tunnels210and the scavenging sub-enclosures. Moreover, these multiple continuously flowing scavenging gas streams serve as an even more of a protective barrier, preventing surrounding contaminants from contacting the substrate surface, and serve as an even more of a scavenger of the substrate gas to produce a substrate-gas-depleted surface than a single scavenging gas stream. The present teachings recognize, however, that a scavenging sub-enclosure of the present arrangements is not limited to the configuration shown inFIG.2and may be of many include different components in different configurations. Regardless of the configuration of the scavenging sub-enclosure, an appropriate value for a feed rate of the substrate sheet ensures that, if not all, at least appreciable amounts of oxygen present in and around the substrate surface is depleted from the substrate surface such that oxygen concertation in and around the substrate surface inside the last tunnel, before entering furnace300, ranges from between about 5 ppm to about 100 ppm. Depending on the length of tunnels210, and to facilitate presence of such low levels of oxygen in and around the substrate surface, pallets212are, preferably, advancing at a rate that ranges from about 1 mm/second to about many tens of mm/second (e.g., about 15 mm/second, about 20 mm/second, about 30 mm/second). Further, there may be one or more oxygen sensors and preferably, three oxygen sensors, provided at the bottom and/or top of the last tunnel before furnace300to ensure that oxygen concentration of the substrate and/or inside the last tunnel is at the requisite low level. Like infeed portion200, outfeed portion400is made from arranging multiple repeating structural units referred herein to as an “outfeed sub-enclosure.” Further, outfeed portion400includes one or more inert gas stream generating subsystems, each of which provides an inert gas at an appropriate pressure to multiple outfeed gas outlets. Each outfeed gas outlet, in turn, generates an inert gas stream inside an associated outfeed sub-enclosure. By way of example, outfeed gas outlets may be one or more laterally-oriented outfeed gas outlets and one or more angularly-oriented outfeed gas outlets. The multiple laterally-oriented outfeed gas outlets are oriented in a direction that is parallel to the substrate holder and the multiple angularly-oriented outfeed gas outlets are oriented in a direction that is at an angle to an axis perpendicular to the substrate holder. The laterally-oriented outfeed gas outlet, in an operational state, protects the substrate sheet from contaminants present around the substrate sheet by generating a laterally flowing stream of the substrate gas scavenging composition. The angularly-oriented gas outlet, in an operational state, generates and directs an angularly flowing stream of the substrate gas scavenging composition to contact the substrate sheet. The present teachings recognize that inside each of the different outfeed sub-enclosures, there are present multiple sets of corresponding locations where outfeed gas outlets may be arranged to form multiple sets of correspondingly located outfeed gas outlets. Each set of corresponding outfeed gas outlets is combined to produce a continuously flowing inert gas stream that spans across multiple scavenging sub-enclosures. In preferred embodiments of the present teachings, multiple sets of correspondingly located outfeed gas outlets produce multiples of such continuously flowing inert gas streams across multiple scavenging sub-enclosures. Further, some of these outfeed gas outlets are oriented to direct at least some portion of the inert gas stream to flow inside infeed tunnels210, over the substrate surface and in a lateral direction away from furnace300and towards an opening in outfeed portion400. A significant amount of heat is removed from the substrate, as explained below, using heat sinks and the continuously flowing inert gas stream from the outfeed gas outlets further facilitates substrate cooling and prevents contaminants from being introduced on the graphene and the substrate surface. FIGS.3A and3Bshow one preferred embodiment of outfeed portion400that includes multiple tunnels410, which are arranged serially and disposed adjacent to, e.g., on, below and/or around, a linear rail system. Each tunnel410has disposed thereon, thereunder and/or therearound chiller plates, e.g., top chiller plates414A resting on top of each tunnel410and bottom chiller plates314B contacts a bottom portion of the outfeed sub-enclosure. These chiller plates are preferably made from an efficient thermal conductor and are, more preferably, made from aluminum. In this figure, pallets412rest on a heat sink422(e.g., preferably made from a good thermal conductor and more preferably made from copper) to further remove heat from pallet412. Like infeed portion200, rollers are also present at outfeed portion400for taking up the substrate sheet. Furthermore, pressure pads may be used in conjunction with the rollers, present at infeed portion200and outfeed portion400, for controlling the substrate roll out and take up. Further, when a speed matching system is employed at the infeed for matching forward pallet speed with the linear amount unrolled, a final section of the rail system at the outfeed is, preferably, speed controlled to control the tension of the overlying substrate sheet, i.e., ensure that the substrate sheet, extending out of the furnace and into outfeed portion400, is at a requisite level of tension for proper retrieval of the graphene formed on the substrate sheet. Such speed control features in the present arrangements are desirable for achieving high yields and high throughput for graphene formation. In certain preferred embodiments of the present arrangements, outfeed portion400includes an exhaust pump420for pulling scavenging gas that is present inside the outfeed tunnels410. Although not shown to simplify illustration inFIG.2, infeed portion200may include provisions similar to exhaust pump420to scavenge substrate gas. The above-mentioned provisions provided at outfeed portion400, for rapidly cooling and the subsequent heat and or gas removal from outfeed tunnels410, provide for efficient and effective downstream removal of graphene from the substrate surface and therefore offer high throughput and high yield when deploying the present systems and methods for graphene formation. According toFIG.4A, a furnace400, according to preferred embodiment of the present arrangements, spanning a lateral distance “L” is made by contiguously arranging multiple repeating furnace sub-structure units302of lateral distance “d,” where n*d=L, and n is a whole number. In this configuration, an enclosure512, disposed inside furnace300, similarly extends a lateral distance “L.”FIG.4Bshows in greater detail furnace sub-structure unit302as including heating coils304, top main purge tube inlets306A, bottom main purge tube inlets306B, exterior lid308,310interior lid, sub-enclosure312, bottom component314and316thermocouples. Multiple sub-enclosures312are contiguously arranged to form an enclosure512inside furnace300that extends the lateral distance “L.” Depending on the type of processing implemented, different processing gases, e.g., substrate gas scavenging composition, annealing gas composition, producing composition or cooling air or gas, are provided inside one or more different sub-enclosures312to create a localized processing environment, e.g., scavenging environment, annealing environment, producing environment or cooling environment, inside the enclosure and the desired type of processing is carried out at a requisite temperature to form or produce graphene on the substrate surface. One or more heat sources, e.g., a plurality of heating coils, are arranged to span the lateral distance “L,” and are disposed on top and/or bottom of enclosure312to heat certain portions or a particular portion thereof, preferably a middle portion of enclosure512or sub-enclosures312that are disposed in the middle portion of enclosure512, to a requisite temperature for carrying out different types of processes therein. In preferred embodiments of the present arrangements, infeed portion200, furnace300and outfeed portion400that include appropriate ones of the above-mentioned localized environments inside them do so in the absence of any physical barriers between and within them. The present teachings consequently recognize that heat, air and/or gas, which may be crucial in creating a desired type of localized processing environment, may undesirably bleed into and interfere with another or an adjacent localized processing environment. As a result, in connection with structural features present inFIGS.2,3A,3B,4A and4Band methods presented in FIGS.12-19, for example, the present teachings describe the manner in which these structural features and carefully selected processing parameters, implemented in creating adjacently disposed localized processing environments inside continuous graphene formation systems100ofFIG.1, minimize the effects of any such bleeding or interference, if it was to occur. Thus, the present arrangements and methods represent a low capital cost design that offers significantly high throughput and high yields for graphene formation. FIG.4Bshows that each furnace sub-structure302includes one or more shields surrounding furnace300. In the embodiment shown inFIG.4B, a bottom component314is disposed below, i.e., in a negative Z-direction, relative to sub-enclosure312. The bottom component314serves as base and is capable of supporting one or more lids thereon. By way of example, interior lid310is disposed on a first leg protruding, i.e., in a positive Z-direction, from bottom component314and exterior lid308is disposed on a second leg also protruding from bottom component314. In this configuration, exterior lid308is disposed above, i.e., in the positive Z-direction from, interior lid310. In this configuration, exterior lid308and interior lid310extend a lateral distance and a combination of bottom component314and exterior lid308/interior lid310have defined therein two laterally extending (i.e., in the X-direction) gas purge paths, i.e., an exterior gas purge path defined from the assembly of bottom component314and exterior lid308and an interior gas purge path defined from the assembly of bottom component314and interior lid310. Inside furnace300, processing gases that escape from one or more sub-enclosures312and collect inside furnace300are purged using one or more such gas purge paths. A purge gas stream made from an inert or reducing gas composition, introduced inside the interior gas purge path, purges processing gases or contaminants that may have escaped from and collected inside the cavity defined by the assembly of bottom component314and interior lid310. This purging prevents the undesired processing gases or contaminants, generated during a particular type of processing, from flowing towards, being reintroduced at another location inside enclosure512, and interfering with another type of processing being implemented at that location. As another preventive measure, the present arrangements allow for purging processing gases and contaminants escaping from the interior gas purge path into the exterior gas purge path. To achieve effective purging, an inert gas stream is introduced inside the exterior gas purge path created inside a cavity resulting from the assembly of bottom component314and exterior lid308. Furnace substructure unit302may further include top and bottom main purge tube inlets306A and306B to keep escaped processing gases and contaminants away from and not collecting around heat sources304and thermocouples316. Thermocouples316are used for measuring the temperature proximate heat sources304to gain an understanding of the processing temperature values that might be present inside one or more sub-enclosures312. Further, based on the measurements obtained from thermocouples316, the present teachings may operate heat sources304to provide the desired temperature values inside one or more sub-enclosures312. Collection of extraneous materials, such as processing gases and contaminants may not only interfere with these objectives but also, over a period of time, degrade heat sources304and thermocouples316, further exacerbating these objectives. In preferred embodiments, exterior lid308, interior lid310and bottom component314of the present arrangements are made from efficient thermally stable materials, e.g., advanced ceramics. Further, these components may be commercially available from Blasch Precision Ceramics Inc. of Menands, New York. FIG.5shows a cutaway view of furnace300ofFIG.4Aexposing an assembly of different internal components including an upper insulation502, heating coils504, lower insulation510, enclosure512(previously shown inFIG.4A), bottom component's protruding exterior leg514, gas injection nozzles520. In this embodiment, heating coils504are serving as heat sources304ofFIG.4B. Exterior lid308is disposed above bottom component's protruding exterior leg514to form an exterior encasing of enclosure512and defines the exterior gas flow path described above for purging processing gases and contaminants. Insulation, e.g., upper insulation502and lower insulation510, prevent undesired dissipation of heat generated from heating coils504to the environment and ensure that most, it not all, of this heat is used for processing inside enclosure512. FIG.6Ashows a side view of furnace300′, which is substantially similar to furnace300ofFIGS.1,3and5, except furnace300′ ofFIG.6Ais oriented to clearly show the arrangements involved in an enclosure and gas distribution subassembly600, including an enclosure612, which is substantially similar to enclosure512ofFIGS.4A and5.FIG.6Bmore clearly shows the details surrounding enclosure612ofFIG.6A. According toFIG.6B, a bottom component614has two protruding legs, i.e., an exterior protruding leg (substantially similar to exterior protruding leg514ofFIG.5) and an interior protruding leg, an exterior lid608(which is substantially similar to exterior lid308ofFIG.4B) disposed on top of the exterior protruding leg and an interior lid610(which is substantially similar to interior lid310ofFIG.4B) disposed on top of the interior protruding leg. FIG.6Bshows enclosure and gas distribution subassembly600also include certain provisions inside a single enclosure612for gas distribution, such as two or more gas injection nozzles, i.e., a first gas injection nozzle620and a second gas injection nozzle620′, and each of them including, at one end, two or more inlets, e.g., a first inlet622and a second inlet624for first gas injection nozzle620and, correspondingly, a first inlet622′ and a second inlet624′ for second gas injection nozzle620′. Preferably, first inlets622and622′ are configured to provide one type of processing composition and second inlets624and624′ are configured to provide another type of processing composition. At another end, a tip of each of gas injection nozzles620and620′ is coupled to their respective nozzle-receiving inlets, e.g., a first nozzle-receiving inlet626and a second nozzle-receiving inlet626′, respectively. In the embodiment ofFIG.6B, single enclosure612has disposed thereon a gas injection plate (e.g., a gas injection plate850or850′ shown inFIGS.8A and8B, respectively) that has defined therein two or more nozzle-receiving inlets, e.g., nozzle-receiving inlets626and626′, communicatively coupled to two or more gas conduits, e.g., a first gas conduit628and a second gas conduit628′, respectively. Two or more gas conduit outlets, e.g., a first gas conduit outlet630and a second gas conduit outlet630′, are defined at or near the opposite end (i.e., opposite to the end that has defined therein nozzle-receiving inlet) of first gas conduit628and second gas conduit628′, respectively. The structure of gas injection plate850or850′ having defined therein multiple nozzle-receiving inlets disposed at one end of multiple gas conduits, which has disposed at the opposite end multiple gas conduit outlets, is described below in greater detail in the discussion ofFIGS.8A and8B. FIG.7shows additional components, which are part of the single gas distribution system, coupling to first inlets622and622′ and second inlets624and624′ andFIGS.8A,8B,9,10A and10Bshow components relevant to defining multiple material flow paths from two or more gas conduit outlets. e.g., first gas conduit outlet630and second gas conduit outlet630′, to gas dispensing apertures defined on gas dispensing surface and deliver processing gases inside the enclosure (e.g., enclosure612ofFIG.6B). FIG.7shows multiple single gas distribution systems, according to one embodiment of the present arrangements, for a single unit (e.g., unit1is hereinafter referred to as “U1”). In this arrangement, multiple mass flow controllers (hereinafter “MFC”) set flow rates of component processing gases drawn from their respective gas reservoirs (e.g., H2reservoir, Ar reservoir and CH4reservoir) and/or reservoirs that do not contain gaseous hydrocarbon material to produce a producing composition, which is described below. Each MFC associated with U1is identified by sequential numbering, i.e., U1MFC1, U1MFC2, U1MFC3. . . U1MFC12. Two or more mass flow controllers740and742, e.g., U1MFC1and U1MFC2, are communicatively coupled to single control valve744, which in turn mixes and balances the component processing gas flowrates, received from U1MFC1and U1MFC2, to form a pure gas and/or mixtures of processing compositions, such as ArH2and ArCH4. Alternately, two or more mass flow controllers740and742, e.g., U1MFC1and U1MFC2, are communicatively coupled to single control valve744, which in turn mixes and balances a mixture of component processing gas and/or processing non-gaseous flowrates to form processing compositions, such as ArCH4. Control valve744delivers substantially the same processing composition through at least two gas lines, e.g., a first gas line722and a second gas line722′, to at least two injection nozzles, e.g., first gas injection nozzle620and second gas injection nozzle620′ shown inFIG.6B, respectively. These lines may not gas lines if non-gaseous processing compositions are used. As explained above with respect toFIG.6B, the same processing composition received at gas injection nozzles620and620′ is conveyed to their respective nozzle-receiving inlets626and626′. FIG.8Ashows a cutaway view of a gas injection plate850disposed above sub-enclosure812A (which is substantially similar to sub-enclosure612ofFIG.6B) and represents a portion of a processing gas or processing composition flow path from one or more gas reservoirs to an interior of the sub-enclosure. FIG.8Bshows a gas injection plate850′, which is substantially similar to gas injection plate850except gas injection plate850′ ofFIG.8Bis shown in a disassembled state, having the underlying sub-enclosure812A removed therefrom. Gas injection plate850′ has defined therein multiple gas flow networks, e.g., a first gas flow network854A, a second gas flow network854B and a third gas flow network854C. Further, gas injection plate850′ includes certain structural features previously presented in connection with the description ofFIG.6B. Consistent with that description, gas injection plate850′ has defined therein a first gas flow path extending from nozzle-receiving inlet826(which is substantially similar to nozzle-receiving inlet626ofFIG.6B) through gas conduit828(which is substantially similar to nozzle-receiving inlet628ofFIG.6B) to gas conduit outlet830(which is substantially similar to gas conduit outlet630ofFIG.6B). Gas conduit outlet830also represents a network inlet because that is a point of entry for the processing composition to make its way to first gas flow network854A. After traversing the various branches of first gas flow network850A, the processing gas exits this network from multiple network outlet apertures832. By way of example, a processing composition entering first gas flow network854A at gas conduit outlet830, travels through the network and exits from 32 network outlet apertures832. Preferably, the exiting processing composition from each network outlet apertures832has substantially the same pressure. Moreover, a second gas flow path, in gas injection plate850′, extends from nozzle-receiving inlet826′ through gas conduit828′ to gas conduit outlet830′. After this stage, the processing composition continues to travel the second gas flow path as it enters second gas flow network854B and exits from network outlet apertures832′. Preferably, the exiting processing composition from each network outlet apertures832′ has substantially the same pressure. The same gas injection plate850′ has a third gas flow path defined by structural components including a third gas flow network854C that are similar to those described in connection with the description of the first and the second material flow paths. FIG.9shows two multiple sub-enclosures812A and812B arranged in series to define a portion of an enclosure. In this figure, first sub-enclosure812A is shown in a disassembled state, without the underlying gas injection plate and second sub-enclosure812B is shown (to simplify illustration) with a cutaway view of the gas injection plate (e.g., gas injection plate850′ ofFIG.8B) having defined therein first and second gas flow networks854A,854B and854C. First sub-enclosure812A is shown to have a gas dispensing surface860having defined thereon a first set of gas dispensing apertures852, which align, in one-to-one corresponding fashion, with the network outlet apertures (e.g., network outlet apertures832ofFIG.8B) defined on the gas injection plate (e.g., gas injection plate850′ ofFIG.8B). As a result, each of the multiple material flow paths described on a single sub-enclosure812A terminate at multiple associated sets of network outlet apertures852. To this endFIG.10Ashows, sub-enclosures812A,812B and812C and similar others are continuously arranged to form the ultimately resulting enclosure512ofFIG.4A. Each of these sub-enclosures are fitted with multiple gas injection nozzles. By way of example, sub-enclosure812A is fitted with gas injection nozzles826and826′. As another example, each sub-enclosure812B and812C are fitted with multiple, e.g., three different gas injection nozzles. As explained below, this combination of multiple gas injection nozzles along with their associated ones of gas flow networks, e.g., gas flow networks854A,854B and854C, form at least parts of multiple material flow paths in a single sub-enclosure. FIG.10Bshows a portion of gas flow path created when a single gas injection nozzle826is coupled to sub-enclosure812A. According to this figure, the processing composition travels from gas injection nozzle826to a gas conduit828and a gas conduit outlet830. Gas conduit828and gas conduit outlet830are substantially similar to gas conduit628and gas conduit outlet630shown inFIG.6B. Further, as explained in connection with the description ofFIG.8B, gas conduit828and gas conduit outlet830are features that are defined in sub-enclosure812A (. As a result,FIG.10Bconveys that flow of processing composition flow from gas injection nozzle826, which is coupled to sub-enclosure812A, enters a gas injection plate850′ disposed above sub-enclosure812A. FIG.10Cshows another portion of a gas flow path created when gas injection nozzle826is coupled to sub-enclosure812A and specifically flow of processing composition through gas injection plate850′ and then ultimately inside the underlying sub-enclosure812A. According to this figure, inside the gas injection plate, the processing composition flows through first gas flow network854A (also shown inFIG.8B) and out of network outlet apertures (e.g., network outlet apertures832ofFIG.8B) associated with gas flow network854A. These network outlet apertures align with a first set of gas dispensing apertures (e.g., gas dispensing apertures852ofFIG.9) such that the processing composition is dispensed through the first set of gas dispensing apertures inside sub-enclosure812A. As a result, the processing composition delivered by each of the multiple gas injection nozzles coupled to a single sub-enclosure812A, as shown inFIG.10A, travels the gas flow path shown inFIGS.10B and10Cand is delivered inside sub-enclosure812A. When at least two gas injection nozzles receive a substantially same processing composition from a control valve (e.g., control valve744) and are dispensed through two sets of gas dispensing apertures, which are a lateral separating distance apart from each other, inside sub-enclosure812A to diffuse the processing composition at least the lateral separating distance inside sub-enclosure812A. The present teachings recognize that, in this manner, by strategically providing the substantially same processing composition inside one or more sub-enclosures (e.g., sub-enclosure812A and812B ofFIG.9), and each sub-enclosure using two or more gas injection nozzles, creates a substantially uniform processing gas environment inside sub-enclosure812A. If the processing gas is any one of a substrate gas scavenging composition, an annealing gas composition or a producing composition,FIGS.10A,10B and10Cconvey that a substantially uniform scavenging environment, annealing environment, or producing environment, respectively, is formed inside one or more sub-enclosure e.g.,812A,812B and/or812C. FIG.11shows two sub-enclosures812A and812B assembled in series which are disposed inside a furnace sub-structure (e.g., furnace sub-structure302ofFIG.4B). At a location of assembly of two sub-enclosures812A and812B, an expansion gap875is defined therebetween to allow either or both of sub-enclosures812A and812B to expand into expansion gap875. To allow for the assembly of sub-enclosures812A and812B, each of sub-enclosures812A and812B include, on one side, a slidable component876, and have defined, on an opposite side, a cavity878that accepts the slidable component. To effect the assembly, slidable component876of sub-enclosures812A slides into cavity878of812B as shown inFIG.11. The other sides of sub-enclosures812A and812B mate with complementary ends of other sub-enclosures to form at least a portion of enclosure (e.g., enclosure512ofFIG.4A). The present teachings therefore recognize that in this manner an entire enclosure is constructed and disposed inside furnace sub-structure (e.g., furnace sub-structure302ofFIG.4B). The present teachings offer many methods for processing the substrate surface for graphene formation. In certain implementations of a graphene formation method, the substrate sheet undergoes electropolishing to clean the substrate sheet before subjecting the substrate sheet to a graphene growing process as described below. The different types of processing, according to preferred embodiments of the present teachings, may use: (1) one or more laterally arranged heat sources (e.g., multiple laterally arranged heating coils504inside furnace300that provide different amounts of heat at different ranges of lateral distances inside enclosure512as shown inFIGS.4A and5), except during scavenging, cooling and post-cooling processing; and (2) multiple gas distribution systems (e.g., one or more scavenging gas distribution systems that provide substrate gas scavenging composition inside a laterally extending infeed portion200ofFIG.2and laterally extending one or more processing gas distribution systems and/or laterally delivering one or more processing gas distribution systems, such as components and features shown inFIGS.6A,6B,7,8A,8B,9,10A,10B and10Cthat both laterally extend and provide different types of processing gases at different ranges of lateral distances inside enclosure512ofFIGS.4A and5). FIG.12shows a flowchart of a method for processing, according to one embodiment of the present teachings, a substrate for graphene formation1200(hereinafter “method1200”) that, preferably, begins with a step of disposing1202. Step1202involves disposing a substrate sheet on a substrate holder (e.g., pallets212ofFIG.12). In disposing step1202, the substrate sheet has located thereon a first surface for processing (e.g., a first surface area or region on the substrate that undergoes processing) and a second surface for processing (e.g., a second surface area or region on the substrate that undergoes processing) such that the first surface for processing is separated a lateral distance (e.g., a distance in the positive X-direction) apart from the second surface for processing. By way of example, the substrate sheet may be made from copper or nickel and may be disposed on a substrate roll (e.g., substrate roll206ofFIG.2). In one embodiment of the present teachings, step of disposing1202involves using a servo motor and an ultrasonic sensor detecting slack loop to dispose the substrate on the substrate holder. If graphite pallets are used, as a substrate holder, they may be about 600 mm long (e.g., in the X-direction), about 400 mm wide (e.g., in the Y-direction) and about 6 mm thick (e.g., in the Z-direction) for effectively facilitating conveyance of the substrate sheet through a graphene formation system of the present arrangements (e.g., continuous graphene formation system100ofFIG.1). In one preferred embodiment, method1200of the present teachings include continuously advancing the substrate sheet in a lateral direction (i.e., in the X-direction) using a linear track that is advanced by a substrate holder advancing mechanism (e.g., continuous belt drive system204that drives pallets212in the lateral direction as shown inFIG.2). As explained below, in preferred embodiments of the present teachings, the substrate sheet is continuously laterally advancing as its surface undergoes different types of processing, e.g., scavenging, annealing, producing and cooling, and different processing conditions (e.g., passivating after cooling), applied on the substrate, may vary as a function of the lateral distance (i.e., a distance value in the X-direction) inside the continuous graphene formation system (e.g., continuous graphene formation system100ofFIG.1). Regardless of whether the step of advancing is carried out, after disposing step1202, method1200proceeds to a scavenging step1204. This step includes scavenging, at a scavenging temperature and using a substrate gas scavenging composition (e.g., an Ar and H2gas mixture), a substrate gas (e.g., including oxygen) present in and around the first surface for processing of the substrate sheet to produce a substrate-gas-depleted surface. Step1204may use an angularly flowing stream and/or a laterally flowing stream of a substrate gas scavenging composition. Preferably, disposed inside infeed portion (e.g., one or more of tunnels210) are multiple scavenging gas outlets, at least some of which are angularly-oriented scavenging gas outlets and laterally-oriented scavenging gas outlets. The angularly-oriented scavenging gas outlets are oriented at an angle with respect to an axis that is perpendicular to the substrate holder. As a result, the angularly-oriented scavenging gas outlets, in an operational state during step1204, provide an angular stream of a substrate gas scavenging composition incident upon the substrate sheet to effectively scavenge substrate gas in and around the substrate sheet. Multiple laterally-oriented scavenging gas outlets are designed to generate multiple continuously flowing streams of substrate gas scavenging composition and, preferably, spanning across multiple scavenging sub-enclosures and flowing in an opposite direction to the direction of laterally advancing substrate sheet. In preferred embodiments of step1204, the multiple continuously flowing streams of substrate gas scavenging composition flow over and in a direction opposite to the direction of laterally advancing substrate to evacuate undesired contents, such as heat and different type of contaminants, that may be present inside the tunnels. As a result, the present teachings recognize that multiple streams of such laterally flowing substrate gas scavenging composition may be more effective for contaminant removal. Although not necessary, step1204may be implemented using one or more scavenging gas stream generating subsystems, which include the above-mentioned angularly-oriented scavenging gas outlets and laterally-oriented scavenging gas outlets. Step1204is, preferably, carried out in absence of an active heating source positioned adjacent to the first surface for processing. As explained below, in this embodiment, some of the heat flowing towards the first surface for processing provides the requisite temperature treatment and may range from about 50° C. to about 100° C. Method1200also includes an annealing step1206that involves annealing, using a flow rate of the substrate gas scavenging composition and/or an annealing gas composition and at an annealing temperature, the second surface for processing of the substrate sheet. Regardless of the gas composition, the processing gas(es) used during annealing may be delivered using a gas distribution system (e.g., components and features shown inFIGS.6A,6B,7,8A,8B,9,10A,10B and10C) that are coupled to multiple processing sub-enclosures, e.g., multiples of sub-enclosure302ofFIG.4B, that may be thought of as annealing sub-enclosures. Annealing step1206using multiple annealing sub-enclosures at the appropriate annealing temperature produces an annealed surface. Further, in step1206, the annealing temperature is higher than the scavenging temperature and is produced using one or more heat sources (e.g., one or more laterally arranged heating coils504ofFIG.5) that are disposed adjacent to the second surface for processing. Some of the heat, resulting from the annealing temperature and the annealing gas composition and/or the substrate gas scavenging composition in step1206, flows towards the first surface for processing and facilitates formation of the substrate gas depleted surface. The annealing gas composition and/or the substrate gas scavenging composition resulting from step1206, preferably, flows backwards (e.g., a negative distance along the X-axis) because the second surface for processing is located, in preferred embodiments of the present arrangement, a positive lateral distance (e.g., a positive distance along the X-axis) from the first surface for processing. Further, step1204and a subsystem used for carrying out step1204(e.g., infeed portion200ofFIG.2) preferably does not include certain structural features shown in a subsystem used for carrying out step1206(e.g., furnace300ofFIG.4A). By way of example, step1204is carried out without using a gas injection plate (e.g., gas injection plate850ofFIG.8Aand gas injection plate850′ ofFIG.8B) operating in conjunction with a gas dispensing surface (e.g., gas dispensing surface860having defined thereon a first set of gas dispensing apertures852shown inFIGS.9and10B) of a sub-enclosure (e.g.,812A ofFIG.10B). The annealing temperature is a temperature inside one or more annealing sub-enclosures and ranges from about 150° C. to about 1100° C. Further, in the absence of a physical barrier between two adjacently disposed scavenging sub-enclosure and annealing sub-enclosure, some of the residual heat (i.e., heat remaining after a significant amount of it is removed from chiller block218and chiller plate214to prevent melting of tunnels210and other components related to scavenging sub-enclosures in infeed portion200ofFIG.2), flows in a lateral direction (e.g., a distance in the negative X-direction) into scavenging sub-enclosures in infeed portion200ofFIG.2. This residual heat further facilitates scavenging of the substrate gases including removal of moisture trapped in the substrate. Preferably, annealing step1206is carried out contemporaneously to scavenging step1204, i.e., the second surface for processing is undergoing annealing at the same time the first surface for processing is undergoing scavenging. The present teachings, however, recognize that step1206may be carried out sequentially and after the conclusion of step1204. More preferably, annealing step1206of the present teachings is carried out when the second surface for processing of the substrate is present inside an annealing environment, e.g., annealing sub-enclosures inside furnace300ofFIGS.1and4A, and scavenging step1204is carried out when the first surface for processing is present inside a scavenging environment, e.g., scavenging sub-enclosures of infeed portion200shown inFIG.2or a location inside enclosure512ofFIGS.4A and5. In even more preferred embodiments of the present teachings, the second surface for processing is subject to annealing step1206inside an annealing environment, e.g., enclosure512ofFIGS.4A and5, at the same time as the first surface for processing is subject to scavenging step1204inside the scavenging environment, e.g., inside scavenging sub-enclosures of infeed portion200ofFIG.2or inside enclosure512ofFIGS.4A and5. FIG.15shows a flowchart of a method for scavenging1500, according to one embodiment of the present teachings and that may be implemented as step1204ofFIG.12. Method1500includes an advancing step1502. This step involves advancing, inside a scavenging environment (e.g., infeed portion200ofFIG.2), a surface (e.g., first surface for processing mentioned in step1202ofFIG.12) a scavenging range of lateral distance. Step1502may be carried out by advancing the substrate sheet in a lateral direction (i.e., in the X-direction) using a linear track that is advanced by a substrate holder advancing mechanism (e.g., continuous belt drive system204that drives pallets212in the lateral direction as shown inFIG.2). The scavenging range of lateral distance of step1502includes an initial scavenging location or region and a subsequent scavenging lateral distance or region such that the subsequent scavenging location or region is a lateral distance away from the initial scavenging location or region. The subsequent scavenging location or region is proximate to an annealing environment, e.g., enclosure512ofFIGS.4B and5, and the initial scavenging location or region is proximate to an exit opening defined at one end of the scavenging environment that is opposite to the other end (of the scavenging environment), which is proximate to the annealing environment. Method1500also includes a step1504, which involves subjecting, during step1502, i.e., the advancing of the surface inside the scavenging environment, the surface to a flow rate profile of the substrate gas scavenging composition that increases from a relatively low flow rate value of the substrate gas scavenging composition at the initial scavenging location or region to a relatively high flow rate value of the substrate gas scavenging composition at the subsequent scavenging location or region. In other words, steps1502and1504are carried out contemporaneously. Further, step1504is, preferably, implemented using one or more scavenging gas distribution systems that deliver, using multiple scavenging gas outlets associated with gas curtains216shown inFIG.2, the substrate gas scavenging composition inside one or more tunnels210ofFIG.2. By way of example, one or more scavenging gas outlets associated with a gas curtain that is located proximate to the exit of the scavenging environment deliver the relative low flow rate value of said substrate gas scavenging composition at the initial scavenging location. As another example, one or more scavenging gas outlets associated with a gas curtain that is located proximate to the annealing environment, e.g., enclosure512ofFIGS.4B and5, deliver the relative high flow rate value of said substrate gas scavenging composition at the subsequent scavenging location or region. The relatively low flow rate value of the substrate gas scavenging composition, preferably, ranges from 1 about liters/minute to 4.5 about liters/minute, and the relatively high flow rate value of the substrate gas scavenging composition, ranges from about 0.5 liters/minute to about 100 liters/minute and in a more preferred embodiment from about 5 liters/minute to about 20 liters/minute. The relatively high flow rate value of the substrate gas scavenging composition near the end of the scavenging environment (e.g., scavenging sub-enclosure of infeed portion200ofFIG.2) not only accomplishes aggressive scavenging of substrate gases before a next phase of processing commences, but also contributes to removing the heat escaping from the annealing environment (e.g., enclosure512ofFIGS.4A and5). Moreover, the relatively high flow rate value of the streams of substrate gas scavenging composition, applied inside the end of the scavenging environment proximate to the annealing environment and flowing outward, away from the annealing environment and towards an opening of the infeed portion, where relatively low flow rate value of the streams of substrate gas scavenging composition are applied, represent preferred embodiments of the present teachings. The flow rate differential creates a significant pressure drop near an entrance of the annealing environment. Further, this significant the pressure drop causes certain incident processing gases, e.g., substrate gas scavenging composition and annealing gas composition, to laterally flow from inside the annealing environment, (e.g., annealing sub-enclosures of enclosure512ofFIGS.4A and5) in an outward direction (e.g., negative lateral direction), towards the exit opening of the scavenging environment that is disposed a negative lateral distance away from the annealing environment. Such outward flow of the incident processing gases does more than—to facilitate scavenging of the substrate gas present in and around the substrate in the scavenging environment. This outward flow of the incident processing gases, present inside an enclosure having disposed therein the annealing environment, prevents these processing gases to undesirably flow into and interfere with a downstream localized (graphene) producing environment inside the same enclosure. FIG.13shows a flowchart of a method for annealing1300, according to one embodiment of the present teachings and that may be implemented as step1206ofFIG.12. In this embodiment, method1300includes a step1302of pre-treating a surface, at a pretreating temperature and using a pretreating incident flow rate of a substrate gas scavenging composition and/or an annealing gas composition, to produce a contaminant-depleted surface. In step1302, it is preferable to use a substrate gas scavenging composition, e.g., a gas mixture of Ar and H2. While not wishing to be bound by theory, the presence of H2, during pretreating, removes metals and carbon-based surface contaminants and thereby prevents undesirable melting of the (metallic, e.g., copper and/or nickel) substrate. Melting of the substrate, prior to undergoing high temperature annealing, degrades the substrate quality and as such, the substrate no longer lends itself for effective graphene formation thereon. As a result, pretreatment in step1302allows the present methods to realize high yields and high throughput for graphene formation. Method1300also includes a step1304, which includes treating the contaminant-depleted surface, at a treating temperature and using a treating incident flow rate of the annealing gas composition, to produce an annealed surface. In certain embodiments of the present teachings, step1304is carried out after the conclusion of step1302. In alternate embodiments of the present teachings, steps1302and1304are carried out contemporaneously. Method1300may be implemented in a batchwise approach of forming graphene. Using a continuous approach (e.g., continuous graphene forming system100ofFIG.1) represents a preferred approach of the present teachings for realizing high yield and high throughput for graphene formation. Regardless of the approach, treatment of the substrate surface in step1304is carried out using an annealing gas composition, preferably, in the absence of a substrate gas scavenging composition. Further, the annealing gas composition may be Ar gas that includes trace amounts of oxygen. While not wishing to be bound by theory, the presence oxygen in trace amounts serves an important function of reacting with removing certain types of surface contaminants that are not removed during pretreatment of the substrate surface using H2in step1302. However, the present teachings recognize that residual amounts of oxygen, which may remain on the substrate surface are undesirable to form graphene used in certain applications. By way of example, to obtain graphene for use in those applications that require large crystalline structures, residual (trace) amounts of oxygen remaining on the substrate surface serve as a nucleation site to undesirably form graphene crystals of relatively small sizes. To this end, alternate methods of annealing described in connection withFIGS.14and18are presented below. Further, in this context, the present teachings recognize that if other applications of graphene desire small crystalline structures, then certain embodiments described in connection withFIGS.12,13,15,16,17,19and20provide high yields and high throughput for graphene formation. FIG.14shows another flowchart of another method for annealing1400, according to alternate embodiments of the present teachings and that may be implemented as part of step1206ofFIG.12. Method for annealing1400includes a pretreating step1402and treating step1404, both of which are substantially similar to pretreating step1302and treating step1304described in connection with the description ofFIG.13. Method for annealing1400, however, includes an additional step, a passivating step1406for passivating the annealed surface. Step1406including passivating an annealed surface (e.g., obtained from steps1304or1404ofFIGS.13and14, respectively), at a passivating temperature range and using the substrate gas scavenging composition to react with oxygen to produce a passivated surface. As explained above, the substrate gas scavenging composition, preferably, reacts with the residual (trace) amounts of oxygen remaining on the substrate surface after annealing has concluded. Method1400is susceptible to being implemented under either the batchwise approach or the continuous approach of graphene formation, but the continuous approach represents a preferred embodiment as it provides high yields and high throughputs for graphene formation. The present teachings offer certain preferred embodiments for forming graphene, including annealing, that comprise: (1) displacing a surface, a pretreating range of lateral distance inside an enclosure; and (2) exposing, during the displacing of the surface inside the enclosure, to the surface a temperature profile that varies as a function of a lateral distance displaced within the pretreating range of lateral distance inside the enclosure; and (3) subjecting, during the displacing of the surface inside the enclosure, the surface to a pretreating incident flow rate profile of a substrate gas scavenging composition that varies as a function of a lateral distance displaced within the pretreating range of lateral distance inside the enclosure. These steps (1), (2) and (3), connected to pretreating of the substrate surface, are carried out contemporaneously. FIG.16shows a flowchart of a method for pretreating1600, according to certain preferred embodiment of the present teachings and that may be implemented as step1302or step1402ofFIGS.13and14, respectively. Method1600includes a displacing step1602for displacing a surface (e.g., second surface for processing of step1206ofFIG.12, or the surface of steps1302or1402ofFIGS.13and14, respectively) a pretreating range of lateral distance inside an enclosure (e.g., enclosure512ofFIGS.4B and5). A substrate surface undergoes annealing inside an annealing environment, which may extend an annealing range of lateral distance that subsumes the pretreating range of lateral distance. In certain embodiments, the pretreating range of lateral distance of the present teachings is a distance value that ranges from about 700 mm from an end of a scavenging environment (e.g., infeed portion200ofFIG.2) or beginning of an annealing environment (e.g., enclosure512ofFIGS.4A and5) to about 1200 mm from the end of the scavenging environment or beginning of the annealing environment. A relatively large pretreating range of lateral distance of about 400 mm or larger, from a location at or near the beginning of an annealing environment, represents a preferred embodiment of the present arrangement because by holding the adjacently disposed (to the substrate surface) one or more heat sources (e.g., laterally arranged heating coils504ofFIG.5that provide heat inside, but are located outside of, enclosure512ofFIG.5) at low temperature conditions or in a deactivated (i.e., turned off) state, avoids forming high heat conditions that flow back into the scavenging environment (e.g., one or more sub-enclosures of infeed portion200ofFIG.2) and cause damage to the substrate surface and/or the structure responsible for creating the scavenging environment. The pretreating range of lateral distance includes an initial pretreating location or region and, disposed a lateral distance away therefrom, a subsequent pretreating location or region. In this context, method1600further includes a step of exposing1604, during displacing step1602inside the enclosure, to heat generated from one or more pretreating heat sources, e.g., heating coils504disposed outside enclosure512ofFIG.5, but that provide heat inside the pretreating range of lateral distance inside the enclosure. In this configuration and in exposing step1604, one or more pretreating heat sources are disposed adjacent to the surface undergoing pretreatment. Further, one or more pretreating heat sources present at the initial pretreatment location or region, provide a minimum value of the annealing temperature at a corresponding location inside the enclosure. Further still, one or more pretreating heat sources present at the at the subsequent pretreatment location or region, provide a maximum value of the annealing temperature at a corresponding location inside the enclosure. In certain implementations of the present teachings, the minimum temperature value ranges from about 100° C. to about 200° C. and the maximum value of the annealing temperature is a value that ranges from about 1000° C. to about 1100° C. Method1600further still includes a step1606that involves, during the displacing (of step1602) of the surface and inside the enclosure, subjecting the surface to an incident flow rate profile of the substrate gas scavenging composition that increases as a function of lateral distance displaced within the pretreating range of lateral distance. Under one approach, incident flow rate value of the substrate gas scavenging composition linearly increases as the gas delivery location that, the surface is subjected to, laterally advances from one delivery location to another along the pretreating range of lateral distance. The present teachings recognize, however, that under an alternate approach, these incident flow rates increase non-linearly as the surface laterally advances along the pretreating range of lateral distance. Regardless of the approach, portions of the processing gas distribution systems, which may laterally extend the pretreating range of lateral distance, deliver at the initial pretreating location or region a relatively low flow rate value of the substrate gas scavenging composition, and deliver at the subsequent pretreating location or region a relatively high flow rate value of the substrate gas scavenging composition. The relatively low flow rate value of the substrate gas scavenging composition, preferably, ranges from about 0.5 liters/minute to 20 liters/minute and more preferably range from about 0.5 liters/minute to 4.5 liters/minute, and the relative high incident flow rate value of the substrate gas scavenging composition ranges from about 5 liters/minute to 100 liters/minute and more preferably ranges from about 5 liters/minute to 20 liters/minute. The present teachings recognize that steps1602,1604and1606are carried out contemporaneously. After the conclusion of pretreatment, annealing of a substrate surface may advance to treating of the substrate surface as explained below. The present teachings offer methods of forming graphene, including treating, that comprise: (1) displacing a surface, a treating range of lateral distance inside an enclosure; and (2) exposing, during the displacing of the surface inside the enclosure, to the surface a temperature profile that remains substantially constant within the treating range of lateral distance inside the enclosure; and (3) subjecting, during the displacing of the surface inside the enclosure, the surface to a treating incident flow rate profile of a substrate gas scavenging composition that varies as a function of a lateral distance displaced within the pretreating range of lateral distance inside the enclosure. These steps (1), (2) and (3), connected to treating of the substrate surface, are carried out contemporaneously. FIG.17shows a flowchart of a method for treating1700, according to preferred embodiments of the present teachings, and that may be implemented as step1304or step1404ofFIGS.13and14, respectively. Method1700includes a step1702that involves displacing a surface a treating range of lateral distance (e.g., treating range of lateral distance of steps1304or1404ofFIGS.13and14, respectively) inside the enclosure (e.g., enclosure512ofFIG.3). A substrate surface undergoes annealing inside an annealing environment, which may extend an annealing range of lateral distance that subsumes the pretreating range of lateral distance and the treating range of lateral distance. The treating range of lateral distance beings after an end of the pretreating range of lateral distance. The treating range of lateral distance is, preferably, a distance value that ranges about 100 mm after an end of the pretreating range of lateral distance to about 3000 mm after the end of the pretreating range of lateral distance. A starting location of the treating range of lateral distance ranges from about 300 mm from a location at or near beginning of the annealing environment to about 5000 mm from the location at or near beginning of the annealing environment and spans a distance that ranges from about 300 mm to about 3000 mm. By way of example, a location at the beginning of the annealing environment is at 0 mm of enclosure512ofFIG.5and the term “near beginning of the annealing environment” refers to a distance ranging from 0.01 mm from the beginning of the enclosure to 5 mm from the beginning of the enclosure. Method1700further includes an exposing step1704of exposing, during step1702, the surface to heat generated from one or more laterally extending treating heat sources disposed (e.g., heating coils504ofFIG.5that extend a treating range of lateral distance) adjacent to the surface. As shown inFIG.5, heating coils504are adjacent to the surface as they provide heat inside, but are located outside of, enclosure512. In this configuration and in exposing step1704, one or more of the “treating” heat sources are maintained at a treating temperature to generate a substantially constant annealing temperature (e.g., allowing a fluctuation of up to about ±5% of the annealing temperature) along the treating range of lateral distance inside the enclosure. The treating temperature may be a temperature value that ranges from about 500° C. to about 1100° C. Further, method1700further still includes a step1706that involves maintaining, during displacing step1702of the surface and inside the enclosure, a substantially uniform incident flow rate of the annealing gas composition along the treating range of lateral distance. Although not necessary, processing gas distribution systems, which laterally extend the treating range of lateral distance, preferably deliver the annealing gas composition along that range of lateral distance. In preferred embodiments, these gas distribution systems of the present arrangements, which extend the treating range of lateral distance or deliver annealing gas compositions to the treating range of lateral distance, do not provide substrate gas scavenging compositions inside the annealing sub-enclosures. Exemplar values of the substantially uniform incident flow rate of the annealing gas composition ranges from about 3 liters/minute to about 5 liters/minute. The present teachings allow a fluctuation of up to about ±5% in the flow rates of the annealing gas composition from one lateral location to another. The present teachings recognize that steps1702,1704and1706are carried out contemporaneously. The present teachings offer further still other methods of forming graphene, including passivating, that comprise: (1) displacing a surface, a passivating range of lateral distance inside an enclosure; (2) exposing, during the displacing of the surface inside the enclosure, to the surface a temperature profile that remains substantially constant within the passivating range of lateral distance inside the enclosure; and (3) subjecting, during the displacing of the surface inside the enclosure, the surface to a passivating incident flow rate profile of a substrate gas scavenging composition that varies as a function of a lateral distance displaced within the passivating range of lateral distance inside the enclosure. These steps (1), (2) and (3), connected to passivating of the substrate surface, are carried out contemporaneously. FIG.18shows a flowchart of a method for forming graphene1800, according to preferred embodiments of the present teachings, including passivating and that may be implemented as step1406ofFIG.14. Method for annealing including passivating1800includes a step1802of displacing, inside an enclosure, a surface along a passivating range of lateral distance that includes an initial passivating lateral distance or region and, disposed a lateral distance away therefrom, a subsequent passivating lateral distance or region. A starting location of the passivating range of lateral distance ranges from about 1700 mm from at or near the beginning of the annealing environment to about 7000 mm from at or near the beginning of the annealing environment and spans a distance that ranges from about 500 mm to about 2000 mm. A substrate surface undergoes annealing inside an annealing environment, which may extend an annealing range of lateral distance that subsumes the pretreating range of lateral distance, the treating range of lateral distance and the passivating range of lateral distance. The passivating range of lateral distance starts after the end of the treating range of lateral distance. Method1800further includes a step1804of exposing, during step1802, the surface to heat generated from one or more heat sources. By way of example, one or more heating coils304ofFIG.4Bthat extend a passivating range of lateral distance provide heat inside, but are located outside, of enclosure512ofFIGS.4B and5are adjacent to the surface undergoing passivation. In this configuration and in exposing step1804, one or more passivating heat sources generate a substantially constant annealing temperature inside the enclosure, e.g., annealing sub-enclosures that span the passivating range of lateral distance and implement step1804. Further, method1800further still includes a step1806of subjecting, during step1802, the surface inside the enclosure to a decreasing incident flow rate profile of the passivating gas composition, e.g., substrate gas scavenging composition, that varies as function of the lateral distance within the passivating range of lateral distance. In certain embodiments, step1806is carried out using multiple gas distribution systems that extend a passivating range of lateral distance or deliver the substrate gas scavenging composition to the passivating range of lateral distance. One or more of the gas distribution systems, which may be disposed at or deliver to the initial passivating lateral distance or region inside furnace300ofFIG.5, apply a relatively high flow rate of the substrate gas scavenging composition to the surface, when it is positioned at, the initial passivating lateral distance or region inside the enclosure. Further, one or more of the gas distribution systems, which may be disposed at or deliver to the subsequent passivating lateral distance or region inside furnace300ofFIG.5, apply a relatively low flow rate of the passivating gas composition. e.g., substrate gas scavenging composition, to the surface, when it is positioned, at the subsequent passivating lateral distance or region inside the enclosure. The relatively high flow rate of the passivating gas composition ranges from 5 liters/minute to about 100 liters/minute and in a more preferred embodiment ranges from about 5 liters per minute to about 20 liters per minute. The relatively low flow rate of the passivating gas composition ranges from about 0.5 liters/minute to about 20 liters/minute and in a more preferred embodiment ranges from about 0.5 liters/minute to about 4.5 liters/minute. The present teachings recognize that steps1802,1804and1806are carried out contemporaneously. In one preferred embodiment of the present teachings for formation of graphene on the substrate surface, the process begins by displacing disposing, on a substrate holder, a substrate sheet having located thereon a first surface for processing and a second surface for processing. The first surface for processing is separated by a positive lateral distance apart from said second surface for processing. This embodiment of the method of producing graphene further includes annealing, in the presence of an annealing gas composition and at an annealing temperature, the first surface for processing of the substrate sheet to produce an annealed surface. In one implementation of this step, the annealing temperature is produced using one or more laterally extending heat sources disposed adjacent to the first surface for processing. Further still, this method of forming graphene includes producing, in presence of a producing composition, graphene on the second surface to produce a graphene deposited surface. In more preferred embodiments, the incident flow rates of producing composition inside the producing sub-enclosures, i.e., sub-enclosures dedicated to carrying out graphene formation, that are in proximate distance to the annealing sub-enclosures, are relatively low and the incident flow rates of annealing gas composition inside the annealing sub-enclosures, which are in proximate distance to the producing sub-enclosures, are also similarly relatively low. More preferred embodiments of the present methods do not, therefore, allow an appreciable amount of the annealing gas composition from the annealing step or location to flow a positive lateral distance towards the location of producing on the second surface for processing and, therefore, does not interfere with the formation of graphene. More preferred embodiments of this method also do not allow the producing composition to flow a negative lateral distance toward the annealing location of the first surface for processing and, therefore, does not interfere with the annealing of the first surface for processing. The present teachings recognize that the above-mentioned steps of annealing and producing graphene are carried out contemporaneously. In alternate embodiments that implement passivating of the annealed surface, prior to graphene formation, the present teachings recognize that relatively high incident flow rates of substrate gas scavenging composition and/or annealing gas composition are delivered inside the annealing sub-enclosures that are positioned relatively further away from the producing sub-enclosures and, similarly, relatively high flow rates of producing composition are delivered inside the producing sub-enclosures that are positioned relatively further away from the annealing sub-enclosure and/or cooling sub-enclosures. Such processing conditions of the present teachings prevents or minimizes cross-contamination between two different types of processing, adjacently implemented, inside the same enclosure. The present teachings offer preferred embodiments for producing graphene on a substrate surface. An exemplar of these embodiments comprises: (1) displacing a surface, a producing range of lateral distance inside an enclosure; (2) exposing, during the displacing of the surface inside the enclosure, a temperature profile that varies as a function of a lateral distance displaced within the producing range of lateral distance inside the enclosure; and (3) subjecting, during the displacing of the surface inside the enclosure, the surface to a producing incident flow rate profile of a substrate gas scavenging composition that varies as a function of a lateral distance displaced within the producing range of lateral distance inside the enclosure. These steps (1), (2) and (3), connected to producing of graphene on the substrate surface, are carried out contemporaneously. FIG.19shows a flowchart of a preferred method for producing1900, according to one embodiment of the present teachings, graphene on a substrate surface. Method for producing1900may begin with a displacing step1902and that includes displacing a surface (e.g., a first or a second surface for processing) a producing range of lateral distance inside the enclosure. By way of example, a starting location of the producing range of lateral distance inside the enclosure ranges from about 250 mm from the beginning of the enclosure to about 9000 mm from the beginning of the enclosure and spans a distance that ranges from about 500 mm to about 10000 mm inside the enclosure. The producing range of lateral distance includes an initial producing location or region, an intermediate producing lateral distance or region and a subsequent producing location or region. The subsequent producing location or region is disposed a lateral distance apart from the intermediate producing lateral distance or region, which, in turn, is disposed a lateral distance apart from the initial producing location or region. In other words, the intermediate producing lateral distance or region is disposed between the initial producing location or region and the subsequent producing location or region. Method for producing1900further includes an exposing step1904, which involves exposing the surface to heat generated from one or more heat sources (e.g., laterally arranged heating coils304or504ofFIGS.3and5, respectively) that extends the producing range of lateral distance and are disposed adjacent to the surface. Step1904may be carried out as the surface travels a portion, e.g., at least half, of the producing range of lateral distance inside the enclosure. The temperature of one or more of these heat sources, extending at least a portion of the producing range of lateral distance, generate a requisite amount of heat in corresponding locations inside the enclosure to have a relatively constant temperature that ranges from about 500° C. to about 1100° C. and in a more preferred embodiment ranges from about 900° C. to about 1100° C. Method for producing1900may further still include a step1906of subjecting, during step1902, the surface to an incident flow rate profile of a producing composition. In this step, a constant relatively low flow rate of the producing composition is applied to the surface at the initial producing location or region. Further, a first maximum flow rate of the producing composition is applied to the surface at the intermediate producing lateral distance or region. Further still, a second maximum flow rate of the producing composition is applied to the surface at the subsequent producing location or region. The second maximum flow rate is, preferably, higher than the first maximum flow rate to realize high yield and high throughput for graphene formation. In a preferred implementation of this incident flow rate profile of the producing gas, the second maximum flow rate is almost twice as higher than the first maximum flow rate. The second maximum value of the flow rate of the producing gas is a flow rate value that ranges from about 5 liters/minute to about 100 liters/minute and in a more preferred embodiment ranges from about 5 liters/minute to about 20 liters/minute and the first maximum value of the flow rate of the producing gas is a flow rate value that ranges from about 0.5 liters/minute to about 20 liters/minute and in a more preferred embodiment ranges from about 0.5 liters liters/minute to about 4.5 liters/minute. The present teachings recognize that steps1902,1904and1906are carried out contemporaneously. After formation of graphene as described in connection withFIG.19, the substrate surface with graphene begins cooling, preferably, inside the same enclosure used for graphene formation. In more preferred embodiments, outside the enclosure and in a cooling environment, e.g., outfeed portion400shown in3A and3B, the substrate surface with graphene undergoes further cooling to a greater extent than the enclosure. In this embodiment of the present teachings, laterally-oriented outfeed gas outlets generate laterally flowing substrate gas scavenging streams towards an exit end of the outfeed tunnels for removing contents, e.g., heat, producing composition and substrate gas scavenging composition, present inside one or more of the outfeed tunnels to form a protective layer above the substrate surface undergoing cooling. Moreover, these outfeed gas outlets provide, preferably, a relatively high flow rate of the substrate gas scavenging composition inside outfeed tunnels410near an interface between the enclosure and outfeed portion400ofFIGS.3A and3B. The outfeed gas outlets also, preferably, provide a relatively low flow rate value of substrate gas scavenging composition at or near an exit end of outfeed tunnels410or outfeed portion400ofFIGS.3A and3B. As a result, contents inside outfeed tunnels proximate to the producing/cooling environment inside the enclosure are flowing outward, away from the producing/cooling environment and towards an opening of the outfeed portion for evacuation. This creates flow rate differential creates a significant pressure drop near an exit of the producing/cooling environment, e.g., enclosure512ofFIGS.4A and5. Further, this significant the pressure drop causes certain incident processing gases, e.g., substrate gas scavenging composition and producing composition, to laterally flow from inside the producing/cooling environment, (e.g., producing/cooling sub-enclosures of enclosure512ofFIGS.4A and5) in an outward direction, towards the exit opening of the cooling environment that is disposed a positive lateral distance away from the producing/cooling environment. Such outward flow of the incident processing gases, e.g., producing gas and substrate gas scavenging composition, prevents these processing gases to undesirably flow into and interfere with the upstream localized (graphene) annealing environment inside the same enclosure or further upstream scavenging environment inside the infeed portion200shown inFIG.2. FIG.20shows a flowchart of a method for processing2000, according to one embodiment of the present teachings, a substrate surface for effectively forming graphene thereon. In one embodiment, method for processing2000of the present teachings begins with a displacing step2002, which includes displacing a surface of a substrate sheet a scavenging range of lateral distance inside a scavenging sub-enclosure (e.g., a lateral distance spanning the infeed portion200ofFIG.2). By way of example, a continuous belt drive system204pushes pallets212disposed on a linear track of infeed portion200, as shown inFIG.2. Further in this example, the substrate sheet is rolled out from substrate roll206and disposed upon pallets212as shown inFIG.2prior to the pallets212advancing in a positive lateral direction. Method2000also includes a step of scavenging2004that is carried out during step of displacing step2002and inside the scavenging sub-enclosure (e.g., sub-enclosures that make up infeed portion200ofFIG.2). According to step2004, the surface undergoes scavenging (e.g., scavenging step1204ofFIG.12and method for scavenging1500ofFIG.15) to remove substrate gas (e.g., oxygen) from the surface, as the surface travels the scavenging range of lateral distance inside a sub-scavenging enclosure to produce a contaminant-depleted surface. In preferred embodiments, method for processing2000of the present teachings includes a step2006, which involves moving the contaminant-depleted surface an annealing range of lateral distance inside an enclosure (e.g., furnace200ofFIG.2) that is located downstream from the scavenging sub-enclosure (e.g., sub-enclosures that make up infeed portion200ofFIG.2). Moving step2006moves the contaminant-depleted surface, preferably, from a location at or near an end of the scavenging range of lateral distance (e.g., where the infeed portion200ends or near an ending location of the lateral distance spanning the infeed portion200ofFIG.2). At this stage, preferably the contaminant-depleted surface is a certain distance inside the enclosure (e.g., a certain distance inside furnace200ofFIG.2). In other words, the annealing range of lateral distance is a lateral distance that begins from a location at or near the end of the scavenging range of lateral distance. Method for processing2000includes a step of annealing2008to produce an annealed surface. In this step, during step2006and inside the enclosure, the contaminant-depleted surface undergoes annealing (e.g., annealing step1206ofFIG.12, method for annealing1300ofFIG.13and steps related to annealing described in methods1400,1600,1700and1800ofFIGS.14,16,17and18). Method for processing2000may also carry out an advancing step2010. This step includes advancing, within the enclosure, the annealed surface a producing range of lateral distance. The annealed surface travels the annealed range of lateral distance from a location at or near the end of the annealing range of lateral distance. Preferably, after the conclusion of annealing step2008to produce the annealed surface, method for processing2000includes a step of producing2012. According to this step, during advancing step2010and inside the enclosure, graphene is produced on the annealed surface to produce a (graphene) produced surface. In other words, in producing step2012, graphene is produced on the substrate surface inside the same enclosure where annealing step2008is carried out. By way of example, method for processing1900ofFIG.19describes various steps for implementing producing step2012. The present teachings, however, recognize that high throughput and high yield graphene systems and methods preferably implement further processing that facilitates downstream efficient recovery of graphene from the substrate sheet, without destroying the yielded graphene structure and the substrate sheet. To this end, method2000contemplates carrying out a conveying step2014. In this step, within and at a location outside the enclosure, the (graphene) produced surface is conveyed a cooling range of lateral distance. The producing surface travels the cooling range of lateral distance from a location at or near the end of the producing range of lateral distance. By way of example, the cooling range of lateral distance begins at a location near the end of furnace200and extends to a location at or near an end of outfeed portion400ofFIG.4A. Method2000also includes a cooling step2016for cooling, during conveying step2014and inside and outside the enclosure, the (graphene) produced surface to form a cooled surface. Although a substantially significant amount of cooling of the (graphene) produced surface takes place in outfeed portion300shown inFIGS.3A and3B, cooling, preferably, begins inside cooling sub-enclosures, i.e., sub-enclosures302ofFIG.4Adedicated to cooling the substrate surface, that are positioned after producing sub-enclosures. The outfeed sub-enclosures which are contiguously arranged to form outfeed portion300are separated by gas curtains216, which have strategically placed outfeed gas outlets to apply an inert gas stream on the (graphene) produced surface. Other provisions for effective cooling of the substrate surface include heat sink322and top and bottom chiller plates314A and314B shown inFIGS.3A and3B, respectively. In more preferred embodiments, method2000includes a passivating step, which involves passivating the cooled surface using an inert or reducing gas to produce a cooled, passivated surface that is ready for recovery of graphene from the substrate sheet it was produced on. Method2000is described in terms of a single region on a surface of the substrate sheet undergoing processing, e.g., scavenging of the substrate gas, annealing, producing of graphene, and cooling off the graphene produced on a region of the substrate surface. The present teachings, however, recognize that the advantages of the present systems and method for producing graphene are not so limited. By way of example, at the same time when a first region of the substrate surface (a “first surface for processing”) is subject to scavenging step2004, a second region of the substrate surface (a “second surface for processing”) is subject to annealing step2008, a third region of the substrate surface (a “third surface for processing”) is subject to producing step2012and a fourth region of the substrate surface (a “fourth surface for processing”) is subject to cooling step2016. As another example, at the same time when a surface area or region is subject to annealing step2008, another surface area or region is subject to producing step2012. In certain implementations of this example, yet another surface area or region is subject to cooling step2016at the same time the other surface areas or regions are undergoing different types of processing. The present teachings recognize that different type of processing on different surface areas or regions of the same substrate surface are carried out at the same time to realize a high throughput for the graphene producing systems and methods. The present teachings also recognize that it is not necessary to carry out displacing step2002, moving step2006, advancing step2010, and conveying step2014to realize the benefits of the present teachings. Further, the advantages of the present teachings are also realized when the substrate sheet is processed for graphene formation using a batchwise process, and not a continuous process, implemented in one or more discrete processing chambers, each dedicated to carrying out one or more different types of processes. Further still, in certain embodiments of the present teachings, annealing (e.g., pretreating, treating and passivating) are not required for producing graphene. In these embodiments, after scavenging, the structural provisions of the present arrangements and processing conditions of the present teachings provide for producing graphene on the substrate and then cooling the substrate with graphene formed thereon. Although the invention is illustrated and described herein as embodied in one or more specific examples, it is nevertheless not intended to be limited to the details shown, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims. By way of example, there is no reason why the advantages and implementations of the present teachings are not realized in batchwise graphene deposition systems and methods. Accordingly, it is appropriate that the appended claims be construed broadly, and in a manner consistent with the scope of the invention, as set forth in the following claims. | 96,808 |
11858814 | DETAILED DESCRIPTION As used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a vector” includes a plurality of such vectors and reference to “the amino acid” includes reference to one or more amino acids and equivalents thereof known to those skilled in the art, and so forth. Also, the use of “or” means “and/or” unless stated otherwise. Similarly, “comprise,” “comprises,” “comprising” “include,” “includes,” and “including” are interchangeable and not intended to be limiting. It is to be further understood that where descriptions of various embodiments use the term “comprising,” those skilled in the art would understand that in some specific instances, an embodiment can be alternatively described using language “consisting essentially of” or “consisting of.” Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs. Although many methods and reagents are similar or equivalent to those described herein, the exemplary methods and materials are disclosed herein. All publications mentioned herein are incorporated herein by reference in full for the purpose of describing and disclosing the methodologies, which might be used in connection with the description herein. Moreover, with respect to any term that is presented in one or more publications that is similar to, or identical with, a term that has been expressly defined in this disclosure, the definition of the term as expressly provided in this disclosure will control in all respects. The reticular synthesis of covalent organic frameworks (COFs), extended porous two-dimensional (2D) or three-dimensional (3D) networks held together by strong, highly directional chemical bonds, has thus far been restricted to small, shape-persistent, molecular building blocks. Traditional COF growth strategies heavily rely on reversible condensation reactions that guide the reticulation toward a desired thermodynamic equilibrium structure. The requirement for dynamic error correction, however, limits the choice of building blocks and thus the associated mechanical and electronic properties imbued within the periodic lattice of the COF. Furthermore, the poor electronic communication across imine and boronate ester linkers, most commonly used in the synthesis of 2D COFs, gives rise to semiconducting materials featuring large band gaps undesirable for advanced electronic applications. Charge-carrier transport in these materials is dominated by interlayer hopping mechanisms rather than through chemical bonds between linkers and the constituent molecular building blocks within a 2D sheet. Introduction of conjugated polymers as 1D conduction paths within a single COF sheet could address this shortcoming, yet the incorporation of macromolecules as building units in COFs has not been demonstrated. Recent advances in the bottom-up synthesis of graphene nanoribbons (GNRs), atomically thin quasi one-dimensional (1D) strips of graphene, have inspired the development of a new class of COF building blocks. The control over key structural parameters in GNRs, width, edge symmetry, dopant atom density, and dopant position gives rise to a highly tunable band structure and the emergence of exotic physical phenomena linked to symmetry protected topological states. As shown in the exemplary studies presented herein, exquisite structural control inherent to bottom-up synthesized GNRs can be adapted to introduce atomically precise spacings of functional groups along the edges of a ribbon, giving access to a shape persistent quasi-1D macromolecular building block for the reticular synthesis of 2D COFs. The disclosure provides for a crystalline graphene nanoribbon-covalent organic framework (GNR-COF) comprising: GNR linked to another GNR by linking ligands. The linking ligands comprise organic molecules. Functional groups on the linking ligands and on the graphene nanoribbons condense to form bonds. In one embodiment, a plurality of graphene nanoribbons (GNRs) are connected or linked together by a plurality of organic linking ligands that comprise functional groups; wherein the GNRs comprise functional groups along the edges of the nanoribbons, and wherein the functional groups of the GNRs form covalent bonds with functional groups of organic linking ligands. In a further embodiment, a GNR-COF of the disclosure has an anisotropic or highly anisotropic crystalline structure. In yet a further embodiment, a GNR-COF disclosed herein has a two-dimensional (2D) sheet or film morphology. In another embodiment, a GNR-COF disclosed herein has a film thickness of 0.5 nm, 0.75 nm, 1 nm, 1.5 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm, 21 nm, 22 nm, 23 nm, 24 nm, 25 nm, 26 nm, 27 nm, 28 nm, 29 nm, 30 nm, 31 nm, 32 nm, 33 nm, 34 nm, 35 nm, 36 nm, 37 nm, 38 nm, 39 nm, 40 nm, 41 nm, 42 nm, 43 nm, 44 nm, 45 nm, 46 nm, 47 nm, 48 nm, 49 nm, 50 nm, or a range that includes or is between any two of the foregoing thickness (e.g., from 2 nm to 25 nm), including fractional increments thereof. In a particular embodiment, a GNR-COF of the disclosure has been delaminated into bilayer and/or trilayer GNF-COF flakes. For example, liquid-phase exfoliation of crystalline cGNR-COFs gives access to vertically stacked few layered cGNR-COF flakes for applications in functional materials and advanced electronics. In a certain embodiment, GNRs used to synthesize a GNR-COF of the disclosure comprises atomically precise spaced functional groups along the edges of the nanoribbons. These functional groups typically participate in formation of covalent bonds between the GNRs and linking ligands. In another embodiment, the plurality of GNRs form covalent bonds with the plurality of organic linking ligands via a reaction commonly used to make COFs, such as a Schiff base reaction, a boronate ester formation reaction, a Knoevenagel reaction, an imide formation reaction, a Michael addition reaction, a phenazine formation reaction, a squaraine formation reaction, or a benzoxazole formation reaction. In a further embodiment, the plurality of GNRs comprise a structure of: wherein, R1-R4are each individually selected from —NH2, —CHO, —CN, or —B(OH)2; and n is an integer>100. In a further embodiment, R1-R4are —NH2or —CHO. In yet a certain embodiment, the organic linking ligands used to make up the GNR-COF of the disclosure is an aryl or heteroaryl that comprises functional groups which can participate in covalent bond formation with the functional groups of GNRs disclosed herein. The organic linking ligands can comprised functional groups, like halos, —OH, —NH2, —COH, —CN, Michael addition adducts, —NO2, boronic acid groups, boronate ester groups, etc. In a particular embodiment, a plurality of organic linking ligands disclosed herein has structure selected from: In a particular embodiment, the plurality of organic linking ligands has a structure of: For example, the disclosure provides, in one embodiment, imine linked GNR-COF films. In particular, large area, homogenous thin, imine linked GNR-COF films of variable thickness can be synthesized using the methods disclosed herein by using interfacial polymerization at a liquid-liquid interface. By modulating the concentration of GNRs in the reaction mixture the film thickness can be controlled over a range of 2-22 nm. Fourier transform infrared (FT-IR) spectroscopy along with control experiments using unfunctionalized cGNRs confirmed that the GNR-COF films are covalently linked through imine bonds. The crystallographic structure of the GNR-COF was probed using wide angle X-ray scattering (WAXS) and transmission electron microscopy (TEM), revealing the extraordinary potential of reticular covalent self-assembly techniques to access densely packed parallel arrays of GNRs. The disclosure also provides methods for making or synthesizing a GNR-COF disclosed herein. In particular embodiment, the method for making or synthesizing a GNR-COF disclosed herein comprises the steps of: adding a first mixture comprising a Lewis Acid and/or Brønsted acid in an aqueous solution, with a second mixture comprising a plurality of graphene nanoribbons (GNRs) and organic liking ligands in an organic solvent system; wherein the GNR-COF is formed through interfacial polymerization at the liquid interface between the first mixture and the second mixture. In particular, the two mixtures should be carefully added so as to form a noticeable layer between the two immiscible mixtures. The GNR-COFs of the disclosure will form in this layer over a period of days. As used herein “Brønsted acid” refers to a molecule or ion that is able to lose, or “donate,” a hydrogen cation (proton, H+). The term “Brønsted acid” explicitly includes, but is not limited to, hydrochloric acid (HCl), hydrofluoric acid (HF), hydrobromic acid (HBr), hydroiodic acid (HI), phosphoric acid (H3PO4), sulfuric acid (H2SO4), boric acid (B(OH)3), tetrafluoroboric acid (HBF4), perchloric acid (HClO4), acetic acid (CH3C(O)—OH), trifluoroacetic acid (CF3C(O)—OH), methanesulfonic acid (CH3SO3H), solid acid resins containing sulfonic acid sites, and solid acid resins containing benzoic acid sites. As used herein, the term “Lewis Acid” refers to moiety capable of sharing or accepting an electron pair. Examples of lewis acids include, but are not limited to, BF3-etherates and metal halides, alkoxides, and mixed halide/alkoxides (e.g., Al(Oalkyl)2Cl, Al(Oalkyl)Cl2). The metals can be aluminum, titanium, zirconium, magnesium, copper, zinc, iron, tin, boron, ytterbium, lanthanum, and samarium. Other Lewis Acids are known in the art. As indicated above the plurality of GNRs are functionalized (e.g., aldehyde groups) along the edges of the GNR so as to be able to form covalent bonds (e.g., imine bonds) with functional groups (e.g., NH2) of the organic linking ligands. A suitable organic solvent system was found to comprise 1,2-dicholorbenzene and chloroform, typically in a 1:1 ratio, although other ratios can be used, e.g., 5:1, 4:1, 3:1, 2:1, 1.5:1, 1:1.5, 1:2, 1:3, 1:4, and 1:5. The Lewis Acid and/or Brønsted acid used in the reaction should be soluble in aqueous solvents and catalyze polymerization of covalent organic framework films (e.g., see Matsumoto et al.,Chem4:308-317 (2018)). In a particular embodiment, the Lewis Acid used to form the GNR-COF is scandium(III)triflate (Sc(OTf)3). Scandium(III)triflate is a highly active catalyst for imine-linked COF formation. The GNR-COFs formed at the interface between the mixtures can be scooped out with a substrate (e.g., glass, membranes, etc.). In a further embodiment, a method disclosed herein further comprises the generating of bilayer and/or trilayer GNF-COF flakes by liquid exfoliation. For example, a dispersion of GNR-COF in acetone is added to 1,2-dicholorbenzene and then agitated by use of rocker, sonification, manual shaking, etc. to form bilayer and/or trilayer GNF-COF flakes. The simplicity of the interfacial GNR-COF growth and liquid-phase exfoliation protocol opens the path to accessing densely packed 2D sheets of parallel GNRs for high-performance electronic device architectures and the exploration of exotic physical phenomena emerging from deterministically engineered stacks of anisotropic layered 2D materials. For example, the disclosure further provides that an electronic device, or battery can comprise bilayer and/or trilayer GNF-COF flakes or a GNF-COF of the disclosure. The following examples are intended to illustrate but not limit the disclosure. While they are typical of those that might be used, other procedures known to those skilled in the art may alternatively be used. EXAMPLES Materials and Methods. Unless otherwise stated, all manipulations of air and/or moisture sensitive compounds were carried out in oven-dried glassware, under an atmosphere of N2or Ar. All solvents and reagents were purchased from Alfa Aesar, Spectrum Chemicals, Acros Organics, TCI America, and Sigma-Aldrich and were used as received unless otherwise noted. Organic solvents were dried by passing through a column of alumina and were degassed by vigorous bubbling of N2or Ar through the solvent for 20 min. Flash column chromatography was performed on SiliCycle silica gel (particle size 40-63 μm). Thin layer chromatography was performed using SiliCycle silica gel 60 Å F-254 precoated plates (0.25 mm thick) and visualized by UV absorption. HOPG substrates were purchased from SPI supplies (3 mm Grade SPI-3). All1H and13C NMR spectra were recorded on Bruker AV-300, AVB-400, AV-600, DRX-500, and AV-500 MHz spectrometers, and are referenced to residual solvent peaks (CDCl31H NMR=7.26 ppm,13C NMR=77.16 ppm; CD2Cl21H NMR=5.32 ppm,13C NMR=53.84 ppm). ESI mass spectrometry was performed on a Finnigan LTQFT (Thermo) spectrometer in positive ionization mode. MALDI mass spectrometry was performed on a Voyager-DE PRO (Applied Biosystems Voyager System 6322) in positive mode using a matrix of dithranol. Gel permeation chromatography (GPC) was carried out on a LC/MS Agilent 1260 Infinity set up with a guard and two Agilent Polypore 300 7.5 mm columns at 35° C. All GPC analyses were performed on a 0.2 mg mL−1solution of polymer in CHCl3. An injection volume of 25 μL and a flow rate of 1 mL min−1were used. Calibration was based on narrow polydispersity polystyrene standards ranging from Mw=100 to 4,068,981 au. Raman spectroscopy was performed on a Horiba Jobin Yvon LabRAM ARAMIS confocal Raman microscope with 532 nm excitation wavelength. Wide-angle X-ray scattering (WAXS) data was acquired on beamline 7.3.3 at the Advanced Light Source with a Pilatus 2M detector. Powder samples were dropcast from acetone, dried in quartz capillaries and put into a helium atmosphere for measurement in transmission geometry. Silver behenate was used for calibration. The Nika package for IGOR Pro (Wavemerics) was used to reduce the acquired 2D raw data to a 1D profile. SEM was performed on a Zeiss Gemini Ultra-55 FESEM with an accelerating voltage between 2-10 kV. Low-dose HR-TEM images were acquired on the TEAM I instrument at the National Center for Electron Microscopy at the Molecular Foundry. TEAM I is a FEI Titan-class microscope operated at 300 kV, with geometric aberrations corrected to third order (with partial correction to fifth order) and chromatic aberrations corrected to the first order. Imaging data were collected at 24° C. with the Gatan K2 direct-detection camera operated in electron-counting mode. Images were recorded with total doses of 100 ek2to minimize sample damage. SEM and TEM samples were prepared via scooping films directly, or drop-casting film dispersions onto lacey carbon TEM grids purchased from Ted Pella. Infrared spectroscopy was conducted with a Bruker ALPHA ATR-FTIR. ATR-FTIR samples were prepared by scooping thick films directly onto aluminum foil. UV-Vis spectroscopic measurements were conducted on a Varian Cary 50 spectrophotometer. 5-bis(4-bromophenyl)-3-phenyl-4-(3-((triisopropylsilyl)ethynyl)phenyl)cyclopenta-2,4-dien-1-one; 2-(4-bromophenyl)-1,3-dioxolane; and unfunctionalized cGNRs were synthesized following the protocols in Rogers et al.J. Am. Chem. Soc.139:4052-4061 (2017) and Wang et al.,Chem. Commun.49:5790 (2013). 3-phenyl-2,5-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-4-(3-((triisopropylsilyl) ethynyl)phenyl)cyclopenta-2,4-dien-1-one (1). An oven dried 200 mL Schlenk flask with reflux condenser was charged under N2with 2,5-bis(4-bromophenyl)-3-phenyl-4-(3((triisopropylsilyl) ethynyl)phenyl)cyclopenta-2,4-dien-1-one (0.50 g, 0.69 mmol), Pd(dppf)Cl2(91 mg, 0.11 mmol), anhydrous KOAc (0.67 g, 6.80 mmol), and bis(pinacolato)diboron (0.68 g, 2.68 mmol) in anhydrous dioxane (80 mL). The reaction mixture was stirred for 5 h at 95° C. The solvent was removed and the crude product was re-dissolved in CH2Cl2, washed with H2O, saturated aqueous NaCl solution, dried over Na2SO4, and concentrated on a rotary evaporator. The crude product was passed through a plug of silica (EtOAc). The solvent was removed and the solid was sonicated in MeOH. This process was repeated until the MeOH filtrate was colorless, yielding 1 (0.47 g, 0.58 mmol, 84%) as a purple solid.1H NMR (400 MHz, CDCl3, 22° C.) δ=7.67-7.59 (m, 4H), 7.33 (dt, J=7.7, 1.4, 1H), 7.29-7.18 (m, 7H), 7.13 (t, J=7.7, 1H), 6.97-6.90 (m, 4H), 1.31 (m, 24H), 1.05 (m, 21H) ppm;13C {1H} NMR (151 MHz, CD2Cl2, 22° C.) δ=200.2, 155.8, 154.6, 134.8, 134.7, 134.2, 134.0, 133.7, 133.6, 133.5, 132.2, 129.9, 129.9, 129.8, 129.7, 129.3, 128.7, 128.6, 126.5, 126.1, 123.8, 106.9, 92.0, 84.4, 25.2, 19.0, 11.8 ppm; HRMS (ESI-TOF) m/z: [C52H62B2O5Si]+calcd. [C52H62B2O5Si] 816.4547; found 816.4523. 2,5-bis(4′-(1,3-dioxolan-2-yl)-[1,1′-biphenyl]-4-yl)-3-phenyl-4-(3-((triisopropylsilyl) ethynyl) phenyl) cyclopenta-2,4-dien-1-one (2). A 25 mL Schlenk flask was charged with 1 (264 mg, 0.32 mmol), 2-(4-bromophenyl)-1,3-dioxolane (2) (224 mg, 0.98 mmol), and Aliquat 336 (6 drops) in 2M K2CO3(3 mL) and dioxane (6 mL). The suspension was degassed via N2sparging for 30 min, after which Pd(PPh3)4(60.4 mg, 0.053 mmol) was added under N2. The reaction mixture was stirred at 100° C. for 20 h under N2. The solution was cooled to 24° C. and diluted with CH2Cl2. The organic phase was washed with H2O, saturated aqueous NaCl solution, dried over Na2SO4, and concentrated on a rotary evaporator. Column chromatography (SiO2; 1-10% EtOAc/CH2Cl2) yielded 2 (189 mg, 0.22 mmol, 68%) as a purple solid.1H NMR (600 MHz, CDCl3, 22° C.) δ=7.64-7.60 (m, 4H), 7.56-7.50 (m, 8H), 7.37-7.33 (m, 5H), 7.31-7.28 (m, 1H), 7.27-7.23 (m, 2H), 7.17 (t, J=7.7, 1H), 7.04-6.98 (m, 4H), 5.81-5.80 (m, 2H), 4.14-4.10 (m, 4H), 4.04-4.01 (m, 4H), 1.06-1.04 (m, 21H) ppm;13C {1H} NMR (101 MHz, CD2Cl2, 22° C.) δ=200.7, 155.4, 154.2, 141.8, 141.8, 140.3, 140.1, 138.0, 133.8, 133.6, 133.6, 132.2, 131.1, 130.6, 130.4, 129.9, 129.7, 129.3, 128.7, 128.7, 127.6, 127.5, 127.4, 127.3, 127.3, 127.2, 125.9, 125.5, 123.8, 106.8, 104.0, 92.0, 65.9, 18.9, 11.8 ppm; HRMS (ESI-TOF) m/z: [C58H56O5Si]+calcd. [C58H56O5Si] 860.3892; found 860.3891. 2,5-bis(4′-(1,3-dioxolan-2-yl)-[1,1′-biphenyl]-4-yl)-3-(3-ethynylphenyl)-4-phenylcyclopenta-2,4-dien-1-one (3). An oven dried 25 mL Schlenk flask was charged under N2with 2 (61.3 mg, 0.07 mmol) in anhydrous THF (7 mL). A solution of TBAF (0.76 mL, 0.076 mmol, 0.1 M in THF) was added dropwise to the solution over a period of 5 min at 24° C. The solution was stirred for an additional 10 min and the reaction was quenched with H2O. The suspension was extracted with CH2Cl2and the organic phase was washed with H2O, dried over Na2SO4and concentrated on a rotary evaporator. Column chromatography (SiO2; 3:2 hexanes/EtOAc) yielded 3 (23.9 mg, 0.034 mmol, 48%) as a purple solid.1H NMR (500 MHz, CD2Cl2, 22° C.) 5=7.64-7.60 (m, 4H), 7.56-7.50 (m, 8H), 7.41 (dt, J=7.7, 1.2, 1H), 7.35-7.32 (m, 4H), 7.31-7.29 (m, 1H), 7.26-7.18 (m, 3H), 7.14-7.12 (m, 1H), 7.03-6.99 (m, 3H), 5.81-5.80 (m, 2H), 4.14-4.11 (m, 4H), 4.04-4.00 (m, 4H), 3.06 (s, 1H) ppm;13C NMR (101 MHz, CD2Cl2, 22° C.) δ=200.7, 155.3, 154.2, 141.8, 141.8, 140.3, 140.1, 138.0, 138.0, 134.3, 133.5, 133.1, 132.7, 131.1, 130.6, 130.3, 130.3, 129.8, 129.3, 128.9, 128.7, 127.6, 127.4, 127.3, 127.3, 127.2, 126.0, 125.4, 122.6, 104.0, 83.3, 78.3, 65.9 ppm; HRMS (ESI-TOF) m/z: [C49H36O5]′ calcd. [C49H36O5] 704.2557; found 704.2558. poly-phenylene precursor (4). An oven dried 5 mL sealable tube was charged under N2with 3 (55.9 mg, 0.079 mmol) in Ph2O (279.5 mg, 0.25 mL). The solution was degassed. The tube was sealed under N2and heated to 230° C. for 18 h. The solution was cooled to 24° C., MeOH was added, and the precipitate was collected via centrifuge. The precipitate was dissolved in THF and reprecipitated with MeOH (1:2 THF/MeOH) and the resulting precipitate was collected via centrifuge. This process was repeated three times yielding 4 (46.8 mg, 87%) as a colorless solid.1H NMR (400 MHz, CD2Cl2, 22° C.) δ=7.61-7.34 (m, 8H), 7.31-6.50 (m, 18H), 5.83-5.71 (br s, 2H), 4.16-3.89 (m, 8H) Aldehyde functionalized poly-phenylene (5). A 20 mL vial was charged with 4 (83.1 mg, 0.12 mmol) in CHCl3(9 mL) under N2. At 24° C. a solution of p-TsOH*H2O (17.1 mg, 0.09 mmol) in acetone (2 mL) was added dropwise. The solution was stirred at 24° C. for 24 h. The reaction was quenched with saturated NaHCO3and the organic phase was collected, washed with H2O, saturated aqueous NaCl solution, and dried over MgSO4. The combined organic phases were concentrated and the polymer was precipitated via addition of MeOH. The solid was collected via centrifuge and reprecipitated from THF:MeOH (1:2). The crude polymer (66 mg, 0.10 mmol, 93%) was further purified via preparative GPC (CHCl3), yielding a colorless solid (25.5 mg, 0.04 mmol, 36%)1H NMR (400 MHz, CDCl3, 22° C.) 5=10.06-9.85 (m, 2H), 7.94-7.29 (m, 10H), 7.21-6.45 (m, 16H) ppm. CHO-cGNR. An oven dried 250 mL Schlenk flask was charged under N2with 5 (21.6 mg, 0.037 mmol) in anhydrous CH2Cl2(120 mL). While sparging with N2, a solution of FeCl3(352.2 mg, 2.17 mmol, 7 eq. per H) in anhydrous MeNO2(3.5 mL) was added at 0° C. The reaction mixture was warmed to 24° C. and stirred for 72 h under a continuous stream of N2. The black reaction mixture was quenched with MeOH and filtered over a membrane filter. The precipitate was washed with MeOH and THF. The solid was sonicated in (1:1) toluene/THF, filtered, then washed with THF, acetone, hexanes, ethyl acetate, and acetone yielding a dark purple precipitate CHO-cGNR (21.5 mg, 99%). Raman (powder) λ−1=253, 1277, 1332, 1603, 2688, 2892, 2942, 3216 cm−1. cGNR-COF thin films. A dispersion of CHO-cGNR (1.349 mg) in (1:1) o-DCB/CHCl3(4 mL), was added to a solution of benzidine (0.431 mg, 0.002 mmol) in (1:1) o-DCB/CHCl3(1 mL) and filtered through a pad of glass wool. A silanized vial was charged with the reaction mixture and carefully layered with a 5 mM Sc(OTf)3(aq.) solution. The vial was left undisturbed for 7 days, during which a gray film began to appear at the interface of the two liquids. The aqueous phase was gently removed by syringe and replaced with H2O. The organic phase was gently removed and replaced with (1:1) o-DCB/CHCl3. The film formed at the interface was scooped onto a substrate. The film was washed by dipping the substrate into water, acetone then isopropyl alcohol. cGNR-COF film powder. A dispersion of CHO-cGNR (1.349 mg) in (1:1) o-DCB/CHCl3(4 mL), was added to a solution of benzidine (0.431 mg, 0.002 mmol) in (1:1) o-DCB/CHCl3(1 mL) and filtered through a pad of glass wool. A silanized vial was charged with the reaction mixture and carefully layered with a 5 mM Sc(OTf)3(aq.) solution. The vial was left undisturbed for 7 days, during which a gray film began to appear at the interface of the two liquids. The aqueous phase was gently removed by syringe and replaced with H2O. The organic phase was gently removed and replaced with (1:1) o-DCB/CHCl3. A maximum amount of aqueous and organic phase was removed without disturbing the film. The interface suspended film was quickly poured into an excess of acetone. The film suspension was allowed to settle and the majority of the acetone was removed and replaced with fresh acetone. This process was repeated four times and the film dispersion was stored in acetone. Liquid-phase exfoliation of cGNR-COF films. A dispersion of cGNR-COF films in acetone (2-3 drops) was added to o-DCB (1 mL) and the suspension was sonicated for 15 min. The resulting dispersion was drop-cast onto the desired substrate at 24° C. and the solvent was removed under a stream of N2. The substrate was gently rinsed with water, acetone, isopropyl alcohol, and dried under a stream of N2. Synthesis of cGNR-COF films. The synthesis of CHO-cGNRs is depicted inFIG.1A. Diels-Alder polymerization of acetal protected cyclopentadienone 3 yields the poly-phenylene precursor 4. Size exclusion chromatography (SEC) shows a bimodal distribution of linear polymers (Mn=26,000 g mol−1) and cyclic oligomers (Mn=3,000 g mol-1) (seeFIG.2) characteristic for a step-growth polymerization mechanism (see Narita et al.,Nat Chem6:126-132 (2014) and Narita et al.,ACS Nano8:11622-11630 (2014)). Acid catalyzed deprotection of crude 4 yields the aldehyde functionalized poly-phenylene 5. Fractionation of the polymer mixture by preparative SEC gave access to samples 20 of high molecular weight linear polymer 5 (Mn=18,500 g mol−1) and low molecular weight cyclic oligomers (Mn=2,100 g mol−1) (seeFIG.1B). MALDI mass spectroscopy of linear polymers 4 and 5 shows families of molecular ions separated by the repeat unit of the polymers, 676 g mol−1and 588 g mol−1for 4 and 5, respectively (seeFIG.1C). The successful deprotection of 4 is further corroborated by the absence of characteristic peaks associated with the acetal protecting group (δ=4.16-3.89 ppm) in1H-NMR spectra of 5 and the appearance of a new peak consistent with the aldehyde group hydrogen atoms (δ=10.06-9.85 ppm) (seeFIG.3). Oxidative cyclodehydrogenation of 5 yields CHO-cGNR as a dark solid. Raman spectra of CHO-cGNRs show the characteristic signatures of cGNRs; a radial breathing like mode (RBLM) (253 cm−1), the D (1332 cm−1), and the G (1603 cm−1) peaks as well as overtone 2D, D+D′, and 2D′ peaks (seeFIG.1D). An overlay of the respective IR spectra of poly-phenylene 5 and CHO-cGNR confirms the presence of aldehyde groups in the GNRs. The relative intensity of the characteristic aldehyde C═O stretching mode at 1699 cm−1, with respect to the C═C stretching mode at 1602 cm−1, remains unchanged following the oxidative cyclodehydrogenation (seeFIG.1E). The UV/vis absorption spectrum of aldehyde functionalized CHO-cGNRs, indistinguishable from an original sample of cGNRs featuring solubilizing alkyl chains (seeFIG.4), along with the characteristic Raman spectra (seeFIG.1D), is further evidence that the oxidative cyclodehydrogenation proceeds to the expected high degree of conversion. Synthesis of cGNR-COF films. Imine cross-linked crystalline cGNR-COFs were grown using a Lewis acid catalyzed interfacial polymerization. The physical separation of the catalyst (Sc(OTf)3), dissolved in an aqueous phase, and the organic building blocks, CHO-cGNRs and the benzidine cross-linker dispersed in an immiscible organic phase, relegate the COF film growth exclusively to the liquid interface. The limited stability of dispersions of CHO-cGNRs in a wide variety of solvents along with the requirement that the density of the organic phase be greater than the aqueous phase to prevent the undesired precipitation of amorphous GNR aggregates at the liquid-liquid interface during film growth, narrowed the selection of organic solvents to mixtures of o-dichlorobenzene (o-DCB) and chloroform. High quality cGNR-COFs were obtained by layering an aqueous solution of Sc(OTf)3(5 mM) over a homogenous dispersion of CHO-cGNRs and benzidine in o-DCB/CHCl3(v/v=1:1). Over the course of 5-7 days gray films form at the liquid-liquid boundary that were scooped from the interface and transferred onto solid substrates (seeFIG.5). A series of control experiments that alternately remove any one of the critical components, CHO-cGNRs, benzidine cross-linker, or Sc(OTf)3, from the reaction mixture preclude the formation of cGNRCOFs even after extended reaction times. Similarly, the replacement of CHO-cGNRs with unfunctionalized cGNRs did not lead to the formation of COF films at the liquid-liquid interface (seeFIG.6). It was concluded that the observed cGNR-COF films formed in the presence of both reaction partners, CHO-cGNRs, benzidine, and the Lewis acid catalyst are not comprised of non-covalently assembled films formed at the interface solely driven by n-n interactions. A structural model for cGNR-COF is presented in Table 1: TABLE 1Structural Model for cGNR-COFcGNR-COFTriclinic, P{tilde over (1)}a = 5.0000 Å, b = 7.4000 Å, c = 25.5000 Åα = 100°, β = 90°, γ = 90°AtomxyzC10.294130.202480.04067C20.095330.241330.08105C30.27601−0.117060.04717C40.07798−0.077940.08740C50.982790.101170.10535C60.391570.021670.02217C70.665200.288120.16958N80.775950.131950.14724C90.41257−0.219650.41913C100.20870−0.196780.45897C110.514590.260450.39936C120.103120.317010.47982C130.716910.242260.35975C140.14755−0.490830.27373C150.34666−0.517760.23359C160.409300.109560.41977C170.205320.139030.45962C180.51633−0.397400.39895C190.10143−0.344710.48017C200.71948−0.431340.35908C210.145820.184770.27476C220.346120.157970.23440C230.450610.306670.21290C240.823100.391540.33881C251.040900.361400.29548C260.59240−0.444610.57963C270.79415−0.468510.54017C280.494650.070020.59898C290.895390.011880.52069H300.381600.318.31.02185H311.023330.388250.09448H320.34191−0.265940.03505H33−0.00948−0.193540.10634H340.728460.421990.15681H351.06905−0.346920.28936H360.42831−0.395510.21691H370.064650.062420.29146H380.425280.014190.21883H390.802500.101160.34310H400.80779−0.312530.34171 Optical visualization and Raman spectroscopy of CGNR-COF films. Optical microscopy of cGNR-COFs transferred onto a Si/SiO2surface reveal large flakes (>1000 μm2) of uniform color contrast (seeFIG.5B). Raman spectra recorded at various positions on cGNR-COF films show the characteristic RBLM, D, and G peaks associated with CHO-cGNRs, supporting the structural assignment (seeFIG.5C, blue and red trace). Areas of the SiO2apparently devoid of cGNR-COFs show only very weak Raman signatures (seeFIG.5C, black trace), attributed to small GNR aggregates or individual ribbons transferred with the solvent during the scooping process. Spatial Raman maps of the G-peak intensity of cGNR-COFs on Si/SiO2seamlessly coincide with the optical contrast in microscopy images (seeFIG.7). Attenuation of the FT-IR spectra recorded on transferred cGNR-COFs reveal the formation of imine bonds within the film. The FT-IR spectrum of the cGNR-COF, as compared to the CHO-cGNR, shows a decrease in the intensity of the characteristic aldehyde C═O stretching mode (λ−1=1702 cm−1) relative to the C═C mode (λ−1=1600 cm−1) (seeFIG.1E). The imine C═N stretching mode resulting from the crosslinking of CHO-cGNRs with benzidine appears as a new shoulder at λ−1=1657 cm−1in the IR spectrum of cGNR-COFs (seeFIG.1E). Electron microscopy visualization of cGNR-COF films. cGNR-COF film morphology and thickness were examined using scanning electron microscopy (SEM) and atomic force microscopy (AFM). SEM images of cGNR-COF films transferred onto TEM grids show large-scale homogeneity and well-defined film morphology (seeFIG.5D). Large areas (>100 μm2) of homogenous, smooth films show little to no amorphous regions or protrusions from the surface (seeFIG.5D). This is further supported by ambient AFM that shows films with height profiles ranging from 2-20 nm (seeFIG.5E,FIG.8). The thickness of cGNR-COF films prepared through Lewis acid catalyzed growth at the liquid-liquid interface scales linearly with the initial concentration of CHO-cGNRs (seeFIG.9). Dilute dispersions of CHO-cGNRs (67 μg mL−1) yield film thicknesses as low as 2 nm while higher concentrations (270 μg mL−1) form films with average thicknesses in excess of 20 nm. Synchrotron X-ray scattering was used to study the crystallographic structure of cGNR-COF films. FIG.10A shows the projected trace of the wide-angle X-ray scattering (WAXS) pattern of powdered samples of cGNR-COFs grown at the liquid-liquid interface. The data was collected by suspending a dried, powdered sample of cGNR-COFs in a quartz capillary perpendicular to the incident beam. The WAXS pattern shows three characteristic reflections at 2q=3.5°, 7.0°, and 12.0° corresponding to d-spacings of 2.5 nm, 1.2 nm, and 0.7 nm, respectively (seeFIG.10A). A structure model for the packing of cGNR-COF constructed in the triclinic space group P-1 with unit cell parameters a=5.0 Å, b=7.4 Å, c=25.5 Å, a=100°, b=90°, and g=90° is depicted inFIG.10B. The predicted diffraction pattern is in good agreement with experimental data. The observed reflections at 2.5 nm, 1.2 nm, and 0.7 nm were assigned to the (001), (002), and (01-1) planes, respectively (FIG.10A). The (001) and (002) Bragg reflections correspond to the distance, and half the distance, between parallel ribbons (2.5 nm and 1.25 nm) whereas the (01-1) corresponds to the spacing of benzidine linkers (0.7 nm) lining the edges of the cGNRs (seeFIG.10B). The Bragg reflections associated with the interlayer Π-stacking between cGNRs is masked by the pronounced background of the quartz capillary in the expected region of the WAXS pattern. A high-resolution transmission electron microscopy (HR-TEM) was used to study the crystalline domain size of cGNR-COF films directly scooped from the liquid-liquid interphase (seeFIG.10C). The micrographs, recorded at a total electron dose of 100 e Å−2to minimize sample damage, display clear lattice fringes corresponding to the distance between linkers (0.7 nm) (seeFIG.10D) and the π-stacking between ribbons (0.35 nm) (seeFIG.10E), respectively. The observed lattice fringes corroborate the molecular model depicted inFIG.10Band can be assigned to the (01-1) and (105) lattice planes, respectively. The fact that the (001) and (002) planes related to the distance between covalently linked cGNRs cannot be observed in the TEM images is attributed to a preferential orientation of the crystallites within the film relative to the TEM grid. Following the scooping transfer the cGNR-COFs adopt orientations in which the lateral spacing between cGNRs (2.5 nm) lies on an axis perpendicular to the surface and remains out of focus leaving only the n-stacking and linker-linker distances to be observed by in-plane elastic scattering. Most notably, the HR-TEM demonstrates that the crystalline domain size (>400 nm2) is 1-2 orders of magnitude larger than previously reported solution processable GNR films formed via n-stacking alone. cGNR-COFs not only self-assemble into larger crystallites but macromolecular reticulation through directional covalent bonds allows for the rational design of highly anisotropic materials. Finally, adopting a liquid-phase exfoliation protocol for the delamination of crystalline 2D COFs, allowed for the access of free-standing few-layer 2D cGNR-COF sheets. A dispersion of multilayer films grown from a saturated CHO-cGNR solution in acetone was transferred to o DCB, sonicated, and drop-cast onto Si/SiO2. The resulting cGNR-COF flakes were analyzed using ambient AFM to determine the film thickness, size, and homogeneity (FIGS.11Aand B). The lateral dimensions of the cGNR-COF flakes are >105 nm2and range in thickness between 0.70 nm (FIG.11C) and 1.05 nm (FIG.11D), corresponding to bilayer and trilayer stacks of 2D cGNR-COF sheets (Π-Π-stacking distance 4=0.35 nm). Some exfoliated films exhibit layered height profiles commensurate with step-edges within a single flake (seeFIG.12). The orthotropic crystal packing adopted by GNRs in 2D COF films represents a unique opportunity to enhance the chemical, physical, and optoelectronic properties of COFs by independently tuning the mechanical and electrical material properties along all three axes of the crystal lattice. A number of embodiments have been described herein. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of this disclosure. Accordingly, other embodiments are within the scope of the following claims. | 35,783 |
11858815 | DETAILED DESCRIPTION One or more embodiments relate to a synthetic absorbent material for hydrocarbon and water separation. The synthetic absorbent material is an alkylamine modified graphene that removes hydrocarbon, such as oil, from a hydrocarbon and water mixture, to be described. The composition and methods of use may be used for produced water in the oil and gas industry; chemical separation; environmental cleanup, like oil spills; produced water treatment; and general water purification. One or more embodiments relates to a composition of matter, including modified graphene derivatives functionalized with linear alkylamines. These molecules may also be called alkylamine modified graphene. The alkylamine modified graphene molecules efficiently absorb hydrocarbon, such as from a mixture of hydrocarbon and water, compared to graphene molecules that are not modified with alkylamine. The separation efficiency of hydrocarbon from water is due in part from the alkylamine functional groups (alkylamine chains on graphene) that allow said separation. These alkylamine functional groups on graphene are hydrophobic by nature and have affinity toward non-polar solvents and molecules. Since water is hydrophilic, the alkylamine modified graphene does not absorb water. The alkylamine modified graphene molecules withstand use in treated water. The molecules may withstand processing conditions such as batch reaction, single-pass, and recycle-pass processes. The type of water may be salt water, acidic oil and water, or other suitable treated water. One or more embodiments relates to a system for mechanical filtration using filtration media that is useful for removal of hydrocarbons from a combination of hydrocarbons and water. The alkylamine modified graphene is useful as a filtration medium for hydrocarbon-contaminated water. The system includes a pump, tubing, filtration device packed with filtration media, and one or more collection tanks. One or more embodiments relates to a method for removal of hydrocarbons from water. The method may include introducing water contaminated with oil, hydrocarbon, non-polar solvents, or mixtures thereof (“hydrocarbon-contaminated water”) into one or more alkylamine modified graphene. The oil, hydrocarbon, non-polar solvents, and mixtures thereof may be referred to as oil or hydrocarbon throughout and may also include organic material that is typically present in the organic media to be separated. As a non-limiting example, hydrocarbon-contaminated water from an oil well may include hydrocarbons including, but not limited to paraffins, naphthenes, aromatics, tars, maltenes, and asphaltenes. Conventional compositions and methods for separating oil, hydrocarbon, and non-polar organic contaminants from water may use porous supporting architectures. A “porous supporting architecture” incorporates a chemical support in the composition, including, but not limited to, carbon nanotubes, carbon nanofibers, metal nanoparticles, nanodiamonds, and architectures used to support molecules having a hydrophobicity. The exterior surfaces (or the faces) of these porous supporting architectures are generally modified to provide super-selective wettable materials that may be classified as superhydrophobic or superhydrophilic materials. In one or more embodiments, the alkylamine modified graphene is not coupled to or impregnated onto a porous supporting architecture. That is, the composition is without a porous supporting architecture. The alkylamine functional groups on alkylamine modified graphene are of hydrophobic nature and have improved affinity toward non-polar molecules compared to alkylamine functional groups of a less hydrophobic nature. So, separation is controlled by the structure of the alkylamine modified graphene molecules rather than by a modified porous supporting architecture. A superhydrophilic material allows the absorption or passage of water through it. preventing absorption or passage of oil, hydrocarbon, or non-polar solvents. Hydrophilic surfaces are defined as having a water contact angle less than 90°. A superhydrophobic material prevents water from passing through it, while allowing non-polar molecules to readily pass through or to be absorbed by the material. Hydrophobic surfaces are defined as having a water contact angle greater than 90°. Composition In one or more embodiments, the composition is an alkylamine modified graphene, which is a synthetic absorbent material. The alkylamine modified graphene is in the form of nanosheets. The alkylamine modified graphene includes a graphene core and an alkylamine functional group, to be described. The general formula for and definition of “alkylamine modified graphene” is R[—CH2-(alkylamine)]x, where R is graphene, where CH2is a methylene carbon, and where x is an amount of alkylamine functional group. In one or more embodiments, x is a non-zero integer. In another one or more embodiments, x is in a range of from 1 to 12, such as from 1 to 11, from 1 to 10, from 2 to 12, from 2 to 11, from 2 to 10, from 3 to 12, from 3 to 11, or from 3 to 10. As depicted inFIGS.1-3, x=3, meaning that there are 3 “[—CH2-(alkylamine)]” functional groups in these depictions. An “alkylamine functional group” is a functional group that has the formula “[—CH2-(alkylamine)].” The “alkylamine” is a saturated n-alkyl-amine of 3 to 12 carbons in length. For example, the alkylamine may be of 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbons in length. The alkylamine functional group may include, but is not limited to, one or more selected from the group consisting of [—CH2-(n-propylamine)], [—CH2-(n-hexylamine)], and [—CH2-(n-dodecylamine)]. It is envisioned that different types of alkylamine functional groups of one or more embodiments may be included on a single graphene core. The alkylamine functional group formula “[—CH2-(n-propylamine)]” may be expressed as “[—CH2—NH—(CH2)2CH3].” The alkylamine functional group formula “[—CH2-(n-hexylamine)]” may be expressed as “[—CH2—NH—(CH2)5CH3].” The alkylamine functional group formula “[—CH2-(n-dodecylamine)]” may be expressed as “[—CH2—NH—(CH2)11CH3].” As depicted in embodimentFIGS.1-3, the alkylamine functional groups are attached to different carbons on the graphene core. However, in one or more embodiments the alkylamine functional groups may be attached to the same carbon on the graphene core. The alkylamine functional group is bound to an outer carbon of the graphene core. Thus, these alkylamine functional groups are concentrated on the edges and corners of the graphene core. In this instance, the edges and corners of the molecules include the outer rings and atoms of the graphene nanosheet. An outer carbon of the graphene core is not limited to a location on an outer ring (as shown inFIGS.1-3) and may include another suitable outer carbon that is not on a ring (such as a ring that has been broken, or an incomplete ring). The carbon-carbon bond between the graphene core and the alkylamine functional group may extend from an SP2hybridized carbon (as shown inFIGS.1-3) or it may extend from an SP3hybridized carbon. Three variations of the alkylamine modified graphene are as follows. The alkylamine modified graphene may include R[—CH2-(n-propylamine)]xcalled “GPA,” where R and x are previously described and where an embodiment thereof is shown inFIG.1. The alkylamine modified graphene may include R[—CH2-(n-hexylamine)]x, called “GHA,” where R and x are previously described and where an embodiment thereof is shown inFIG.2. The alkylamine modified graphene may include R[—CH2-(n-dodecylamine)]x, called “GDA,” where R and x are previously described and where an embodiment thereof is shown inFIG.3. The weight ratio of alkylamine functional group to graphene core may be in a range of from about 20:1 to 30:1 in the alkylamine modified graphene, such as 21:1 to 30:1, 22:1 to 30:1, 23:1 to 30:1, 20:1 to 29:1, 21:1 to 29:1, 22:1 to 29:1, 23:1 to 29:1, 20:1 to 28:1, 21:1 to 28:1, 22:1 to 28:1, 23:1 to 28:1, 20:1 to 27:1, 21:1 to 27:1, 22:1 to 27:1, 23:1 to 27:1, 20:1 to 26:1, 21:1 to 26:1, 22:1 to 26:1, 23:1 to 26:1, 20:1 to 25:1, 21:1 to 25:1, 22:1 to 25:1, or 23:1 to 25:1. This weight ratio of alkylamine functional group to graphene core increases hydrophobicity of the alkylamine modified graphene, thereby contributing to absorption capacity properties. The absorption capacity of the alkylamine modified graphene may be stable at conditions such as batch or dynamic mode (to treat water with flow rate), where stable means that the absorption capacity remains within the specified range. In one or more embodiments, the graphene core is a reduced graphene oxide (rGO). Generally, graphene oxide (GO) may include epoxides, alcohols, and other oxygenated functional groups, whereas rGO may include an absence of select bonds such as single or double bonds, carbon to carbon bonds, and carbon to oxygen bonds on the graphene rings. Thus, the structure of the functionalized and reduced graphene core (rGO) in alkylamine modified graphene may vary slightly fromFIGS.1-3, to be described. In one or more embodiments, a nitrogen functional group is coupled to the graphene core in trace amounts. The phrases “trace” or “trace amounts” represent a quantity that is 100 parts per thousand or less. Thus, in addition to an alkylamine functional group, the composition may include one or more nitrogen functional group, including, but not limited to, amides, amines, and alkylammonium salts. Such nitrogen functional groups may be present from an addition or reduction process. In one or more embodiments, an oxygen functional group is coupled to the graphene core in trace amounts. Thus, the alkylamine modified graphene may include one or more oxygen functional group, including but not limited to, oxides; alcohols; diols, such as vicinal diols; carbonyls; amides; epoxides; acids; other oxygen-containing functional group; or other oxidized functional group. Such oxygen functional groups may be present from an incomplete reduction process. Trace amounts of an oxygen functional group on the alkylamine modified graphene may provide a contact angle greater than 150° (contact angle with water). This contact angle corresponds with the contact angle of a superhydrophobic material. Where an oxygen functional group on the alkylamine modified graphene is absent, a zero amount, then the contact angle may be greater than 160°. The alkylamine modified graphene may have broken bonds from those shown in the figures. Such broken bonds may arise from a reduction process. Examples of these broken bonds include, but are not limited to, broken single, double, or aromatic bonds on a graphene (or a reduced graphene oxide) ring. For example, there may be one or more partial ring saturations on the alkylamine modified graphene. The broken bonds may be present on the corners or edges of the alkylamine modified graphene. The broken bonds may be present in reduced amounts on the faces of the alkylamine modified graphene compared to the corners or edges. In this instance, the faces of the alkylamine modified graphene (front face and back face) include bonds that are not on the corners or edges of the graphene core. As previously described, the alkylamine modified graphene is a graphene nanosheet. A “nanosheet” is an individual molecule of alkylamine modified graphene. The nanosheet has a length, a width, and a height. The ‘nano’ dimension is measured along the height of the molecule from a front face to a back face. The height of the molecule ranges from about 7 to 30 nanometers (nm), such as from 8 to 30 nm, 9 to 28 nm, 10 to 26 nm, and 12 to 24 nm. The length of the nanosheet is in the range of about 2 to 20 micrometers (μm), such as 3 to 20 μm, 4 to 20 μm, or 5 to 20 μm. The width of the nanosheet is in the range of about 2 to 20 micrometers (μm), such as 3 to 20 μm, 4 to 20 μm, or 5 to 20 μm. The shape of the nanosheet is not particularly limited and may include an overall rectangle shape, a square shape, or other geometric shape. This 2 to 20 μm length and width range of nanosheet is considered longer (or larger) than nanosheets of a smaller size range, even though a smaller size range may overlap a portion of the 2 to 20 μm range. Longer (or larger) nanosheets may be stable mechanically and thermally, while providing good separation efficiency, as compared to nanosheets of a smaller size range. For example, the alkylamine modified graphene nanosheets of one or more embodiments provide separation efficiency of 75% or greater, such as 80% or greater, 85% or greater, 90% or greater, or 95% or greater. When graphene is not functionalized according to one or more embodiments, the graphene (GO or rGO) may provide insufficient separation efficiency, such as separation efficiency less 75%, less than 70%, less than 65%, less than 60%, less than 55%, or less than 50%. The alkylamine modified graphene contact angle is between about 135° to 170°, such as between 135° to 165°, 140° to 165, 145° to 165°, 150° to 168°, 150° to 165°, 151° to 170°, 151° to 165°, 152° to 170°, 152° to 165°, or 152 to 163°. GPA has a contact angle within a range of from about 140° to 150°, such as 141° to 150°, 142 to 150°, 143° to 150°, 144° to 150°, or 145° to 150°. GHA has a contact angle within a range of from about 145° to 155°, such as 146° to 155°, 147° to 155°, 148° to 155°, 149° to 155°, or 150° to 155°. GDA has a contact angle within a range of from about 155° to 170°, such as 156° to 170°, 157° to 170, 158° to 170°, 159° to 170°, 160° to 170°, 160° to 169°, 160° to 168°, 160° to 167°, 160° to 166°, or 160° to 165°. The contact angle of the alkylamine modified graphene demonstrates that the molecules are hydrophobic. This further indicates that an oxygen containing group is present in trace amounts on the alkylamine modified graphene. In general, the composition does not include any sponge material, such as melamine sponge. The composition does not include carbonized foam material. Such carbonized foam material may be polymerized foam that forms a hydrophobic oleophilic material. Further, the composition does not include carbon nanotubes. Advantageously, the alkylamine modified graphene provides a water rejection in the range of about 95% or more, such as 96% or more, 97% or more, 98% or more, 99% or more. In one or more embodiments, the alkylamine modified graphene provides a water rejection of 100%. Process to Prepare Composition Graphene oxide (GO) is prepared from graphite by a modified Hummer's method. Alkylamine is added to react with the carboxylic acids on the graphene oxide to form amides. The resultant alkylamide functionalized GO is then reduced. The reduction simultaneously reduces amides to amines while removing a substantial amount of oxygen atoms from the alkylamide functionalized GO to form an alkylamine functionalized rGO, the alkylamine modified graphene. A “substantial amount of oxygen atoms” in this instance is an amount of oxygen atoms that results in trace amounts of oxygen functional groups on the alkylamine modified graphene. System The filtration system of one or more embodiments is shown inFIG.4. A mechanical filtering system is envisioned. The system includes an input tube102(configured to allow flow of oil, hydrocarbons, non-polar solvents, and water mixtures) and an output hydrocarbon tube110(configured to allow flow of oil, hydrocarbons, and non-polar solvents), as well as an output aqueous tube108(configured to allow flow of water, polar solvents, and mixtures thereof). Between the input and output tubes are various parts of the system that work together that are configured to separate hydrocarbon from a fluid comprising a hydrocarbon and water. The system includes a holding tank100configured to contain an amount of fluid comprising hydrocarbon and water. For example, the holding tank may house a hydrocarbon and water combination to be separated. The holding tank may be a physical tank. When a physical tank is not provided, the holding tank may be an input from another source of fluid comprising hydrocarbon and water that feeds the input tube102. In this instance, the fluid comprising hydrocarbon and water may be an immiscible mixture. In other instances, the fluid comprising hydrocarbon and water may be a moderately or fully miscible mixture. The system includes a pump104that is configured to control flow rate. The pump is downstream of the holding tank and upstream of a membrane housing106. A suitable pump is one with a controlled flow rate, including, but not limited to, a peristaltic pump. A suitable pump may be a static or variable pressure or volume pump, with an ability to control flow rate. The pump may have a revolution per minute (rpm) range of from about 1 rpm to 400 rpm. The flow rate is dependent on other factors, such as the diameter of the tubing (or for a pump other than a peristaltic pump, the volumetric size of the pump). In one or more embodiments, a pressurized tube116is included between the pump and the membrane housing. In one or more embodiments, the pump is coupled directly to the membrane housing. As mentioned, the system includes a membrane housing106packed with filtration media200that is downstream of the holding tank. The filtration media200is the alkylamine modified graphene of one or more embodiments. The filtration media may be one type of alkylamine modified graphene, or multiple types of alkylamine modified graphene in combination. The membrane housing106includes two or more membranes. The filtration media is packed (or is present) between two or more membranes within the membrane housing106. The two or more membranes are positioned within the membrane housing to prevent loss of filtration media. For example, one membrane may be positioned between the pressurized tube116and the filtration media200. Another membrane may be positioned between the filtration media200and the output aqueous tube108. Further, another membrane may be positioned between the filtration media200and the output hydrocarbon tube110. The amount of membranes is not particularly limited and may include, but is not limited to, two membranes, three membranes, four membranes, or more than four membranes. Where more than two membranes are included, multiple membranes may be layered together without filtration media between or they may be separated with filtration media between them. The membranes are permeable to hydrocarbons and water but impermeable to the filtration media. The membranes may be made of a polysulfone material. As previously mentioned, the system includes tubing to couple the parts of the system. Such tubing may couple the holding tank and the pump (input tube102). Tubing may couple the pump and the membrane housing and is configured to provide pressurized flow of hydrocarbon and water (pressurized tube116). Tubing may couple the membrane housing to a collection tank. The amount of output tubes is not particularly limited and may include 2 or more output tubes. In one or more embodiments, an output aqueous tube108couples the membrane housing and a water collection tank112and is configured to provide flow of decontaminated water. In one or more embodiments, an output hydrocarbon tube couples the membrane housing and a hydrocarbon collection tank114and is configured to provide flow of separated hydrocarbon. The tubing may withstand pressures of from 0.1 to 50 Pascal. The system may include one or more collection tank. The one or more collection tank may include one or more water collection tank112. The one or more collection tank may include one or more hydrocarbon collection tank114. When a physical tank is not included, the collection tank may be an outlet, such as a hydrocarbon outlet and a water outlet. A combination of an outlet with one type of collection tank is envisioned. For example, the system may include a hydrocarbon outlet and a water collection tank. In another example, the system may include a water outlet and a hydrocarbon collection tank. A combination of multiple outlets without a collection tank is also envisioned. In general, the system removes oil, such as crude oil or other non-polar solvents or hydrocarbons, from an emulsified or contaminated water stream. The system is designed to recover decontaminated water or recovers decontaminated water. A hydrocarbon-contaminated water enters the system at the holding tank100and is pulled through the input tube102via the pump104, which allows the hydrocarbon-contaminated water to flow into the membrane housing106. The filtration media200is superhydrophobic and hydrocarbon-absorbent. The filtration media within the filtration device absorbs oil, hydrocarbon, and non-polar solvent, while repelling water out of the filtration device via output aqueous tube108into the water collection tank112. When the filtration media is saturated with absorbed hydrocarbon, it is called hydrocarbon-absorbed alkylamine modified graphene. The oil, hydrocarbon, or non-polar solvent is pushed out of the filtration media and membrane housing via output hydrocarbon tube110and into the hydrocarbon collection tank114. Methods In one or more embodiments, a method is provided that includes introducing the composition, alkylamine modified graphene, as a filtration media into a hydrocarbon contaminated water. In another one or more embodiments, a method is provided that includes introducing a hydrocarbon contaminated water into alkylamine modified graphene, as a filtration media. Prior to use, the alkylamine modified graphene is a solid, such as a powder. The method includes absorbing hydrocarbon from the hydrocarbon-contaminated water using the filtration media (alkylamine modified graphene). In one or more embodiments, the step of absorbing hydrocarbon includes absorbing a mass of hydrocarbon that is in a range of from about 25 to 65 times the weight of the filtration media (with 95% or more water rejection, such as up to 100% water rejection). The method includes creating a hydrocarbon-absorbed filtration media (alkylamine modified graphene) and recovered water. The method includes separating of an oil phase and a water phase, where the oil phase includes the hydrocarbon-absorbed filtration media (oil, hydrocarbon, non-polar solvents and alkylamine modified graphene) and the water phase includes recovered water. In one or more embodiments, the method includes recovering the separated oil phase from the water phase. In one or more embodiments, the method includes further recovering the separated oil phase from the hydrocarbon-absorbed alkylamine modified graphene. In one or more embodiments, 75% or more of the hydrocarbon from the hydrocarbon-absorbed alkylamine modified graphene is recovered. For example, 80% or more, 85% or more, 90% or more, 95% or more, or 99% or more of the hydrocarbon from the hydrocarbon-absorbed alkylamine modified graphene may be recovered. In one or more embodiments, about 95% or more of the water in the hydrocarbon-contaminated water is recovered. For example, 95% or more, 96% or more, 97% or more, 98% or more, 99% or more, or 100% of the water in the hydrocarbon-contaminated water is recovered in the recovered water. In one or more embodiments, the method does not include forming of an emulsion to collect hydrocarbon, as this may affect and reduce the performance of the alkylamine modified graphene for absorbing hydrocarbon compared to when no emulsion is formed. In some instances, however, hydrocarbon-contaminated water includes, in part, an emulsion of oil and water. In such instances, it is envisioned that oil absorption into alkylamine modified graphene proceeds as designed. In one or more embodiments, a sponge material is not used to absorb oil, hydrocarbon, or non-polar solvent. The method is a treatment method for oil and water combination or oil- or hydrocarbon-contaminated water. The method may be used as a secondary or tertiary step to improve separation of oil and water. For example, the method may be used downstream of a bottom or tops skimmer from a chemical plant. The method may ensure removal of hydrocarbons (from water) that flow through and are not skimmed off the top or separated from the bottoms. The method may further treat wastewater from a water treatment facility, for example, where microbes have not broken down the hydrocarbons. A method of treatment involving produced water recovers the oil that was previously trapped in produced water. When treating produced water with the method of one or more embodiments, oil that is trapped in the produced water is not re-injected back into the well, such as in traditional injection or disposal wells. The method of treatment involving produced water may be used for flooding and fracturing applications. This method of treatment may reduce oil concentration in produced water compared to without the method, thereby avoiding and preventing damage to the well formation. A method of treatment involving a gas oil separation plant (GOSP) may reduce chemical injections in the treatment process by removing oil and hydrocarbons from the water. System Method In one or more embodiments, a low flow rate (at lab scale, or small scale, this is about 1 to 500 milliliters per minute (mL/min)) of hydrocarbon-contaminated water is provided to condition the filtration device. After conditioning, the flow rate is increased with the pump. The outlets are then opened to collect the separated hydrocarbon in the hydrocarbon collection tank and the rejected water in the water collection tank. EXAMPLES The examples include absorption capacity, oil absorption, and separation efficiency tests using the composition and method of one or more embodiments. Materials The materials used are as follows. The natural graphite powder (99.9%) was commercially purchased from Fluka™ AG, Chemische Fabrik, Buchs (Switzerland). Sulphuric acid (98%), hydrochloric acid (35%), sodium nitrate (98%), hydrogen peroxide (30%), hydrazine hydrate (80%), and potassium permanganate (99%) were obtained from Sigma-Aldrich Co. (USA) and were used without further purification. n-propylamine (PA), n-hexylamine (HA), and n-dodecylamine (DA) were purchased from Merck Schuchardt OHG (Germany) and were used as received. Cyclohexane, n-hexane, n-decane, n-heptane, and ethanol (99.8% purity) were supplied by Sigma-Aldrich Co. (USA) and used as received. Deionized water (DI) was used throughout as a water source. Synthesis of Alkylamine Modified Graphene The synthesis of graphene oxide precursor is as follows. Graphene oxide (GO) nanosheets were prepared by a modified Hummer's method. Graphite powder (2 grams (g)) and sodium nitrate (2 g) were added to 90 milliliters (mL) of sulfuric acid (98%, mass fraction) and stirred for 4 hours (h) at 0-5° C. under atmospheric conditions. Potassium permanganate (12 g) was added, keeping the temperature below 15° C. 184 mL of water was added, and the mixture was stirred for 2 hours. The ice bath was removed, and the mixture stirred for 2 hours at 35° C. Next, the mixture was refluxed at 98° C. for 10-15 min. The temperature was reduced to 30° C., which gave a brown colored solution. The solution was treated with 40 mL hydrogen peroxide while the solution changed to a yellow color. 200 mL of water was added and stirred for 1 hour followed by sitting without stirring for 3-4 hours, where particles settled at the bottom. The resulting mixture was neutralized, which included filtering and washing by centrifugation (7000 revolutions per minute for 15 minutes) with 10% HCl followed by DI water until it formed gel-like substance with neutral pH. The supernatant was decanted, and the gel-like substance was dried under vacuum at 60° C. to obtain graphene oxide (GO) nanosheets in powder form. The synthesis of alkylamine modified graphene is as follows. The as-synthesized GO nanosheets in powder form were dispersed in DI water (0.5 g GO/100 mL DI water) and the resulting suspension was sonicated for 1 hour. Alkylamine (about 12 g) was dissolved in 200 mL ethanol, and the GO water suspension was added to the alkylamine-ethanol solution. 1.0 g of GO was added to about 0.1 to 0.5 moles alkylamine. 1.0 g of GO to about 0.05 to 4 moles of alkylamine may be used in some scenarios. The mixture was stirred for a day at room temperature to create the alkylamine modified graphene oxide, which was separated out by centrifuge. This synthetic step relies on amidation between alkylamine and carboxy groups. Weight ratio of alkylamine to graphene is 24:1 in the solution and in the final alkylamine modified graphene. Reduction of alkylamine-functionalized graphene oxide proceeded by adding 5 mL hydrazine hydrate, and the mixture was refluxed for 3 hours at 95° C. The resultant alkylamine modified graphene was washed by filtration with ethanol-water mixture (1:1) to eliminate unreacted hydrazine hydrate or excess alkyl amine. The material was dried under vacuum at 60° C. for a day or more. The resulting solid was vacuum dried at 60° C. for 24 hours or more. This procedure was used to synthesize GPA, GHA, and GDA. The synthesis does not include octylamine, dodecylamine, and hexadecylamine. The synthesis does not rely on interaction between a potential epoxy group on GO and an alkylamine. The synthesis does not include microwave assisted thermal expansion. No surface protection procedure, such as addition of wax, is applied that may coat a particle prior to its modification. The synthesis does not include thionyl chloride before addition of alkylamine. That is, halogenated functional groups are not present on the alkylamine modified graphene. Other various forms of carboxylic acid activation are not envisioned, such as Lewis acid activation, anhydride activation, or other forms of activation. Graphene oxide is not refluxed with an organic solvent of alkylamine at a high temperature. “High temperature,” such as 300° C. or greater, may affect the stability of (break down) the alkylamine modified graphene, and are avoided. Analysis of Alkylamine Modified Graphene FTIR spectra of the materials were obtained using Thermo Nicolet™ 6700 FTIR spectrophotometer. Potassium bromide (KBr) was ground with the sample to prepare the pellet for better resolution of the peaks. The samples were scanned in the wavenumber range of 400 to 4000 1/centimeter (cm−1). FIG.5shows FTIR data of GO, as compared to the alkylamine modified graphene: GPA, GHA, and GDA. One difference between the GPA, GHA, and GDA spectra and the FTIR spectra relative to that of GO is the disappearance of the bands corresponding to some oxygen-containing functionalities (such as the OH stretch at a wavenumber of 3426 1/centimeter (cm−1), C═O stretch at 1724 cm−1, and C—O stretch at 1225 and 1054 cm−1). This may be attributed to the presence of alkylamine-terminated organic groups (alkylamine functional groups) in the alkylamine modified graphene. Such covalent linkages may reduce the FTIR stretch of functional moieties previously present on GO (for example, COOH) at the edges of the graphene sheets, through amide bonding and subsequent amide reduction to amine. Also, the loss of oxygen functional peaks is indicative of the reduction of the modified graphene oxide by hydrazine hydrate. This chemical reduction further exposes more aromatic islands or pi systems at the basal plane compared to the GO. Such lack of oxide and other oxygen functional groups is indicated by the aforementioned absence of oxygenated bonds in the FTIR and the presence of C═C bonds at the basal plane, which can be confirmed from the C═C stretching at ˜1630 cm−1. In addition, the bands at 3435 cm−1with symmetric peak shape are indicative of the N—H stretching on GDA, GHA, and GPA. The doublet at 2921 cm−1may correspond to the asymmetric C—H vibrations of the alkyl groups. The doublet at 2853 cm−1may correspond to the symmetric C—H vibrations of the alkyl groups. FIG.6shows Raman spectra of GO as compared to the alkylamine modified graphene: GPA, GHA, and GDA, at a 633 nanometer (nm) laser excitation. Raman spectra were obtained using a HORIBA LabRAM spectrometer (HORIBA Jobin Yvon Raman Division) with backscattered confocal configuration. A long working distance objective with a magnification of 50 times was used both to collect the scattered light and to focus the laser beam on the sample surface Samples were scanned from Raman shift of 700 to 2000 cm−1. Raman spectroscopy identification provides an overview of the particle morphology of carbon-based materials. There are at least two prominent bands for such materials, such as the D and G bands, as shown inFIG.6. The G band, which peaks at 1587 cm−1inFIG.6, corresponds to a primary in-plane vibrational mode of sp2hybridized carbon atoms, such as those present in rings and chains, or having pi orbital systems. The disorder band (D band), which peaks at 1331 cm−1inFIG.6, is indicative of a different in-plane vibration (compared to the G band), which can be described as the structural disorder caused by the sp3hybridized carbon atoms. Such sp3hybridized carbons include those covalently bonded to other functionalities in the alkylamine modified graphene. The ratio of the peak intensity of D to G bands (ID/IG) is used to evaluate the extent of disorder in graphene-based materials. A more intense D band compared to a G band indicates more broken ordered graphene sp2bonds as compared to unmodified GO (or non-functionalized rGO), and more newly formed sp3bonds as compared to unmodified GO (or non-functionalized rGO), resulting in more elastic scattering. The peak intensity ratio (ID/IG), of GDA (ID/IG=1.41), GHA (ID/IG=1.40) and GPA (ID/IG=1.31) increased compared to that of GO (ID/IG=1.14). This fractional increase in peak intensity ratio demonstrates that new defects are present in GDA, GHA, and GPA as compared to GO. The contact angles of the alkylamine modified graphene was measured using a Biolin Scientific Attension Theta Flex optical tensiometer. The contact angle for GPA was measured to be within a range of from about 140° to 149°. The contact angle for GHA was measured as 152°. The contact angle for GDA was measured as 163°. Example 1 Absorption Capacity Tests Experiments were carried out to assess the quantitative oil absorption performance of the alkylamine modified graphene. In typical absorption capacity measurements, oil and common organic solvents including decane, cyclohexane, and hexane were selected as models. In these tests, GPA, GHA, and GDA were placed in separate beakers containing the respective oil or organic solvent to be absorbed. The alkylamine modified graphene was submerged under 10 mL of the absorbate and pressed in the liquid for oil absorption. The material was then taken out and compressed manually with the aid of a quick-grip clamp. Mass (weight) measurements before and after oil absorption were taken to evaluate the absorption capacity of the prepared materials for oil and three different organic solvents (hydrocarbons). The original weight of the sample was weighed and recorded as Mi. Then, the sample was placed into the oil or organic solvent for absorption. The sample was weighed when, with the increase of absorption time, its weight was unchanged. This weight was recorded as Mt. The absorption capacity of materials (Q) for oil and various organic solvents was calculated according to the equation Q(gg)=Mt-MiMi, where Mtis the weight of the material after absorption of oil or organic solvents in time t and Miis the weight of the dry material. The absorption capacities, “Q” (gram/gram (g/g)), of the alkylamine modified graphene in both oil and organic liquid media (non-polar hydrocarbon solvents) are shown in in Table 1 andFIG.7. TABLE 1Absorption capacities of alkylamine modified graphene.Weight gain (gram per gram)GPADecane26 g/gCyclohexane47 g/gHexane53 g/gOil28 g/gGHADecane32 g/gCyclohexane60 g/gHexane58 g/gOil35 g/gGDADecane34 g/gCyclohexane64 g/gHexane60 g/gOil28 g/g As a control test, unmodified graphene oxide (GO, without alkylamine functional groups, and without reduction) provided 50% separation efficiency or less for oil and organic liquid media in the same tests. GPA displays absorption capacities ranging from 26 to 53 times its own weight for the absorbates used. GHA displays absorption capacities ranging from 32 to 60 times its own weight for the absorbates used. GDA displays absorption capacities ranging from 34 to 64 times its own weight for the absorbates used. Of the alkylamine modified graphene compounds tested, GDA provided improved absorption capacity compared to GPA and GPA. Regarding GPA, these absorption capacity results may be due to an increase of GPA hydrophilicity as compared to GHA and GDA, from the existence of more nitrogen atoms per mass. Of the absorbates tested, cyclohexane and hexane were absorbed more efficiently than decane or oil. With the alkylamine modified graphene compounds tested, the method is simple and easily scaled up to large batch fabrication (100 times or more compared to the small or lab scale tests in the examples). These absorption capacities are in a rage of from about 25 to 65 times the weight of the alkylamine modified graphene, based on the density and viscosity of the oil and solvents. Without wanting to be bound by theory, the absorption capacity performance and selectivity of lower molecular weight absorbates may be associated with the structures that result from alkylamine modified graphene particle agglomeration and the superoleophilic and superhydrophobic properties these materials. Example 2 Oil Absorption Tests The procedure for the oil absorption tests was performed as follows. The initial weight of the alkylamine modified graphene was measured. The alkylamine modified graphene was then dipped in a mixture 20:2 of dyed water and hydrocarbon for 5-10 minutes until the hydrocarbon was fully adsorbed. The final weight of the alkylamine modified graphene and time of adsorption was noted. Afterward, the alkylamine modified graphene went through a desorption process to separate from the hydrocarbon. The initial weight of the alkylamine modified graphene was measured again, to ensure no hydrocarbon remained. The procedure was repeated with a different hydrocarbon and a fresh sample of alkylamine modified graphene. Oil absorption tests were performed on GDA, which initially showed improved absorption capacities from Example 1 compared to GPA and GHA. The results of the oil absorption tests performed with GDA are shown in Table 2. TABLE 2Oil absorption tests with GDA.Time ofInitialWetActualHydrocarbonfullweight ofmaterialSpecificabsorbedEntry(HC)absorptionmaterialweightGravityHC in mLComments12 milliliters5 minutes0.28 grams1.3g0.659g/mL2mLComplete(mL) hexane(min)(g)absorptionof HC22mL heptane5min0.28 g1.2g0.6838g/mL1.75mLCompleteabsorptionof HC32mL octane10min0.28 g1.14g0.692g/mL1.64mLSlightlyless HCabsorbed The alkylamine modified graphene provided high hydrocarbon absorptivity in these tests. “High hydrocarbon absorptivity” means that the material absorbs over 3 times its initial weight of hydrocarbon (light n-alkyl hydrocarbons). “Complete absorption of HC” means 100% separation efficiency (hydrocarbon absorption). “Slightly less HC absorbed” means 99% separation efficiency or more (hydrocarbon absorption). Example 3 Separation Efficiency Tests The separation efficiency of alkylamine modified graphene was assessed by measuring the weight percentage of collected oil or solvent in an oil-water or an organic solvent-water mixture (which are examples of hydrocarbon-contaminated water). Methylene blue dye was used as a coloring agent for the water layer, to visually distinguish the water layer from the organic layer. For these tests, fresh samples of GPA, GHA, and GDA were dipped in the respective oil or solvent/water mixture (5 mL:45 mL). As the alkylamine modified graphene powders physically approached the liquid mixtures, they selectively and quickly absorbed the solvent or oil that floated on the surface of the water, leaving behind water in the system. The alkylamine modified graphene (with or without absorbed hydrocarbon) also tended to float on the surface, even when initially immersed by an external force. The results of the separation efficiency tests are shown in Table 3 andFIG.8. TABLE 3Separation efficiencies of alkylamine modified graphene.Separation Efficiency (%)GPAn-Decane84%n-Hexane85%n-Cyclohexane82%Oil79%GHAn-Decane96%n-Hexane97%n-Cyclohexane93%Oil92%GDAn-Decane100%n-Hexane100%n-Cyclohexane95%Oil96% The oil or organic solvent (hydrocarbon) was recovered by a mechanical squeezing process and the respective materials were reused repeatedly with similar separation efficiency. The separation efficiency of the hydrophobic and oleophilic alkylamine modified graphene nanosheets for the organic solvents and oil is 75% or more, such as 79% or more, 92% or more, or 95% or more. The GDA molecules had improved separation efficiency compared to GPA and GHA in these tests. As previously mentioned, the alkylamine modified graphene instantly absorbed oil or organic solvent once the material was in contact with the oil or organic solvent. This differential affinity to an organic phase shows that the alkylamine modified graphene is oleophilic and hydrophobic. Without being bound by theory, the oil or organic solvent may flow rapidly into the space that exists between individual molecules of alkylamine functionalized graphene. The space existing between individual molecules may result from aggregation of the alkylamine modified graphene molecules. The collective analytical and test results from the alkylamine modified graphene of one or more embodiments show that these molecules provide superhydrophobic properties. Further, it is shown that alkylamine modified graphene may provide up to 100% water rejection. As used here and in the appended claims, the words “comprise,” “has,” and “include” and all grammatical variations thereof are each intended to have an open, non-limiting meaning that does not exclude additional elements or steps. “Optionally” means that the subsequently described event or circumstances may or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not occur. When the word “approximately” or “about” are used, this term may mean that there can be a variance in value of up to ±10%, of up to 5%, of up to 2%, of up to 1%, of up to 0.5%, of up to 0.1%, or up to 0.01%. Ranges may be expressed as from about one particular value to about another particular value, inclusive. When such a range is expressed, it should be understood that another one or more embodiments is from the one particular value to the other particular value, along with all particular values and combinations thereof within the range. Although a few example embodiments have been described in detail, those skilled in the art will readily appreciate that many modifications are possible in the example embodiments without materially departing from this disclosure. All modifications of one or more disclosed embodiments are intended to be included within the scope of this disclosure as defined in the following claims. In the claims, means-plus-function clauses are intended to cover the structures previously described as performing the recited function and not only structural equivalents, but also equivalent structures. It is the express intention of the applicant not to invoke 35 U.S.C. § 112(f) for any limitations of any of the claims, except for those in which the claim expressly uses the words ‘means for’ together with an associated function. It is noted that one or more of the following claims utilize the term “where” or “in which” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.” For the purposes of defining the present technology, the transitional phrase “consisting of” may be introduced in the claims as a closed preamble term limiting the scope of the claims to the recited components or steps and any naturally occurring impurities. For the purposes of defining the present technology, the transitional phrase “consisting essentially of” may be introduced in the claims to limit the scope of one or more claims to the recited elements, components, materials, or method steps as well as any non-recited elements, components, materials, or method steps that do not materially affect the novel characteristics of the claimed subject matter. The transitional phrases “consisting of” and “consisting essentially of” may be interpreted to be subsets of the open-ended transitional phrases, such as “comprising” and “including,” such that any use of an open-ended phrase to introduce a recitation of a series of elements, components, materials, or steps should be interpreted to also disclose recitation of the series of elements, components, materials, or steps using the closed terms “consisting of” and “consisting essentially of.” For example, the recitation of a composition “comprising” components A, B, and C should be interpreted as also disclosing a composition “consisting of” components A, B, and C as well as a composition “consisting essentially of” components A, B, and C. Any quantitative value expressed in the present application may be considered to include open-ended embodiments consistent with the transitional phrases “comprising” or “including” as well as closed or partially closed embodiments consistent with the transitional phrases “consisting of” and “consisting essentially of.” The words “comprise,” “has,” and “include” and all grammatical variations thereof are each intended to have an open, non-limiting meaning that does not exclude additional elements or steps. While one or more embodiments of the present disclosure have been described with respect to a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised, which do not depart from the scope of the disclosure. Accordingly, the scope of the disclosure should be limited only by the attached claims. | 46,672 |
11858816 | DETAILED DESCRIPTION Before the present methods and systems are disclosed and described, it is to be understood that the methods and systems are not limited to specific synthetic methods, specific components, or to particular compositions. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Ranges may be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not. Throughout the description and claims of this specification, the word “comprise” and variations of the word, such as “comprising” and “comprises,” means “including but not limited to,” and is not intended to exclude, for example, other additives, components, integers or steps. “Exemplary” means “an example of” and is not intended to convey an indication of a preferred or ideal embodiment. “Such as” is not used in a restrictive sense, but for explanatory purposes. Disclosed are components that can be used to perform the disclosed methods and systems. These and other components are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these components are disclosed that while specific reference of each various individual and collective combinations and permutation of these may not be explicitly disclosed, each is specifically contemplated and described herein, for all methods and systems. This applies to all aspects of this application including, but not limited to, steps in disclosed methods. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the disclosed methods. Disclosed herein are three-dimensional porous substrates having porous struts radiating from the surfaces of the substrate. The struts can radiate from the outer surface of the substrate, as well as from the surfaces of the pores permeating the substrate. Exemplary struts include dendrites, which include branched structures and acicular structures radiating from the substrate. As used herein, the term “ramified” refers to object bearing dendritic structures. The struts can be attached to the substrate at a single point of attachment, and individual struts are not connected to other struts. The porous dendrites can have an average pore size from 1-10,000 nm, 1-5,000 nm, 1-2,500 nm, 1-2,000 nm, 1-1,500 nm, 1-1,000 nm, 10-1,000 nm, 100-1,000 nm, 100-500 nm, 500-1,000 nm, or 500-2,000 nm. The substrate and struts can include materials such as graphite, conductive metals, silicon and conductive polymers. Exemplary conductive metals include copper, nickel, iron, cobalt, gold, platinum, rhodium, and mixtures thereof. Exemplary conductive polymers include poly(pyrrole), poly(acetylene), poly(phenylene vinylene), poly(thiophene), poly(3,4-ethylenedioxythiophene), poly(aniline), poly(phenylene sulfide), and mixtures thereof. In some instances, the substrate and struts may be made of the same material, wherein in others the substrate and struts are made of different materials. Three dimensional substrates include those in which the shortest dimension is at least 100 μm, at least 200 μm, at least 300 μm, at least 400 μm, at least 500 μm, at least 600 μm, at least 700 μm, at least 800 μm, at least 900 μm, or at least 1,000 μm thick. The substrate may include a porous foam, for instance a three dimensional foam. Three-dimensional foams can have an average pore size from 1-1,000 μm, 10-1,000 μm, 10-500 μm, 50-500 μm, or 100-500 μm. The substrate can have a multilevel porosity, for instance a core level having a first porosity, and a shell level having a second porosity. The core can have an average pore size from 1-1,000 μm, 10-1,000 μm, 10-500 μm, 50-500 μm, or 100-500 μm. The core can include materials such as graphite, conductive metals, silicon and conductive polymers. In some instances the pores in the shell are smaller than the pores in the core, for instance, the shell can have an average pore size that is less than 50%, 40%, 30%, 20%, 10%, 5%, or 1% the average pore size of the pores in the core. In some embodiments, the shell portion has an average pore size from 1-100 μm, 1-50 μm, 1-25 μm, 2-25 μm, 2-15 μm, 2-10 μm, 2-8 μm, 2-5 μm, 5-25 μm, 5-15 μm, 5-10 μm or 5-8 μm. The shell can include materials such as graphite, conductive metals, silicon and conductive polymers. In some instances, the core and the shell are made from the same materials, whereas in other cases the core is made of a different material than the shell. In certain embodiments, the core, shell, and dendrites are all porous graphite, while in other embodiments the core, shell, and dendrites are all porous metal. Preferred metals include nickel, copper, and mixtures thereof. When the shell and core are the same material, the two levels will typically have different porosities. However, the shell and core are different materials, they may have the same porosities, or different porosities. The porous dendritic structures are characterized by high surface area. For instance, the structures can have a BET surface area of at least 5.0 m2/g, at least 5.5 m2/g, at least 6.0 m2/g, at least 6.5 m2/g, at least 7.0 m2/g, at least 7.5 m2/g, at least 8.0 m2/g, at least 8.5 m2/g, at least 9.0 m2/g, at least 9.5 m2/g, or at least 10.0 m2/g. In some instances, the structures can have an areal density of at least 0.01 mg2/cm, at least 0.05 mg2/cm, at least 0.10 mg2/cm, at least 0.15 mg2/cm, at least 0.20 mg2/cm, at least 0.25 mg2/cm, at least 0.30 mg2/cm, at least 0.35 mg2/cm, at least 0.40 mg2/cm, at least 0.45 mg2/cm, or at least 0.50 mg2/cm. In some embodiments, the substrate can have a volumetric surface area of at least 0.01 m2/cm3, at least 0.05 m2cm3, at least 0.10 m2/cm3, at least 0.15 m2/cm3, at least 0.20 m2/cm3, at least 0.25 m2/cm3, at least 0.30 m2/cm3, at least 0.35 m2/cm3, at least 0.40 m2/cm3, at least 0.45 m2/cm3, at least 0.50 m2/cm3, at least 0.55 m2/cm3, at least 0.60 m2/cm3, at least 0.65 m2/cm3, at least 0.70 m2/cm3, at least 0.75 m2/cm3, at least 0.80 m2/cm3, at least 0.85 m2/cm3, at least 0.90 m2/cm3, at least 0.95 m2/cm3, or at least 1.0 m2/cm3. The BET surface area, areal density, and volumetric surface area can be determined using the 5-point BET surface area test, such as performed by Pacific Surface Science Inc. Samples are prepared with nitrogen gas at 200° C. for 2 hours before test. The 5-point BET test is carried out by nitrogen adsorption at 77K. To obtain data with different units shown as above the planar area, mass, and volume of a sample can be combined with the total surface area of the sample (as provided by Pacific Surface Science Inc.). The three-dimensional porous substrates having porous struts radiating from the surfaces of the substrate can be obtained by depositing struts on the surface of a conductive substrate. The conductive substrate can be a commercially available metal foam, for instance a nickel foam, a copper foam, an iron foam, a zinc foam, an aluminum foam, or a tin foam. In some embodiments, the substrate can be a multilayered three-dimensional substrate, for instance a core-shell substrate. The substrate can be immersed in an electrolyte solution, wherein the electrolyte solution is in electrical communication with an electrode. The electrolyte solution can include metal ions, such as copper ions, nickel ions, cobalt ions, and mixtures thereof. The ions can be provided in the form of metal salts. An electric current can be applied via the electrode in order to precipitate dissolved ions onto the surfaces of the substrate in the shape of dendritic structures. The size and shape of the dendritic structures can be tuned by controlling the parameters of the electrochemical deposition. In some instances, the electrodeposition is conducted at an applied current of at least −25 mA, at least −50 mA, at least −75 mA, at least −100 mA, at least −125 mA, at least −150 mA, at least −175 mA, or at least −200 mA. The electrodeposition can include an applied voltage from −2.5 V-2.5 V, from −2.0 V-2.5 V, from −1.5 V-2.5 V, from −1.0 V-2.5 V, from −1.0 V-2.0 V, or from −1.0 V-1.9 V. The electrodeposition can include depositing on the substrate from 25-500 C/in2, from 25-400 C/in2, from 25-300 C/in2, from 50-300 C/in2, from 50-200 C/in2, from 50-150 C/in2, from 75-150 C/in2, from 75-125 C/in2, from 100-125 C/in2, relative to the surface area of the substrate. In some embodiments, the electrodeposition can be conducted over a series of electrodeposition cycles. After a period of electrodeposition, the substrate is rotated relative to the electrode, followed by additional electrodeposition. The substrate can be rotated 30°, 60°, 90°, 120°, 150°, or 180° relative to the electrode, and can be rotated along one or two axes. For instance, the substrate can be rotated 180° along two axes. The electrodeposition can be conducted over at least 2, 3, 4, 5, 6, 7, 8, 9 or 10 cycles. In some instances, the current is discontinued during the rotation phases, while in others, the substrate is rotated while the current is still applied. In yet other embodiments, the substrate is continuously rotated over the course of electrodeposition. By rotating the substrate a more uniform deposition of dendrites can be achieved. After depositing the dendrites on the substrate, the substrate/dendrites can be annealed to give a dendritically porous foam. Typical annealing conditions include heating the dendritic substrate under a gas flow, for instance hydrogen, nitrogen, and mixtures thereof. Exemplary gases include H2at 1-10 sccm, 2-8 sccm, 3-7 sscm or 5 sccm, in combination with N2at 1-100 sccm, 10-90 sccm, 25-75 sccm, 40-60 sccm, or 50 sccm. The annealing can be conducted at a temperature between 500-1,500° C., between about 750-1,250° C., or between about 900-1,100° C. The heating can be performed for at least 1 minute, at least 2 minutes, at least 5 minutes, or at least 10 minutes, for instance, for about 1-20 minutes, 1-15 minutes, 2-15 minutes, 2-10 minutes, 2-8 minutes, or 3-7 minutes. The graphite network can be obtained using chemical vapor deposition or hydrothermal deposition. For instance, chemical vapor deposition can be performed with a carbon source, such as a C2-4hydrocarbon, including, but not limited to, ethylene, acetylene, propylene, propyne, butadiene and mixtures thereof. The deposition can be conducted using a carrier gas, for instance hydrogen. Generally, the deposition can be conducted at a temperature less than about 1,000° C., less than about 900° C., less than about 850° C., less than about 800° C., less than about 750° C., less than about 700° C., less than about 650° C., less than about 600° C., less than about 550° C., or less than about 500° C. In some embodiments, the deposition can be conducted at a temperature between about 500-1,000° C., between about 500-900° C., between about 600-900° C., between about 600-800° C., or between about 650-750° C. In some instances, the deposition is conducted at a temperature around 700° C. The thickness of the struts can be controlled by varying the deposition conditions, such as growth time. The thickness of struts is determined by measuring the areal density of the obtained samples. The deposition can be conducted for at least 1 hour, at least 2 hours, at least 5 hours, at least 10 hours, or at least 15 hours. For instance, the deposition may be conducted for 1-20 hours, 2-20 hours, 2-15 hours, 5-15 hours, or 10-15 hours. After the graphite network has been prepare, the substrate can be removed to give a dendritic graphite structure. In the case of metal foams, the substrate can be removed by etching, for instance chemical etching, such as with one or more acids. In some instances, the substrate can be removed by treatment with a mineral acid, such as HCl, HBr, HI, HF, HNO3, H2SO4, H3PO4, and mixtures thereof, optionally in combination with one or more Lewis acids, for instance a transition metal salt such as FeCl3, FeBr3, BCl3, BF3, AlCl3, AlBr3, Al(OiPr)3, SnClr, TiCl4, or Ti(OiPr)4. The dendritic graphite foams can be combined with a variety of active materials to prepare supercapacitor electrodes. As used herein, such materials can be designated dendritic graphite foam composites (“RPGM”). Suitable active materials include manganese oxides like MnO2and Mn3O4, cobalt oxides like Co3O4, ruthenium oxides like NiO, ferric oxides like Fe3O4, as well as mixed metal oxides like NiCo2O4and MnFe2O4. The active material may be deposited on the surface of the dendritic graphite foams as nanoparticles using conventional techniques, for instance hydrothermal reaction. The loading efficiency of the dendritic graphite foams is substantially improved over conventional foams. Conventional foam composites can be designated “GM.” For instance, the active material can be loaded in an amount greater than 0.5 mg/cm2, greater than 1.0 mg/cm2, greater than 1.5 mg/cm2, greater than 2.0 mg/cm2, greater than 2.5 mg/cm2, greater than 3.0 mg/cm2, greater than 3.5 mg/cm2, greater than 4.0 mg/cm2, greater than 4.5 mg/cm2, or greater than 5.0 mg/cm2. After loading, the active material can constitute at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% of the total weight of the graphite/active material composite. In some embodiments, the active material is loaded in an amount greater than 3 mg/cm2and constitutes at least 70% of the total weight of the graphite/active material composite. In other embodiments, the active material is loaded in an amount greater than 3.5 mg/cm2and constitutes at least 75% of the total weight of the graphite/active material composite. In preferred embodiments, the active material is loaded in an amount greater than 4.0 mg/cm2and constitutes at least 80% of the total weight of the graphite/active material composite. The dendritic graphite foam composites are more electrically conductive than GM composites with similar loading density and growth time of active materials such as Mn3O4nanoparticles [FIG.9a]. It has been demonstrated that an increase in the thickness of Mn3O4impedes the ion diffusion and migration process, resulting in a higher charge transfer resistance. Because of the increased internal surface area provided by the diverging graphitic microbranches and micropores, dendritic graphite foams permit a much thinner and sparser coating of active material even though the loading density is the same compared to conventional graphite foams. For instance, dendritic graphite foam samples (e.g. loading density ˜0.8 mg cm2, Rc=6Ω) possess lower charge transfer resistance than that of GM samples (e.g. loading density ˜0.8 mg cm−2, Rc=27Ω). This is even observed for dendritic graphite foams with a higher areal loading of Mn3O4than conventional foam, of which the reaction time is same (˜1.6 mg cm−2, Rc=13 Ω, 4 h reaction). Supercapacitors can be prepared using the dendritic graphite foam composites disclosed herein as electrode material. Two dendritic graphic foam composites can be separated by an electrolyte and sandwiched between two conductive films. Suitable electrolytes include gel-based electrolytes in which the relevant electrolyte ion (lithium, sodium, potassium, ect) is dispersed in a liquid polymer such as polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, polyvinylidene fluoride, and polyvinyl alcohol. Ionic liquids and conventional liquid electrolytes can also be used (e.g., an organic solvent like propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, or ethyl methyl carbonate). The improved electrical conductivity of dendritic graphite foams also enables enhanced pseudocapacitive performance compared to those of conventional graphite foam based composites. The shapes of CV curves of RPGM (2 h) are more rectangular and symmetric than those of GM (4 h). The number in parenthesis refers to the length of time of the loading reaction. At the same loading density of Mn3O4, the dendritic graphite foam (2 h) exhibits much higher areal capacitances (290 to 120 mF cm−2) compared to those of conventional graphite foam (4 h) (230 to 60 mF cm−2) at scan rates of 1-200 mV s−1[FIG.9b]. The areal capacitance of dendritic graphite foam (2 h) only decreases by 59% when the scan rate increases from 1 to 200 mV s−1, whereas the capacitance of conventional graphite foam (4 h) is attenuated by 74% at the same condition. With a higher loading of Mn3O4(1.57 mg/cm2, 4 h reaction), an even greater areal capacitance of 460 mF cm−2at 1 mV s−1and 400 mF cm−2at 2 mA cm−2can be achieved as shown inFIG.9c-d. The quasi-rectangular shape with small redox peaks in CV curves [FIG.9c] is consistent with the pseudocapacitive characteristics of Mn3O4reported previously. The GCD curves [FIG.9d] are fairly symmetric at current densities of 2 to 40 mA cm−2, indicating high reaction reversibility and coulombic efficiency. By extending the growth time of Mn3O4to 6 and 8 hours, the areal capacitance of dendritic graphite foam is further improved to 670 and 820 mF cm−2(1 mV s−1), respectively [FIG.9e]. After 3,000 continuous charging and discharging cycles at 20 mA cm−2, RPGM-8h still retains 88% of its peak areal capacitance [FIG.9f]. Moreover, the coulombic efficiency maintains 98% after 5,000 consecutive cycles [FIG.9f]. These results suggest a superb electrochemical stability of the dendritic graphite foam composite electrodes. Moreover, owing to the strategically improved specific surface areas, dendritic graphite foams exhibit excellent rate capability compared to those reported previously. The dendritic graphite foam (˜3.91 mg cm−2Mn3O4loading, 8h reaction) offers very high capacitances of 820, 760 and 670 mF cm−2at the scanning rate of 1, 2 and 5 mV s−1, respectively. More importantly, they can maintain a capacitance of 430 mF cm−2at a higher scan rate of 20 mV s−1[FIG.9f]. In comparison, with a similar loading of 3.9 mg cm−2, GF/CNT/MnO2composites offer capacitances of 500 and 250 mF cm−2at 5 and 20 mV s−1, respectively. Though the capacitance can be improved to 750 mF cm−2(5 mV s−1) with a higher loading of the active material at 6.2 mg cm−2, the rate capability is compromised to 280 mF cm−2when the scan rate is increased to 20 mV s−1. Cyclic Voltammogram (CV) curves are acquired from the full cell at 2 to 20 mV s−1[FIG.10bandFIG.21a]. The specific capacitances determined from the CV curves agree excellently with those determined in the aforediscussed half-cell tests. For instance, at 2 mV s−1, the specific capacitance of 191 mF·cm−2obtained with a two electrode setup, corresponding to 764 mF cm−2in a three-electrode testing system, agrees well with that determined in the half-cell experiments (760 mF cm−2). Consistently, an areal capacitance of 200 mF cm−2at a current density of 0.5 mA cm−2, is determined by the GCD tests as shown inFIG.10candFIG.21b. The areal capacitance is among the best of all reported manganese oxide foam supercapacitors, where most full-cell values are below 100 mF cm−2. The dendritic graphite foams disclosed herein maintain their electrical properties (capacitance, conductivity, resistance even when subjected to severe, repeated mechanical strains. For instance, supercapacitors as described above can be bent at a radius of 3.5 mm for 1,000 continuous cycles while maintaining at least 60%, 70%, 75%, 80%, 85%, 90%, or 95% capacitance relative to the initial capacitance prior to any bending. This robustness ensures the dendritic graphite foams can be advantageously deployed in flexible electronics. The dendritic graphite foams can be used to obtain self-powered and portable system for manipulation of nanomotors, i.e. to transport nanomotors made of Au with controlled speed along arbitrary trajectories. The photograph of the device and the schematic illustration of the working principle are shown inFIG.10aandFIG.11a, respectively. The test began with one-dimension (1D) manipulation. As shown inFIG.11b, when the supercapacitor powered one pair of the orthogonal microelectrodes, Au nanomotor can instantly transport in the corresponding direction and then move backward upon reversion of the electric polarity. By integrating two to three supercapacitors, the applied voltages can be readily tuned to 2V and 3V, respectively, compelling the nanomotors to higher velocities than those at 1V. Analysis shows that the translational speed linearly increases with the applied voltage due to the electrostatic interactions as depicted inFIG.11c. Next, by alternating the connections of the supercapacitors with the two orthogonal pairs of microelectrodes amidst controlled duration and sequence, two dimensional manipulation can be obtained. The self-powered device can compel Au nanomotors to trace letters “U” and “T” as shown inFIG.11d. The demonstration of flexible all-solid-state supercapacitors for powering nanomotors evinces the potential of nanomanipulation and nanorobotics for portable and wearable applications enabled by high-performance energy devices. EXAMPLES The following examples are set forth below to illustrate the methods and results according to the disclosed subject matter. These examples are not intended to be inclusive of all aspects of the subject matter disclosed herein, but rather to illustrate representative methods, compositions, and results. These examples are not intended to exclude equivalents and variations of the present invention, which are apparent to one skilled in the art. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in ° C. or is at ambient temperature, and pressure is at or near atmospheric. There are numerous variations and combinations of reaction conditions, e.g., component concentrations, temperatures, pressures, and other reaction ranges and conditions that can be used to optimize the product purity and yield obtained from the described process. Only reasonable and routine experimentation will be required to optimize such process conditions. Example 1: Fabrication of Porous Nickel Foam A 4 by 2 cm2Ni foam was immersed in dilute H2SO4(1M) for 20 min to remove the oxidized layer on the surface and then a layer of Cu was conformably electroplated on all interconnected struts of Ni foam at a current of −700 mA for 800 coulombs in an electrolyte made of 2 M CuSO4and 1 M HBO3. Next, the Cu—Ni composite was dried and annealed in nitrogen (50 SCCM) and hydrogen (5 SCCM) gas atmosphere at the temperature of 1000° C. for 5 min for interfacial atomic diffusion. The deposited Cu—Ni was then partially electrochemically etched from the obtained Cu—Ni alloy foam at current of 350 mA in the same electrolyte for 350 coulombs, resulting in arrays of second-level micropores of ˜2 μm on the surface of Cu—Ni alloy foam networks (porous Ni foam). Example 2: Direct Growth of Ni Dendrites on Planar Substrates or 3-D Ni Foams A planar conducting substrate, such as Ni and Cu foils, or a 3-D Ni foam was immersed in 1M H2SO4to remove the oxide layer and then transferred to Ni—Cu electrolyte (0.1 M nickel chloride, 0.5 M nickel sulfamate, 0.0025 M copper chloride and 0.323 M boric acid). After electrodeposition at a current of −350 mA for 150 coulombs, the sample was turned upside down, and the surface pointing to the reference electrode was also reversed. Then another deposition is continued. Totally four such depositions were carried out on each sample. Next, the obtained Ni—Cu dendrites on porous nickel foam were enforced by annealing in nitrogen (50 SCCM) and hydrogen (5 SCCM) gas atmosphere at the temperature of 1000° C. for 5 min. Example 3: Direct Growth of Ni Dendrites on Porous Nickel Foam The obtained porous nickel foam from Example 1 was immersed in 1M H2SO4to remove the oxide layer and then transferred to Ni—Cu electrolyte (0.1 M nickel chloride, 0.5 M nickel sulfamate, 0.0025 M copper chloride and 0.323 M boric acid). After electrodeposition at a current of −350 mA and 150 coulombs, the sample was turned upside down, and the surface pointing to the reference electrode was also reversed. Totally four such depositions are carried out on each sample. Next, the obtained Ni—Cu dendrites on porous nickel foam were enforced by annealing in nitrogen (50 SCCM) and hydrogen (5 SCCM) at the temperature of 1000° C. for 5 min, resulting in a three-dimensional (3-D) porous nickel foam with hierarchical dendrites and micropores (dendritically porous nickel foam). Example 4: Synthesis of Graphite on Dendritic Structures A piece of dendritic nano structures from Examples 1, 2 and 3 were loaded into a stable heating zone of a quartz tube furnace at 700° C. in the flow of H2(20 SCCM) for 40 min to clean the surface. Then C2H4(10 SCCM) was introduced into the reaction zone to grow graphite on the Ni catalysts for 2.5-15 hour. Next, the sample was slowly cooled to the ambient temperature and then immersed into the mixed solution of 1 M iron chloride (FeCl3) and 2 M hydrochloride (HCl) at room temperature for overnight etching. After rinsing the sample with deionized water several times and drying at 60° C. for 4 hours, a freestanding flexible dendritically porous graphite (GF) thin film (or 3-D foam) was obtained. Example 5: Loading of Active Materials After the growth of Mn3O4for 1 hour, dendritically porous graphite retains 0.569 mg/cm2Mn3O4. In contrast, non-porous graphite retained only 0.076 mg/cm2Mn3O4. Porous graphite prepared as described in 2015/0360952 retained 0.284 mg/cm2Mn3O4. Compared to non-porous graphite, dendritically porous graphite) can substantially increase the volumetric capacitance from 0.062 F/cm2to 0.213 F/cm2[Mn3O4loading duration (1 hr)]. The specific capacitance is also increased from 164 to 260 F/g (1 mV/sec). Comparing to the porous graphite disclosed in US 2015/0360952 the dendritically porous graphite can substantially increase the volumetric capacitance from 0.124 F/cm2to 0.213 F/cm2[porous GF of the same areal density of GF (0.249 mg/cm2) and reaction time of Mn3O4(1 hr)]. The specific capacitance is also increased from 232 to 260 F/g. DendriticallyNon-porousPourousPorousGraphiteGraphiteGraphite(5 hr)(5 hr)(1.5 hr)Mn3O4Reaction Time1 hrMn3O4(mg/cm2)0.0760.2840.569GF (mg/cm2)0.3020.2490.249Mn3O4@ GF (mg/cm2)0.3780.5330.818Specific capacitance164232260(F/g) @ 1 mV/sVolumetric capacitance0.0620.1240.213(F/cm2)@ 1 mV/s Example 7: Synthesis of Porous Cu—Ni Foams A piece of rolled commercial nickel foam (2.5×4 cm2, 200 μm in thickness, MTI Corporation, CA, USA) was soaked in sulfuric acid (H2SO4, 1M) for 20 min to remove the native nickel oxide layer. Then, a thin layer of Cu film was electroplated at −1.8V (vs. Ag/AgCl) for 800 coulombs from an electrolyte made of copper sulfate (CuSO4, 2M) and boric acid (H3BO3, 1M) with copper foil serving as the counter electrode (MTI Corporation, CA, USA). Next, the Cu—Ni composite foams were annealed at a temperature of 1000° C. in a gas flow of hydrogen (H2, 5 sccm) and nitrogen (N2, 50 sccm) at 420 mTorr for 5 min. Finally, the annealed composite was electrochemically etched at +0.6 V (vs. Ag/AgCl) in the same electrolyte for 350 coulombs, resulting in large arrays of micropores uniformly distributed on the interconnected microstruts of the foam. Example 8: Synthesis Cu—Ni Dendrites on Porous Cu—Ni Foams The diverging Cu—Ni dendrites were electrodeposited on the obtained porous Cu—Ni foams at a potential of −1.2 V (vs. Ag/AgCl) for 150 coulombs from an electrolyte made of nickel sulfamate [Ni(SO3NH2)2, 0.5M], nickel chloride (NiCl2, 0.1M), copper chloride (CuCl2, 0.0025M), and boric acid (H3BO3, 0.323M) with nickel foil (Alfa Aesar, MA, USA) working as the counter electrode. The electrodeposition was sequentially repeated four times with the porous Cu—Ni foam substrate rotated upside-down each time to ensure an even coverage of the dendrites. The electrolyte was also replaced every two depositions to replenish the copper ions available for the formation of diverging branches. Upon completion of all four electrodepositions, the Cu—Ni foams were rinsed with deionized water and annealed at 1000° C. in a gas mixture (H2, 5 sccm and N2, 50 sccm) for 5 min to enhance the adhesion between the Cu—Ni dendrites and Cu—Ni foam struts. Example 9: Growth of Dendritic Porous Graphite Foams Rolled commercial nickel foams (200 μm in thickness) or the dendritic porous Cu—Ni foams were annealed in hydrogen (H2) gas flow (20 sccm) at 700° C. for 40 minutes for the removal of surface oxides. Then ethylene (C2H4, 10 sccm) was introduced to grow ultrathin graphite on the nickel foam at a total pressure of 400 mTorr for controlled growth of graphite. The reaction time was 30 h for commercial foam and 15 h for dendritic foam to obtain identical areal mass density of ˜1 mg cm−2for each type of samples. Next, the temperature was rapidly reduced to room temperature in the original growth gas mixture. By selectively etching Ni or Cu—Ni alloy catalysts in a mixture of iron chloride (FeCl3, 1 M) and hydrochloric acid (HCl, 2 M) at 60° C. overnight, free-standing graphite foams were obtained. Afterwards, the ultrathin graphite foam was rinsed with deionized water and ethanol for a few times, and finally dried at 60° C. for 4 hr. Example 10: Growth of Mn3O4 A 1 by 2 cm2graphite foam, prepared in Example 9, was immersed in 4 M HNO3at 50° C. for two hours to activate the surface of the graphite to be hydrophilic. Then the samples were washed with deionized water and dried at 60° C. for 6 hours. Next, potassium permanganate (KMnO4, 0.1 M) and sodium nitrate (NaNO3, 0.1 M) was mixed in a 1:1 ratio under vigorous stirring. Subsequently, the well-mixed solution (30 mL) was transferred into an autoclave and heated to 150° C. for the preset time (1, 2, 4, 6, 8 h). Finally, the obtained graphite/Mn3O4foams was washed with deionized water several times before dried at 60° C. for 10 hours. Example 11: Assembly of all-Solid-State Dendritic Graphite Foam Supercapacitors A dendritic graphite foam (8 h) sample (1 by 2 cm2in area) was affixed to Au (100 nm) coated polyester (PET) film (0.08 mm thickness, ePlastics, CA, USA) with silver epoxy, serving as a half electrode. Then, a LiCl/PVA (polyvinylalcohol) (mass ratio, 8.5:4) gel electrolyte was infiltrated to the RPGM/Au-PET composite followed by 20 min of degassing. Finally, two pieces of RPGM/Au-PET was sandwiched together, followed by drying in an oven at 50° C. overnight, to form an all-solid-stated symmetric supercapacitor. Example 12: Fabrication of Nanomanipulation Device and Au Nanomotors The quadruple microelectrodes with a gap of ˜500 μm were patterned by photolithography. The microelectrodes are made of Au (90 nm)/Cr (10 nm) thin films. The Au nanowires were electrodeposited into nanoporous anodized aluminum oxide and the length of Au nanowires was controlled by the amount of electric charges passing through the circuit. Example 13: Materials Characterization The CV, GCD and EIS of GMs, and RPGMs half-cell tests was carried out in a three-electrode cell setup with sodium sulfate (1M Na2SO4) as the electrolyte, platinum foil as a counter electrode, and Ag/AgCl as a reference electrode. The EIS spectra was tested from 100 kHz to 0.01 Hz. SEM images were recorded by Hitachi S-5500 and FEI Quanta 650 scanning electron microscopes. Transmission electron microscopy (TEM) images were recorded by a high-resolution TEM JEOL 2010F. X-ray diffraction (XRD) patterns were recorded by Philips XPERT Theta-Theta Diffractometer. Raman spectra were recorded by a customized micro-Raman system with a laser of 532 nm. The specific surface areas were measured with the 5-point Brunauer, Emmett and Teller (BET) method (Pacific Surface Science Inc., Oxnard, CA). All the materials were weighed on a high precision electronic balance (CAHN-C30). The mass loading of Mn3O4was measured by weighing the mass difference before and after the growth of Mn3O4on graphite foams. MassMassloadingcontentElectrode SupportMaterial(mg cm−2)(wt %)Loading method(mg cm−2)Ref.Graphene/2.04.84 h hydrothermal reaction,Nickel foam (40)Lee, J. W.Mn3O4powderthen pasted on Nickel foam(2012)[4]MnO2/CNT/Not83 h hydrothermal reactionNickel foamZhu, G.Graphene foammentioned(2014)[5]Mn3O4/RGO1-1.53.64 h CVD, then coated onNickel foamYang, X.Nickel foam(40)(2016)[6]MnO2/Not92.36 h Hydrothermal reactionGraphene foamDong, X.graphene foammentioned(2012)[7]3D9.892.823 h electrodepositionGraphite foamHe, Ygraphene/MnO25.09012 h electrodeposition(0.7-0.75)(2013)[8]compositeGraphene6.288.66 h hydrothermal reactionGraphene foamLiu, Jfoam/CNT/MnO23.983.06 h hydrothermal reaction(0.8)(2014)[3]w/lower concentrationGraphite2.1 (PEDOT-95450 s electrodepositionGraphite foamXia, Xfoam/Co3O4/PEDMnO2)with reduced(2014)[9]OT-MnO2pore size(0.1)Graphite1.0133 h Hydrothermal reactionGraphite foamSun, X.foarn/MnO2(2014)[10]Multilevel porous0.2965.91 h Hydrothermal reactionPorous GraphiteLi, WGraphitefoam (0.15)(2017)[11]foam/Mn3O4NanocrystalsGraphene0.252180 min HydrothermalGraphene foamQin, Tfoam/PPy/MnO2reaction(0.86)(2016)[12]Porous Graphite3.91788 h Hydrothermal ReactionRamified PorousThis workfoams withGraphite foamdiverging(1.1)microtubes/Mn3O4Nanocrystals(This work)GravimetricAreal Capacitance (mF cm−2)capacitance*DemonstratedMaterialHalf cellSymmetric full cell(F g−1)applicationsRef.Graphene/228(5 mV s−1)Not mentioned114 (5 mV s−1) **NoLee, J. W.Mn3O4powder−0.1-0.7 V VS(2012)[4]Ag/AgClMnO2/CNT/Not mentioned27 F g−1(10 mV s−1)251 (1 A g−1) **Light, light-Zhu, G.Graphene foam−0.2-0.8 Vemitting diode(2014)[5](LED)Mn3O4/RGO517(1 A g−1)Not mentioned517 (1 A g−1)**NoYang, X.−0.9-0.1 V VS(2016)[6]Ag/AgClMnO2/Not mentionedNot mentioned250 (1.2 A g−1)NoDong, X.graphene foam0-0.5 V VS(2012)[7]Ag/AgCl, big IRdrop whencharging to 1.0 V3D1420(2 mV s−1)30130 (2 mV s−1)FlexibleHe, Ygraphene/MnO2500(20 mV s−1)(0-1.0 V, 0.3 mA0-1.0 V VSsupercapacitors(2013)[8]composite35.2% retentioncm−2)Ag/AgClat 20 mV s−1w/0.4 mg cm−2750(2 mV s−1)loadingNot mentioned300(20 mV s−1)40% retentionat 20 mV s−1Graphene750(5 mV s−1)Only demonstrated80 (5 mV s−1)Power LEDsLiu, Jfoam/CNT/MnO2280(20 mV s−1)asymmetric0-1.0 V VS(2014)[3]37.3% retentionsupercapacitors w/Ag/AgClat 20 mV s−12.1 mg cm−2loading500(5 mV s−1)due to large electric128 (5 mV s−1)250(20 mV s−1)resistance50% retentionat 20 mV s−1GraphiteNot mentionedPower LEDsXia, Xfoam/Co3O4/PED(2014)[9]OT-MnO2Graphite210(2 A g−1)Not mentioned210 (2 A g−1)NoSun, X.foam/MnO2On MnO2(2014)[10]0-0.9 VSAg/AgClMultilevel porous114(1 mV s−1)52 (0-1.0 V,260 (1 mV s−1)Self-poweredLi, WGraphite10 mV s−1)−0.2-1.0 VSstrain sensors(2017)[11]foam/Mn3O4w/0.29 mg cm−2Ag/AgClNanocrystalsGraphene150(5 mV s−1)40126 (5 mV s−1)FlexibleQin, Tfoam/PPy/MnO2(0-10 V, 10 mV s−1)supercapacitors(2016)[12]w/0.25 mg cm−2Porous Graphite820(1 mV s−1)191(2 mV s−1)164 (1 mV s−1)Self-poweredThisfoams with760(2 mV s−1)126(10 mV s−1)−0.2-1.0 V VSand portableworkdiverging670(5 mV s−1)204(.5 mA cm−2)Ag/AgClnanomotormicrotubes/Mn3O4570(10 mV s−1)(0-1.0 V)manipulationNanocrystals430(20 mV s−1)w/3.91 mg cm−2system(This work)High ratecapability(52.4%retentionat 20 mV s−1)[1]Z. 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Liu; Y. Wen; Z. Wang; X. Jiang; Z. Wan; S. Peng; G. Cao; D. He,J. Mater. Chem. A2016, 4, 9196 The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative compositions and method steps disclosed herein are specifically described, other combinations of the compositions and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein or less, however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated. The term “comprising” and variations thereof as used herein is used synonymously with the term “including” and variations thereof and are open, non-limiting terms. Although the terms “comprising” and “including” have been used herein to describe various embodiments, the terms “consisting essentially of” and “consisting of” can be used in place of “comprising” and “including” to provide for more specific embodiments of the invention and are also disclosed. Other than in the examples, or where otherwise noted, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood at the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, to be construed in light of the number of significant digits and ordinary rounding approaches. | 39,319 |
11858817 | DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS In the following description, for purposes of explanation and not limitation, specific details are set forth in order to provide a thorough understanding of the present disclosure. However, it will be apparent to one skilled in the art that the present subject matter may be practiced in other embodiments that depart from these specific details. In other instances, detailed descriptions of well-known methods and devices are omitted so as to not obscure the present disclosure with unnecessary detail. Disclosed herein is the ability to enable highly reductive chemistry in water. The ability to chemically reduce highly stable contaminants in water is a difficult and unmet challenge that is present in the environment. The impact of nanodiamond photochemistry on the degradation of one of the more resilient in the class of PFASs, PFOS, is demonstrated. Time-dependent spectroscopic methodologies, including nanosecond UV-Vis transient absorption spectroscopy, and prolonged photolysis were used to directly probe the mechanism of PFOS degradation by eaq−under varying environmentally relevant conditions, such as pH. This work demonstrated that hydrogen terminated detonation nanodiamond (HDND) is a promising source of eaq−for PFAS degradation. The method may provide:Highly reductive chemistry in waterPotential to remove difficult contaminants such as PFAS from drinking waterPotential to remediate chem-bio contaminationDoes not require photon energies >5.5 eV (UVC) as does macroscopic diamondCould be “dusted” onto wet surfaces to decontaminate under UVCould be implemented as a packed bed flowthru photochemical reactorPure carbon “photocatalyst” that is not caustic.Safer alternative to liquid ammonia solvated electron technologyEffective in water over a broader pH range than UV-Sulfite solvated electron photochemistry, namely as low as pH 5 The method uses a composition comprising: water and hydrogen-terminated nanodiamonds. The water may already contain, or be suspected of containing, one or more fluoroalkyl compounds. Alternatively, the composition may be added to a possibly contaminated material or surface. The nanodiamonds have an average size of less than 100 or 10 nm in their greatest dimension. Next, the composition is irradiated with light having a wavelength that generates water-solvated electrons from the nanodiamonds. The wavelength may be for example, 225-295 nm or 254 nm.FIG.1illustrates that light may be of lower energy than the bulk diamond bandgap of 5.47 eV. This produces a composition comprising water, the nanodiamonds, and water-solvated electrons. The solvated electrons may react with and degrade any fluoroalkyl compounds that are present. Example fluoroalkyl compounds include, but are not limited to, perfluoroalkyl surfactants, perfluoroalkane sulfonates, perfluoroalkyl acids, perfluorooctane sulfonate, and perfluorooctyl acid. The amount of the fluoroalkyl compound in the composition may be monitored. While monitoring, the irradiation of the composition may be continued until the amount of the fluoroalkyl compound in the composition has been reduced to a target amount.FIG.2shows sample data confirming the degradation of PFOS using HDND and 254 nm light. ODND with light and HDND without light did not cause degradation. The following examples are given to illustrate specific applications. These specific examples are not intended to limit the scope of the disclosure in this application. Preparation of hydrogenated detonation nanodiamond (HDND)—One gram of purified nanodiamond powder (˜6 nm particle size) was placed in a quartz boat and inserted into a horizontal tube furnace. With the constant hydrogen flow of 29.0 sccm and hydrogen pressure of 280 Torr the temperature was raised in steps from ambient to 450° C. during the following 15 days. At the end of 16th day, the treated powder was cooled in a hydrogen atmosphere to 50° C., transferred to a warm glass jar, and placed in a nitrogen-purged box for storage until use. Preparation of oxidized detonation nanodiamond (ODND)—One half gram of purified nanodiamond powder (˜6 nm particle size) was placed in quartz boat and inserted into a horizontal tube furnace. The tube was left open to the room atmosphere and temperature was gradually increased from 25° C. to 445° C. over seven hours. At the end of this time, the powder was cooled to 100° C., transferred to a warm glass jar, and stored in the nitrogen-purged box for storage until use. Probing decomposition of PFOS—Experiments probing the decomposition of PFOS resulting from prolonged irradiation of surface treated detonation nanodiamond were carried out in a Rayonet RPR-100 photochemical reactor equipped with 16 UV lamps (253.7 nm, 35 W max. output, RPR-2537A). The sample solutions were comprised of 100 mg HDND or ODND suspended in 100 mL ultra-pure water (nanopure filtration system, 18 MΩ) containing ˜3 μM PFOS. The experiments were carried out under anaerobic conditions by continually purging the solutions with N2. Aliquots of the UV-irradiated solutions were collected periodically throughout the course of the experiment to monitor the temporal progression of the PFOS decomposition. Degradation of PFOS was quantified by LC-MS using a Varian 500-MS ion trap mass spectrometer working in tandem with Varian 212-LC chromatography pumps. Transient absorption spectroscopy—Transients formed upon UV-light excitation were probed by transient absorption spectroscopy. Details of the transient absorption setup are in Maza et al., Nanosecond transient absorption studies of the pH-dependent hydrated electron quenching by HSO3−. Photochemical&Photobiological Sciences2019, 18(6), 1526-1532. Sample solutions were prepared by suspending ˜10 mg HDND in 20 mL deionized water and filtering through 0.1 μm syringe filter twice to remove larger aggregates and minimize effects due to scattering. Solutions were excited using the 5 ns pulse from a Continuum Minilite II Nd:YAG laser tuned to 266 nm (˜1 mJ/pulse) and probed using either a 790 nm continuous wave (cw) diode laser (Thorlabs model CPS780S) or a 200 W Xe arc lamp (Newport). The pump and probe were directed into the sample collinearly and the change in intensity of the probe was monitored with a Hamamatsu R375 photomultiplier tube (9 ns rise time, 70 ns transit time); the signals were digitized on a 200 MHz Tektronix TDS 420A oscilloscope with a 100 MS s−1sampling rate. Using nanosecond transient absorption it was found that hydrated electrons result by photodetachment from hydrogen-terminated (negative electron affinity) detonation nanodiamond (HDND) suspensions in water upon sub-bandgap (266 nm) irradiation. Hydrated electron photogeneration from oxygen-terminated (positive electron affinity) detonation nanodiamond (ODND), on the other hand, is not observed. The transient absorption data suggest the presence of an interaction between PFOS and HDND and, more so, an interaction between PFOS and the hydrated electrons evidenced by a shorter average lifetime of the hydrated electron in the presence of PFOS. Finally, it was found that prolonged sub-bandgap (254 nm) irradiation of aqueous HDND in the presence of PFOS leads to full decomposition of PFOS by reductive fragmentation, consistent with hydrated electron reductive chemistry. Specifically, 254 nm photolysis of a solution containing 100 mg HDND and 3 μM PFOS (C8F17SO3) results in ˜30% degradation of PFOS within 30 minutes. Nearly complete loss of PFOS is observed within 4 hours of photolysis. The loss of the PFOS LC-MS signal is accompanied by the appearance and growth of product signals corresponding to formation of degradative products including C8F16HSO3(481 m/z), C5F10HSO3(331 m/z), and C4F8HSO3(281 m/z) within the first hour of photolysis. After ˜90 minutes these photoproduct signals monotonically decrease consistent with further degradation. The identity of lower molecular mass (m/z<250) degradative products, however, could not be resolved due to instrument detection limitations. Materials characterization—Nanodiamond surface chemistry was monitored with X-ray photoelectron spectroscopy (XPS). XPS data were acquired using a K-Alpha X-ray Photoelectron Spectrometer (ThermoFisher Scientific). XPS confirmed that sorption onto nanodiamond surfaces is not responsible for the observed depletion of PFOS from solution with UV exposure. Obviously, many modifications and variations are possible in light of the above teachings. It is therefore to be understood that the claimed subject matter may be practiced otherwise than as specifically described. Any reference to claim elements in the singular, e.g., using the articles “a”, “an”, “the”, or “said” is not construed as limiting the element to the singular. | 8,815 |
11858818 | Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or can be learned by practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure, as claimed. DETAILED DESCRIPTION The disclosures herein will be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all possible embodiments are shown. Indeed, disclosures may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements. Like numbers refer to like elements throughout. Many modifications and other embodiments disclosed herein will come to mind to one skilled in the art to which the disclosed compositions and methods pertain having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the disclosures are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation. As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure. Any recited method can be carried out in the order of events recited or in any other order that is logically possible. All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited. The publications discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided herein can be different from the actual publication dates, which can require independent confirmation. Definitions Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and should not be interpreted in an idealized or overly formal sense unless expressly defined herein. As used herein, nomenclature for compounds, including organic compounds, can be given using common names, IUPAC, IUBMB, or CAS recommendations for nomenclature. As used herein, “comprising” is to be interpreted as specifying the presence of the stated features, integers, steps, or components as referred to, but does not preclude the presence or addition of one or more features, integers, steps, or components, or groups thereof. Additionally, the term “comprising” is intended to include examples encompassed by the terms “consisting essentially of” and “consisting of.” Similarly, the term “consisting essentially of” is intended to include examples encompassed by the term “consisting of.” As used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a coal material,” “a flux agent mixture,” or “a secondary carbon material” includes mixtures of two or more such coal materials, flux agent mixtures, or secondary carbon materials, and the like. As used herein, “caking coal” is coal that softens and forms a solid residue on heating to high temperatures (i.e., >1100° C.) to drive off volatile matter in low-to-no oxygen environments. Alternatively, a “non-caking coal” is one that forms a char when heated to devolatilizing conditions. “Caking coal” is also referred to as “coking coal” if the solid residue is coke. In some aspects, “caking” is also referred to as “agglomerating.” As used herein, “bituminous coal” is a soft coal containing bitumen, which is a viscous form of petroleum. Typically, bituminous coal contains greater than 5% volatile matter. Bituminous coal can be high volatile or low volatile as defined herein. “Low volatile” bituminous coal can have about 5% volatile matter, whereas “high volatile” bituminous coal can have up to 30% volatile matter. In one aspect, bituminous coal is useful as a starting material for carbon foams in the processes described herein. “Lignite” coal is sometimes referred to as brown coal and has a fixed carbon content of about 25%, a high moisture content, and an ash content ranging from 6-19%. Lignite coal typically has a high content of volatile matter. As used herein, “sub-bituminous” coal has properties between those of lignite coal and those of bituminous coal. “High volatile” bituminous coal as used herein is coal that has a volatile matter content of greater than about 31% (or has a fixed carbon content of less than 69%). As used herein, “low volatile” bituminous coal is used to refer to coal that has a volatile matter content of between about 14% and about 22% (or has a fixed carbon content of from 78% to 86%). A “flux agent” or “fluxing agent” or “flux material” as used herein refers to any material that responds to the heating method useful herein and further interacts with the coal used herein to generate heat necessary to fuse coal particles together during carbon foam formation. In some aspects, the flux agent responds to the frequency range of microwave radiation used herein. As an example, the flux agent may have hydroxyl groups free to rotate and to absorb energy of the frequency of microwave radiation. In some aspects, the flux agent may be fructose or a carbohydrate syrup and may also include kerosene and/or recovered coal volatiles from the coal conversion process. In a further aspect, these recovered volatiles may include phenanthrene. In one aspect, high volatile bituminous coals will require lower amounts of flux agent than low volatile bituminous coals. “Pitch” as used herein is a complex mixture of high boiling point organic molecules that is normally a solid at room temperature but that becomes a viscoelastic fluid when heated. Pitch is derived, as used herein, from coal tar. In some aspects, pitch can be incorporated into foaming mixtures as a flux agent for transferring heat to coal particles and/or otherwise assisting in carbon foam preparation. In other aspects, pitch can be used as a carbon source for carbon foams made without coal particles. Meanwhile, a “foaming pitch” is a coal tar distillate that can be made from sub-bituminous, bituminous, or lignite coal. In one aspect, a foaming pitch can be used as an additional agent or a flux agent, thereby assisting in the process of forming green foam from carbon materials. “Microwave” radiation may be useful in the processes disclosed herein. Microwave radiation is electromagnetic radiation with a wavelength of about 1 m to 1 mm and a frequency between 300 MHz and 300 GHz. In one aspect, the microwave radiation can be from a household microwave oven or an industrial microwave chamber. In some aspects, microwave radiation is absorbed by hydroxyl groups in a flux agent, which causes heating that is then transferred to coal particles, which in turn absorb heat and give off volatile matter, producing a porous structure. “Induction heating” or “inductive heating” as used herein refers to heating an electrically conductive object using electromagnetic induction. In one aspect, an induction heater passes an alternating current through an electromagnet, which causes an alternating magnetic field to penetrate the object, generating eddy currents. In a further aspect, the eddy currents heat the object. In one aspect, inductive heating is useful herein for heating graphite or other electrically conductive carbons; the heat thus generated is transferred to coal particles. In some aspects, the processes disclosed herein are “pyrolysis” processes. As used herein, pyrolysis is the first of two heating steps used to produce a carbon foam. Prior to pyrolysis as disclosed herein, coal materials, additional agents, and the like, are mixed. Exemplary methods for mixing the coal materials and additional agents can be found in the Examples. During pyrolysis, the foam precursor components (i.e., coal particles) become heated and devolatilize, beginning to stick together. The pyrolysis process produces a “green foam” or a “soft coal.” In one aspect, a green foam is a closed-cell foam. In a typical closed cell foam, cells are pressed together and air and moisture cannot enter. In one aspect, a closed cell foam is rigid and stable. “Calcination” as used herein refers to a thermal treatment to bring about further chemical changes to the carbon foams disclosed herein. In one aspect, calcination improves stability and/or mechanical strength of the foams. In another aspect, calcination causes the foams to become electrically conductive. In one aspect, any calcination step disclosed herein can be conducted in a non-oxidizing environment. In another aspect, the calcination step can be conducted in a kiln, a microwave, an induction heater, or by another method. In one aspect, calcination is carried out at a temperature between about 900° C. and 1350° C. A “carbohydrate syrup” as used herein is any viscous aqueous solution of sugars. In some aspects, carbohydrate syrups are useful as flux agents in the processes disclosed herein. In one aspect, the carbohydrate syrup can be high fructose corn syrup, corn syrup, honey, maple syrup, brown rice syrup, barley malt syrup, molasses, date syrup, or another natural, artificial, or semi-synthetic syrup containing freely-rotating hydroxyl groups susceptible to microwave excitation. Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, a further aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms a further aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed. References in the specification and concluding claims to parts by weight of a particular element or component in a composition denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight component Y, X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound. A weight percent (wt %) of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included. As used herein, the terms “optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not. Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including: matters of logic with respect to arrangement of steps or operational flow; plain meaning derived from grammatical organization or punctuation; and the number or type of embodiments described in the specification. Processes for Producing Carbon Foams In accordance with the purpose(s) of the disclosure, as embodied and broadly described herein, the disclosure, in one aspect, relates to processes for preparation of a carbon foam material, the process comprising heating a mixture comprising a coal material and an electrically conductive carbon material and/or flux agent. In some aspects, other components may be included in the compositions, including, but not limited to, foaming pitch materials, solvents, and the like. In some aspects, the compositions disclosed herein can form a pseudo-fluid material following heating (i.e., following pyrolysis) that can be transferred to a mold and further heated to form a carbon foam, or may form a carbon foam directly after pyrolysis. In either of these aspects, the carbon foam can be further calcined to improve mechanical or electrical properties. The disclosure, in further aspects, relates to carbon foams and other materials prepared using the disclosed processes. Coal In one aspect, the processes disclosed herein require a coal material as a raw material for producing carbon foams. In a further aspect, the coal material is a caking coal. In a further aspect, caking properties can be measured by free swelling index and/or Gessler Plasticity. In a still further aspect, the free swelling index is between about 3.5 and about 5.0 as determined by ASTM D 720, or is about 3.5, 3.75, 4, 4.25, 4.5, 4.75, or about 5, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In a still further aspect, the coal material is a bituminous coal. In one aspect, the bituminous coal can be a Lower Kittanning coal or bituminous coal from another source. In a further aspect, Lower Kittanning coal is a low-volatile, low-ash coal derived from a coal seam wherein the mined coal product can be used to make coke in a traditional coking oven. In some aspects, the coal material is ground prior to blending with additional starting materials. In any of these aspects, the bituminous coal can be a low-volatile bituminous coal, a high-volatile bituminous coal, or a combination thereof. In a further aspect, the level of volatiles in a coal sample can be determined in the ASTM Standard Proximate Analysis Test using, for example, a thermogravimetric analyzer. In one aspect, coal can be received as any size particle for the disclosed process and further processed by any known means including, but not limited to, a hammer mill, a rock crusher, a mortar and pestle, or another means, to reduce the size further. In still another aspect, sieves with various mesh values can be used to separate the carbon particles into desired size ranges. In one aspect, the coal can be provided in bulk form. Further in this aspect, the coal pieces or particles can be reduced in size prior to being used in the disclosed processes. In one aspect, for example, the coal can be milled in a hammer mill or similar apparatus until the desired particle size is achieved. In one aspect, the coal can be milled in a hammer mill until it has a particle size of from about 1 to about 5 mm, or about 1, 2, 3, 4, or about 5 mm, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In a further aspect, the coal is milled in a hammer mill to an average particle size of 2 mm. In another aspect, after milling, coal can be fed into a coal pulverizer for further reduction in particle size. In one aspect, following pulverization, the pulverized coal can be sifted through sieves of various sizes to select coal particles having a particular size range. In another aspect, several sieve trays with different mesh sizes can be stacked and shaken together to simultaneously separate pulverized coal into several grouped portions, wherein particles within each portion have like particle sizes, but different portions have different overall particle size ranges. In one aspect, the compositions disclosed herein include a coal material having a particle size range of between about 10 mesh and about 400 mesh. In a further aspect, the coal material has a particle size of about 10 mesh; about 15 mesh; about 20 mesh; about 25 mesh; about 30 mesh; about 35 mesh; about 40 mesh; about 45 mesh; about 50 mesh; about 55 mesh; about 60 mesh; about 65 mesh; about 70 mesh; about 75 mesh; about 80 mesh; about 85 mesh; about 90 mesh; about 95 mesh; about 100 mesh; about 105 mesh; about 110 mesh; about 115 mesh; about 120 mesh; about 125 mesh; about 130 mesh; about 135 mesh; about 140 mesh; about 145 mesh; about 150 mesh; about 155 mesh; about 160 mesh; about 165 mesh; about 170 mesh; about 175 mesh; about 180 mesh; about 185 mesh; about 190 mesh; about 195 mesh; about 200 mesh; about 205 mesh; about 210 mesh; about 215 mesh; about 220 mesh; about 225 mesh; about 230 mesh; about 235 mesh; about 240 mesh; about 245 mesh; about 250 mesh; about 255 mesh; about 260 mesh; about 265 mesh; about 270 mesh; about 275 mesh; about 280 mesh; about 285 mesh; about 290 mesh; about 295 mesh; about 300 mesh; about 305 mesh; about 310 mesh; about 315 mesh; about 320 mesh; about 325 mesh; about 330 mesh; about 335 mesh; about 340 mesh; about 345 mesh; about 350 mesh; about 355 mesh; about 360 mesh; about 365 mesh; about 370 mesh; about 375 mesh; about 380 mesh; about 385 mesh; about 390 mesh; about 395 mesh; about 400 mesh; any set or combination of the foregoing values; or any range utilizing the foregoing values to define a sub-range within about 10 mesh to about 400 mesh. In one aspect, as the mesh rating number increases, the coal particle size decreases. Conductive Carbon Compound In some aspects, the processes disclosed herein may include a conductive carbon compound. In one aspect the conductive carbon compound can be a carbon fiber, a carbon nanofiber, a carbon nanotube, a carbon flake, a carbon black such as, for example, acetylene black, lamp black, or furnace black, an amorphous carbon, an isotropic carbon, an anisotropic carbon, a needle coke, a graphene, a graphene oxide, a graphite, or a combination thereof. In one aspect, the particle size of the conductive carbon compound can vary based on the heating methods disclosed herein. In one aspect, when microwave energy is used in the disclosed processes, the particle size of the conductive carbon can be from about 3 μm to about 40 μm, or can be about 3, 4, 5, 10, 15, 20, 25, 30, 35, or about 40 μm, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In an alternative aspect, when inductive field heating is used in the disclosed procedures, the particle size of the conductive carbon can be from about 3 μm to over 10 mm, or can be 3, 10, 100, or 500 μm, or 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mm, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the conductive carbon compound is graphite and has an average particle size of about 6 μm. In any of the above aspects, the conductive carbon compound can be finely ground. Without wishing to be bound by theory, for microwave heating applications, a finely ground conductive carbon compound has a higher surface area per unit volume and can thus make more extensive contact with the coal material for the purpose of heat transfer. In one aspect, the processes disclosed herein can be classified as “high carbon,” “low carbon,” or “no carbon.” In a further aspect, this classification indicates the weight percent of conductive carbon compound in the disclosed compositions and mixtures. In one aspect, a “high carbon” sample includes up to about 10% by weight of the conductive carbon compound. In another aspect, a “low carbon” sample includes approximately 1% by weight of the conductive carbon compound. In still another aspect, a “no carbon” sample is substantially free of conductive carbon compound. Other weight percentages of conductive carbon are also contemplated including 2%, 3%, 4%, 5%, 6%, 7%, 8%, and 9%, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In some aspects, when a specific conductive carbon compound is used such as, for example, graphite, samples can be referred to as “high graphite,” “low graphite,” and the like. In one aspect, the presence of a conductive carbon compound aids in foam formation by pyrolysis. In a further aspect, samples having about 1% conductive carbon by weight take less time to form green foam via pyrolysis than samples that are substantially free of conductive carbon. In another aspect, samples having about 5% conductive carbon by weight require less time to form green foam via pyrolysis than samples having 1% conductive carbon by weight. In another aspect, samples having about 10% conductive carbon by weight require less time to form green foam via pyrolysis than samples having 5% conductive carbon by weight. Without wishing to be bound by theory, it is believed the presence of conductive carbon assists the mixtures in reaching the temperatures required to devolatilize flux mixtures, regardless of whether high-volatile or low-volatile bituminous coal is used as the carbon source. In a further aspect, levels of conductive carbon are believed to contribute more to foam formation than different particle sizes of coal and/or different microwave power levels. In one aspect, the largest impact of increasing conductive carbon concentration on foam formation time is observed at low microwave power levels. In some aspects, foam formation can be accomplished using a conductive carbon compound as disclosed herein even when an additional agent such as, for example, a flux agent, is not used. Without wishing to be bound by theory, the inclusion of a conductive carbon compound such as, for example, graphite, in the compositions disclosed herein additionally allows for microwave-assisted calcination of the disclosed carbon foams since the conductive carbon compounds allow the compositions to reach the desired calcination temperatures. Additional Agent(s) In another aspect, the processes disclosed herein are optionally carried out in the presence one or more additional agents. In a further aspect, the one or more additional agents include, but are not limited to, carbohydrate syrups, coal tar distillates, and solvents. In some aspects, an additional agent is not used. In some aspects, the additional agent is a flux agent (also referred to as a fluxing agent). In one aspect, a “flux agent” as used herein is defined as a compound or mixture of compounds that, when blended with bituminous coal, absorbs microwave energy in such a way as to heat the coal material to its pyrolysis temperature. Flux Agent(s) In a further aspect, when the one or more additional agents includes a flux agent, coal and flux agent can be mixed together to form a composition that can be from about 30% to about 70% by weight of coal particles, or is about 30, 35, 40, 45, 50, 55, 60, 65, or about 70% by weight of coal particles, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the inherent percentage of volatile components of the coal can be a primary determinant of the flux:coal ratio. In one aspect, a high volatile bituminous coal will require a lower amount of flux agent than a low volatile bituminous coal. In another aspect, the chemical makeup of the flux agent and/or any additives used, particle size distribution of the coal, and properties of the desired final products can also affect the flux:coal ratio. As used herein, “coal flux material” refers to a mixture of coal particles and flux agent. In one aspect, coal flux material is typically viscous and semi-fluid. In one aspect, if a high enough temperature is reached and enough volatiles have been removed, a carbon foam sets as the particles fuse together. In an alternative aspect, if the coal particles begin to fuse into a foam but are still fluid, the coal flux material can be molded or extruded into various sizes and shapes. In some aspects, the flux agent includes a secondary component such as, for example, recovered coal volatiles, a liquid product from the petroleum industry such as, for example, kerosene, or a combination thereof. In one aspect, when the flux agent includes recovered coal volatiles as a secondary component, the recovered coal volatiles have boiling points ranging from about 80° C. to about 300° C. In a further aspect, the secondary component of the flux agent is heated during pyrolysis by the primary component and alters the interaction between the primary component and the coal particles. In some aspects, the secondary component may contain phenanthrene or related compounds. In one aspect, the additional agent and/or fluxing agent includes a carbohydrate syrup alone or in combination with a secondary component such as, for example, recovered coal volatiles as described above. Further in this aspect, when both a carbohydrate syrup and recovered coal volatiles are included in the fluxing agent, the fluxing agent is from about 92 to about 98 wt % carbohydrate syrup and from about 2 to about 8 wt % recovered coal volatiles. In one aspect, the carbohydrate syrup can be about 92, 93, 94, 95, 96, 97, or about 98 wt % of the fluxing agent and the recovered coal volatiles can be about 2, 3, 4, 5, 6, 7, or about 8 wt % of the fluxing agent, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In another aspect, the fluxing agent is about 95% carbohydrate syrup by weight and about 5% recovered coal volatiles by weight. Further in this aspect, the mixture of coal particles and fluxing agent can include additional carbohydrate syrup that is added separately to the mixture (i.e., not part of the fluxing agent). In one aspect, flux agent can be mixed with the coal by any suitable mechanical means including stirring. In some aspects, an initial amount of flux agent is added to the coal particles, mixing occurs, and then additional flux agent is added to the coal/flux mixture to achieve sufficient wetting of the coal particles. In one aspect, if the coal/flux mixture is particularly viscous, it can be kneaded by hand using rubber gloves or other suitable hand protection. In one aspect, homogeneous mixing of the coal/flux mixture is important to the consistent and predictable formation of carbon foam with desired properties. In one aspect, when low-volatile bituminous coal is used, the final ratio of coal particles to flux agent is from about 1:1 to 3:1, or is about 1:1, 1.5:1, 2:1, 2.5:1, or about 3:1, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, 50 g of flux agent is used for every 100 g of coal. Further in this aspect, initially, 30 g of flux agent is added to 100 g of coal, the sample is mixed, and then 20 g of additional flux agent is added to the coal/flux mixture. In some aspects, carbon foam can be produced at atmospheric pressure using high volatile bituminous coal in a single heating step. Without wishing to be bound by theory, when a coal source has a higher volatile amount, a lower amount of flux agent is needed to create the pseudo-liquid state required for particle fusing during microwave radiation. In one aspect, a coal to flux ratio of about 10:1 to about 2:1 is used. In a further aspect, the coal to flux ratio is about 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, about 2:1, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the coal to flux ratio is 4:1. In some aspect, a coal to flux ratio of 4:1 is useful when the flux agent is high fructose corn syrup without added carbon conversion process volatiles. In a further aspect, a particle size of 30-50 mesh for the coal is useful herein, but other particle sizes will also work. In one aspect, larger particle sizes may lead to more consistent mixing with less time and effort required. In many aspects, when high-volatile coal is used, it is not required to knead the coal and flux mixture by hand to achieve homogeneity. In a further aspect, the carbohydrate syrup is susceptible to microwave excitation. Further in this aspect, the carbohydrate syrup is capable of absorbing the energy band in the microwave region. In one aspect, any compound that has hydroxyl groups that are free to rotate is capable of absorbing energy of this frequency. In one aspect, it is desirable that susceptible carbohydrate molecules in the syrup would generate enough heat to fuse coal particles, while volatile compounds given off by the induced pyrolysis would cause foams to form. In one aspect, the carbohydrate syrup is high fructose corn syrup. In one aspect, carbohydrate syrups such as high fructose corn syrup are inexpensive and widely available. In a further aspect, when high fructose corn syrup is heated, it devolatilizes and forms a weak, coke-like material. In another aspect, high fructose corn syrup naturally contains from about 15% water to about 25% water, or about 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25% water, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the high fructose corn syrup contains about 18% water. In an alternative aspect, the high fructose corn syrup contains about 21% water. When incorporated into coal flux materials as a fluxing agent and heated, in one aspect, high fructose corn syrup releases vapors, causing fused coal to rise into a foam. Further in this aspect, water vapor is eventually driven off, but the remaining high fructose corn syrup material continues to decompose, giving off heat that causes coal particles to devolatilize and form a green foam, which is porous. In one aspect, green foam has low crush strength and almost no electrical conductivity. In any of the aspects described herein, regardless of how green foam is formed and regardless of whether a carbohydrate syrup was present in the initial mixture, green foam can be calcined, a process that imparts conductivity and improves crush strength. Coal Tars, Coal Tar Distillates, Petroleum Residues, and Pitches In another aspect, the additional agent or fluxing agent includes a coal tar, a coal tar distillate, a petroleum residue, or a related product. In some aspects, the flux agent is a complex mixture of compounds. In one aspect, the additional agent includes a coal tar distillate such as, for example, a foaming pitch. In a further aspect, foaming pitch can be made from lignite coal or another coal form. In one aspect, to make foaming pitch, lignite coal can be ground and passed through a sieve. In a further aspect, the sieve can be 60 mesh, although the particle size can be varied without departing from the processes disclosed herein. In some aspects, the particle size is altered in order to facilitate scaling of foaming pitch production for commercial production. In another aspect, following grinding and sieving, a slurry is prepared by adding ground coal to a solvent. In one aspect, the solvent can be condensed and recycled volatiles from previous coal-processing experiments and/or industrial processes. In still another aspect, hydrogenated vegetable oil can also be added to the mixture. In one aspect, and without wishing to be bound by theory, hydrogenated vegetable oil can act as a hydrogen donor during the pitch conversion reaction. In one aspect, the ratio of coal to solvent is from about 1:1 to about 1:3, or is about 1:1, 1.5:1, 2:1, 2.5:1, or about 3:1, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, for 15 lbs of coal, 42 lbs of solvent are required. In another aspect, the ratio of coal to hydrogenated vegetable oil is from about 10:1 to about 1:1, or is about 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or 1:1, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, for 15 lbs of coal, 3 lbs of hydrogenated vegetable oil are used. In another aspect, a slurry formed from coal, solvent, and vegetable oil is transferred into a reaction vessel of appropriate size. In a further aspect, the reaction vessel is capable of maintaining homogeneity in the mixture throughout the disclosed process. In some aspects, the slurry is heated to a temperature of from about 105° C. to about 130° C., or about 105, 110, 115, 120, 125, or about 130° C., or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the slurry is heated to a temperature of 120 \] degree. Further in this aspect, heating of the slurry allows water and other low boiling point volatiles to vaporize. In some aspects, these vapors can be vented to a moisture collection vessel and removed from the reaction mixture. Once low boiling point volatile compounds have been driven off, in some aspects, the reaction vessel is then isolated and the temperature increased. In a further aspect, the temperature is increased to from about 450° C. to about 650° C., or about 450, 500, 550, 600, or about 650° C., or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the temperature is increased to about 550° C. In a further aspect, increasing the temperature of the reaction vessel may lead to an increase in pressure as higher boiling point volatiles are driven off. In one aspect, pressure in the vessel is maintained between about 400 to about 700 psig, or at about 400, 450, 500, 550, 600, 650, or about 700 psig, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, pressure in the vessel is maintained between 500 and 600 psig with venting as necessary to maintain the pressure range. In some aspects, excess volatiles escaping at high temperatures are allowed to flow from the reaction vessel into an expansion tank. In a further aspect, compounds in the expansion tank can be later cooled and recycled back into the solvent mixture useful in the processes disclosed herein. In some aspects, non-condensable gases are formed. In a further aspect, these non-condensable gases can be vented to a scrubber to prevent environmental release. In one aspect, the non-condensable gases include hydrogen sulfide. In one aspect, heating at increased pressure is conducted for from about 30 minutes to about 90 minutes, or for about 30, 45, 60, 75, or about 90 minutes, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, heating at increased pressure is conducted for one hour. In one aspect, when the reaction is complete, the reaction vessel can be vented to release pressure. In another aspect, when the reaction is finished, a low-softening point mixture remains in the reaction vessel. In some aspects, this low-softening point mixture contains a quantity of ash that must be removed (i.e. “de-ashing”) prior to further use. Still further in this aspect, the low-softening point mixture can be transferred into another vessel to cool. In a further aspect, cooling is required prior to centrifugation due to instrument limitations. In one aspect, the low-softening point mixture contains reacted coal and mineral matter. In a further aspect, following cooling, this mixture can be further separated, by a method such as, for example, centrifugation. In one aspect, centrifugation occurs in a flow-driven centrifuge. Further in this aspect, ash from the low-softening point mixture can be collected in a rotating spindle in the centrifuge. Still further in this aspect, depending on the properties of the coal used as a starting material, the ash may be enriched in rare earth elements (REEs) and may be further refined. In an alternative aspect, de-ashing can be accomplished using filtration. The low-softening point mixture is, in some aspects, further distilled following the de-ashing process. In one aspect, distillation can be carried out in a vacuum distillation apparatus with a vacuum level of from about 25 to about 100 torr, or of about 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or about 100 torr, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the vacuum level is about 50 torr. In another aspect, distillation can be carried out at a temperature of from about 260° C. to about 300° C., or at about 260, 265, 270, 275, 280, 285, 290, 295, or about 300° C. In one aspect, distillation of the pitch mixture is carried out at 280° C. In some aspects, the vacuum distillation apparatus is equipped with a low flow rate nitrogen sparge to facilitate the flow and removal of volatiles from the pitch. In another aspect, and without wishing to be bound by theory, the nitrogen sparge may facilitate orientation of various moieties in the carbon pitch as it forms. In one aspect, the distillation system is equipped with collection vessels and condensers in parallel to collect fractions from the distillation. In some aspects, these fractions have commercial value. In another aspect, the pitch can be drained from the distillation column as a liquid at elevated temperature and allowed to cool to room temperature, at which point it solidifies. In one aspect, the low softening point mixture, after this process, has an increased softening point and can, in some aspects, be referred to as “pitch” at this point if it is solid at room temperature. In another aspect, the low softening point mixture or pitch is free of material that is insoluble in quinolone (i.e., “quinolone insoluble free”). Further in this aspect, quinolone insoluble free material such as the low softening point mixture or pitch can be used in the production of carbon fibers. In any of the above aspects, following the devolatilization step, the pitch can be removed from the coking vessel. Further in this aspect, the pitch is in the form of hard pieces ranging in size from roughly 0.5 to 8 cm. In one aspect, the larger pieces can be crushed by any known means such as with a hand-operated rock crusher. In another aspect, smaller pieces can also be crushed by any known means, such as using a mortar and pestle. Following crushing and/or grinding, the pitch particles can be separated into size fractions using sieve trays. In one aspect, the sieve trays are stacked into a series such that larger particles are maintained on the top tray while smaller particles fall through successive trays, with the smallest particles landing on a collection tray at the bottom of the stack of trays. In some aspects, the particle sizes are ranges (i.e., 20-50 mesh, 50-100 mesh, and >100 mesh) but any size range desired can be selected by the operator as needed. In any of the above aspects, when particles become compacted, they can be scraped off the trays and further crushed using a rock crusher or mortar and pestle as appropriate. Lignin-Based Materials In one aspect, the additional agent or fluxing agent includes a lignin-based material. In one aspect, large quantities of lignin-based materials are currently produced as waste products in the paper industry and related industries, particularly from the pulping process. One lignin-based waste material is “black liquor” and typically contains lignin residues, hemicellulose, and inorganic paper processing chemicals. Black liquor has approximately 15% solids by weight and is typically burned due to its lack of commercial or industrial value. In some aspects, sodium lignosulfonate can be synthesized from components of black liquor or other paper and/or wood industry byproducts. In one aspect, the additional agent or fluxing agent contains sodium lignosulfonate and is or is derived from black liquor or another paper industry waste. Solvents In still another aspect, the additional agent includes a solvent. In one aspect, the solvent is kerosene, NMP, or a mixture thereof. In another aspect, the solvent can be recovered volatiles from the processes disclosed herein, as described previously. In a further aspect, when the solvent is NMP, the NMP can be from about 20 to about 50% by weight of the mixture, or can be about 20, 25, 30, 35, 40, 45, or about 50% by weight of the mixture, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the NMP is present in an amount of about 35% by weight of the mixture. In some aspects, when NMP or kerosene or another solvent is present, no carbohydrate syrup or flux mixture is required. In one aspect, NMP or another solvent can solubilize volatile material from coal but must be removed prior to foaming or pyrolysis. In some aspects, graphite can be added to the NMP. Further in these aspects, during microwave heating, the graphite can increase in temperature to a point where NMP can be distilled while simultaneously devolatilizing the coal. Homogenization of Coal Flux Material In one aspect, in order to produce a carbon foam with a consistent composition and the desired properties using the methods disclosed herein, it is first necessary to produce a homogeneous mixture. In one aspect, when preparing a coal flux material as disclosed herein, the mixture of coal particles and flux agent must be homogeneous. In one aspect, this requires that the surface of all coal particles must be uniformly wetted with the flux agent in order for proper fusion into a carbon foam. In many aspects, the coal flux material is a high viscosity substance and intensive mixing is thus required. In one aspect, when an additional agent is used in the methods disclosed herein, the conductive carbon and the additional agent are first mixed or blended, followed by the addition of the coal material. In an alternative aspect, the conductive carbon and/or the additional agent such as a flux agent can be added incrementally while coal particles are agitated. In one aspect, following homogenization of the coal flux material, the coal flux is prepared for the foaming step. In a further aspect, the coal flux material is placed into a container and compressed to remove any void spaces or air pockets. In one aspect, the container is made from a ceramic material. In some aspects, a release agent is applied to the container prior to adding the coal flux material. Further in this aspect, the release agent aids in the removal of the final carbon foam product by preventing it from sticking or binding to the container. In another aspect, the release agent can be a natural oil, such as a cooking oil. In some aspects, the release agent is provided in spray form. In another aspect, additional materials can also be added to the coal flux material at this time. In one aspect, carbon fibers can be added to add strength to the foam material, alter its conductive properties, or both. In some aspects, the coal flux material can be layered and additional volatile additives can be placed between the layers to create sp2hybridized carbon layers within the final foam product. In another aspect, the additional materials can include, but are not limited to, previously made foam particles, carbon micro- and nanoparticles, carbon micro- and nanofibers, diamond powder, graphene and/or graphene oxide particles, graphite, and/or graphite flakes can be added to create composite carbon foams. In another aspect, composite foams can be produced by layering foams with different coal flux materials prepared from different feedstocks. In still another aspect, composite foams can be produced by using coal flux materials with different particle sizes. Heating Methods Useful Herein In one aspect, when subjected to microwave energy, conductive carbon materials quickly increase in temperature. In a further aspect, conductive carbon materials absorb microwave energy via eddy current heating. In another aspect, conductive carbon materials may absorb radio waves as in, for example, inductive heating. In one aspect, either microwave heating or inductive heating can be used in the processes disclosed herein. In one aspect, microwave heating can be conducted in a household microwave oven or another microwave apparatus with a frequency range that matches or overlaps with that of a household microwave oven. In some aspects, a household microwave oven has a frequency range that is essentially monochromatic with a maximum amplitude in the —OH rotation range. In another aspect, a microwave oven or apparatus can be tuned to match rotation energies of other functional groups. Further in this aspect, tuning a microwave oven to a different frequency would enable the selection and use of different flux materials, which could, in turn, affect the final properties of any carbon foams produced. In one aspect, when the flux agent is or contains coal tars, petroleum residues, and the like, a household microwave may not be used and a different, tunable microwave or a microwave apparatus tuned to a different frequency may instead be employed in the disclosed processes. In one aspect, the processes disclosed herein are conducted in a household microwave oven or another microwave apparatus with preprogrammed power settings. In another aspect, such a microwave oven or apparatus is capable of heating at different power settings. In one aspect, a high power setting (e.g., 100% power) is subjected to microwave power for the entire heating time. In another aspect, a medium or middle power setting (e.g., 50% power) involves power cycles. Further in this aspect, if a sample is heated at 50% power for 1 minute, the sample is exposed to radiation repeating intervals of 10 seconds on, 10 seconds off, or the like, until total cycle time reaches the programmed microwave time. In another aspect, when subjected to microwave energy, some additional agents such as, for example, carbohydrate syrups are subject to dielectric heating when exposed to microwave energy. In another aspect, shrinkage of foam during calcination may cause defects in the foam and the defects may, in turn, lead to foam failure. Without wishing to be bound by theory, defects and shrinkage may be due to nonlinear heating; that is, foams are heated at the surface and in the interior at unequal rates, since the foams are thermal insulators. In some aspects, inclusion of graphite or another conductive carbon material uniformly throughout the foam should lead to uniform heating with low shrinkage levels and thus no or low distortion and strain. Further in these aspects, however, the inclusion of conductive carbon compounds may cause the entire foam sample to become electrically conductive and can, in some cases, lead to sparking in the system. In some aspects, inductive heating can be used instead of or in addition to microwave heating for calcination. Further in this aspect, manufactured carbon foam samples are placed into a space between the coils in an inductive heater, which can be turned on for an appropriate time based on the power level and sample size. In one aspect, inductive heating takes place in one or more 30 second intervals. Further in this aspect, calcination can be considered complete when conductivity of the carbon foams as measured by a multimeter ceases to increase. In one aspect, calcination using inductive heating completes quickly due to the depth of penetration of the inductive fields into the carbon foam samples. In either of the above aspects, regardless of the energy source or heating mechanism, when conductive carbon materials and/or additional agents are exposed to microwave or inductive heating, these conductive carbon materials and/or additional agents then transfer heat to the coal materials disclosed herein. In one aspect, after the processes disclosed above are completed, a green foam-like product is produced. In a further aspect, although this product has some mechanical strength, a further calcination step can improve this and related properties. In one aspect, green foam-like foam is removed from the container in which it has been heated. In a further aspect, the surface of this initial foam may have some cracking or other defects. Initial Heating Step In one aspect, prior to calcination, samples are subjected to an initial heating step. In a further aspect, coal compositions (i.e., coal/flux mixtures and/or mixtures containing coal and conductive carbon compounds) can be placed into a ceramic cup or crucible as required by the sample size. In one aspect, crucible or cub loading can be accomplished by placing a sufficient amount of coal/flux, coal/graphite, or other mixtures disclosed herein to cover the bottom of the container and roughly fill the container. In a further aspect, the mixture can then be compressed by hand and additional amounts of the mixture added until the container is filled. In a further aspect, the top of the material can be scraped with a flat object to remove excess material. In any of the above aspects, the crucible or cup can then be weighed to determine how much foam precursor has been loaded into the crucible or cup. In a further aspect, the container used was previously coated with a release agent such as, for example, a vegetable oil spray. In another aspect, after the containers are filled with coal samples, the containers are covered, either with a ceramic tile or crucible lid as appropriate for the container being used. In one aspect, the samples thus prepared are placed into a microwave. In some aspects, a home microwave oven is used. In other aspects, a commercial microwave device can be used. In either of these aspects, the microwave oven is closed, a power level is chosen as discussed previously, and a time increment is selected. In one aspect, the time increment is from about 30 seconds to about 15 minutes, or is about 30 seconds, 60 seconds, 90 seconds, 2 minutes, 2 minutes 30 seconds, 3 minutes, 3 minutes 30 seconds, 4 minutes, 4 minutes 30 seconds, 5 minutes, 5 minutes 30 seconds, 6 minutes, 6 minutes 30 seconds, 7 minutes, 7 minutes 30 seconds, 8 minutes, 8 minutes 30 seconds, 9 minutes, 9 minutes 30 seconds, 10 minutes, 10 minutes 30 seconds, 11 minutes, 11 minutes 30 seconds, 12 minutes, 12 minutes 30 seconds, 13 minutes, 13 minutes 30 seconds, 14 minutes, 14 minutes 30 seconds, or about 15 minutes, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. After a heating cycle is completed, in one aspect, the heated sample is removed from the microwave chamber and inspected. In some aspects, the samples rose during heating. Further in these aspects, samples that had risen were compressed and additional heating cycles were performed until the samples solidified and rising was not observed. In some aspects, samples were microwaved in a crucible that had been placed inside a glass beaker covered with a watch glass. In these aspects, this arrangement allowed for the release of volatile compounds. In a further aspect, volatile compounds condensed on the beaker and/or watch glass and could be collected for later analysis. Following microwave heating, in one aspect, some microwaved samples were observed to be outwardly bulging. Without wishing to be bound by theory, it is believed that the bulging portion was formed as volatile components escaped from the foam; thus, the carbon foam and the bulging portion are malleable and can be molded or shaped. Again, without wishing to be bound by theory, it is believed that the carbon material occupies a pseudo-fluid state at high temperatures and does not form a solid foam until cooling. In one aspect, then, it is possible to mold or extrude a partially formed carbon foam into a specific size or shape. In one aspect, swelling of the samples can be reduced by heating the samples to an elevated temperature to drive off moisture and low boiling point volatiles prior to the first microwave heating step. In one aspect, the samples can be heated to a temperature of from about 100 to about 120° C., or to about 100, 105, 110, 115, or about 120° C., or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the samples can be heated to 105° C. prior to the first microwave step. In any of the above aspects, samples formed after the initial microwave stage are placed into ceramic crucibles for calcination. Calcination Step In one aspect, calcination can be carried out in an inert or reducing environment. In various aspects, the non-oxidizing atmosphere used in the calcining step can comprise oxygen present in an amount less than or equal to about 10% (v/v); about 9% (v/v); about 8% (v/v); about 7% (v/v); about 6% (v/v); about 5% (v/v); about 4% (v/v); about 3% (v/v); about 2.5% (v/v); about 2% (v/v); about 1.5% (v/v); about 1% (v/v); about 0.5% (v/v); a percentage (v/v) of oxygen value or set of percentage of oxygen values within any of the foregoing ranges of percentage of oxygen values; or a range of percentage of oxygen values that is a sub-range of the foregoing ranges of percentage of oxygen values. In a further aspect, the non-oxidizing atmosphere in the calcining step is essentially oxygen free. In various aspects, the non-oxidizing atmosphere used in the calcining step can comprise one or more inert gases; and wherein the inert gas is argon, nitrogen, or a mixture of both in an amount that is greater than about 70% (v/v). In a further aspect, the amount of inert gas in the non-oxidizing atmosphere comprises greater than about 75% (v/v); about 80% (v/v); about 85% (v/v); about 90% (v/v); about 95% (v/v); about 96% (v/v); about 97% (v/v); about 98% (v/v); about 99% (v/v); a percentage (v/v) value of inert gas or set of percentage (v/v) of values of inert gas within any of the foregoing ranges of inert gas values; or a range of percentage of inert gas values that is a sub-range of the foregoing ranges of percentage of inert gas values. Furnace Calcination In other aspects, calcination can be conducted with samples placed in closed crucibles under graphite chips and several layers of steel wool. Without wishing to be bound by theory, the steel wool acts as an initial oxygen scavenger and the graphite chips are believed to oxidize to CO2upon introduction of oxygen, thus removing any oxygen from the atmosphere before it reaches the carbon foam samples. In a further aspect, when graphite and steel wool are used to scavenge oxygen, no purges or flows of inert gas are required to maintain an inert or reducing environment. In one aspect, the graphite chips have an average particle size of from about 0.5 mm to about 4 mm, or of about 0.5, 1, 1.5, 2, 2.5, 3, 3.5, or about 4 mm, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the graphite chips have an average particle size of about 2 mm. Exemplary procedures for using graphite chips and steel wool as oxygen scavengers are provided in the examples. Without wishing to be bound by theory, it is believed that heating foam samples in an oxidizing environment would lead to combustion of the green foams, resulting in the production of ash rather than of stable carbon foams. In one aspect, calcination can be carried out in a furnace. Further in this aspect, calcination can be carried out in a steel box or a ceramic bowl with a cover such as, for example, a ceramic tile. In either of these aspects, green foam pieces are placed in crucibles with appropriately sized lids and buried with graphite chips. Further in these aspects, several layers of steel wool can be added to the top of the box or bowl. In any of these aspects, after the addition of steel wool, the box or bowl can be closed and placed in a muffle furnace. In some aspects, two heating steps can be employed. Further in these aspects, the foams can be inspected between heating steps. In one aspect, the furnace is programmed as follows:(a) the temperature is increased from room temperature at an initial rate to a first temperature;(b) the rate is decreased to a second rate until a second temperature is reached;(c) the temperature is held at the second temperature for a first time;(d) the furnace is turned off and allowed to cool for a second time. In one aspect, the initial rate is from about 150 to about 250° C. per hour, or is about 150, 175, 200, 225, or about 250° C. per hour, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the initial rate is about 200° C. per hour. In another aspect, the first temperature is from about 300 to about 500° C., or is about 300, 325, 350, 375, 400, 425, 450, 475, or about 500° C., or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the first temperature is about 400° C. In yet another aspect, the second rate is from about 50 to about 150° C. per hour, or is about 50, 75, 100, 125, or about 150° C. per hour, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the second rate is about 100° C. per hour. In another aspect, the second temperature is from about 500 to about 700° C., or is about 500, 525, 550, 575, 600, 625, 650, 675, or about 700° C., or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the second temperature is 600° C. In still another aspect, the first time is from 2 to 4 hours, or is 2 hours, 2.25 hours, 2.5 hours, 2.75 hours, 3 hours, 3.25 hours, 3.5 hours, 3.75 hours, or about 4 hours, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the first time is 4 hours. In another aspect, the second time is from 6 to 14 hours, or is about 6, 7, 8, 9, 10, 11, 12, 13, or about 14 hours, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the second time is 10 hours. In another aspect, a second heat treatment can be performed to drive off additional volatile components, increase the carbon content of the foam, and increase the strength and crush resistance of the foam. Further in this aspect, foam samples are placed into crucibles and covered with lids, and the crucibles are then covered with graphite chips and steel wool as previously described. Still further in this aspect, the steel box or ceramic bowl containing the crucibles is covered and placed back into the furnace and the following heating program is used for the furnace:(a) the furnace is heated at a third rate until a third temperature is reached;(b) the heating rate is reduced to a fourth rate until a fourth temperature is reached;(c) the heating rate is reduced to a fifth rate until a fifth temperature is reached;(d) the heating rate is reduced to a sixth rate until a sixth temperature is reached;(e) the temperature is held at the sixth temperature for a third time period;(f) the furnace is turned off and allowed to cool for a fourth time period. In one aspect, the third rate is from about 400 to about 600° C. per hour, or is about 400, 425, 450, 475, 500, 525, 550, 575, or about 600° C. per hour, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the third rate is 500° C. per hour. In another aspect, the third temperature is from about 300 to about 500° C., or is about 300, 325, 350, 375, 400, 425, 450, 475, or about 500° C., or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the third temperature is 400° C. In one aspect, the fourth rate is from 50 to 150° C. per hour, or is 50, 75, 100, 125, or about 150° C. per hour, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the fourth rate is 100° C. per hour. In one aspect, the fourth temperature is from about 450° C. to about 650° C., or is about 450, 475, 500, 525, 550, 575, 600, 625, or about 650° C., or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the fourth temperature is 550° C. In another aspect, the fifth rate is from about 20 to about 80° C. per hour, or is about 20, 30, 40, 50, 60, 70, or about 80° C. per hour, or a combination of any of the foregoing values or a range encompassing any of the foregoing values. In one aspect, the fifth rate is about 50° C. per hour. In one aspect, the fifth temperature is about 600, 625, 650, 675, 700, 725, 750, 775, or about 800° C., or a combination of any of the foregoing values or a range encompassing any of the foregoing values. In one aspect, the fifth temperature is 700° C. In still another aspect, the sixth rate is from about 15 to about 35° C. per hour, or is about 15, 20, 25, 30, or about 35° C. per hour, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the sixth rate is about 25° C. per hour. In another aspect, the sixth temperature is from about 800 to about 1350° C., or is about 800, 825, 850, 875, 900, 925, 950, 975, 1000, 1025, 1050, 1075, 1100, 1125, 1150, 1175, 1200, 1225, 1250, 1275, 1300, 1325, or 1350° C., or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the sixth temperature is about 900° C. In another aspect, the third time period is from about 30 minutes to about 90 minutes, or is 30, 45, 60, 75, or about 90 minutes, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the third time period is 60 minutes. In another aspect, the fourth time period is from about 8 hours to about 16 hours, or is 8, 9, 10, 11, 12, 13, 14, 15, or about 16 hours, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the fourth time period is about 12 hours. In one aspect, furnace calcination can be accomplished in a single step. Further in this aspect, the furnace can be programmed by an initial quick ramp to a first temperature and then slower heating at a first rate to a second temperature, followed by holding the samples for a first time period at the second temperature. Following heating, in this aspect, the samples are then allowed to cool to room temperature. In a further aspect, the first temperature can be between about 450 and about 650° C., or can be about 450, 475, 500, 525, 550, 575, 600, 625, or about 650° C., or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the first temperature is about 550° C. In another aspect, the first rate can be from about 55 to about 95° C. per hour, or can be about 55, 60, 65, 70, 75, 80, 85, 90, or about 95° C. per hour, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the first rate is 75° C. per hour. In yet another aspect, the second temperature is from about 800 to about 1350° C., or is about 800, 825, 850, 875, 900, 925, 950, 975, 1000, 1025, 1050, 1075, 1100, 1125, 1150, 1175, 1200, 1225, 1250, 1275, 1300, 1325, or 1350° C., or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the second temperature is 900° C. In still another aspect, the first time period is from about 1 to about 5 hours, or is 1, 2, 3, 4, or about 5 hours, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the first time period is about 4 hours. In either of the above aspects, following calcination, carbon foam weight and electrical conductivity can be determined. In one aspect, a typical piece of carbon foam contracts by from about 10 to about 50 vol % during calcination, or by about 10, 20, 30, 40, or about 50 vol % during calcination, or a combination of any of the foregoing values or a range encompassing any of the foregoing values. In one aspect, the carbon foam contracts by about 30 vol % during calcination. In some aspects, following calcination, a typical piece of carbon foam becomes harder, stronger, and more electrically conductive. In some aspects, when heating is not uniform, contraction of the foam can cause internal strains which may result in the formation of cracks in some instances. Microwave-Assisted Calcination In some aspects, microwave-assisted calcination was implemented. In one aspect, microwave-assisted calcination was especially useful for samples containing a conductive carbon compound. In a further aspect, microwave-assisted calcination was useful in addressing the issue of internal strains and cracks as discussed previously. In some aspects, non-calcined foam samples with a conductive carbon compound can be heated in a microwave in intervals until a specific exposure time has been reached. In one aspect, the intervals can be from about 1 to about 10 minutes long, or were 1, 2, 3, 4, 5, 6, 7, 8, 9, or about 10 minutes long, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the intervals can be about 5 minutes long. In another aspect, the exposure time is from about 30 minutes to about 90 minutes, or is 30, 45, 60, 75, or about 90 minutes, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the exposure time is about one hour. In a further aspect, after the microwave-assisted procedure, the samples possess electrical conductivity. In one aspect, finding electrical conductivity in a carbon foam sample is indicative of calcination having occurred. In another aspect, microwave calcination must take place in a non-oxidizing environment. Further in this aspect, the microwave chamber can be equipped to allow flow of an inert gas such as, for example, argon, nitrogen, or helium through the microwave chamber during the microwave-assisted calcination step. Inductive Field Calcination In other aspects, an inductive field calcination process was attempted. In some aspects, during microwave-assisted calcination, samples containing conductive carbon species sparked due to high conductive carbon content and, without wishing to be bound by theory, it was believed that inductive field heating would avoid the sparking problems but still successfully result in calcination of the carbon foams. Further in this aspect, a carbon foam sample is placed between the coils of an inductive coil heater (also known as an induction heater). After a specified interval, in some aspects, the sample can be removed and tested for conductivity. In one aspect, the interval is from 10 seconds to one minute, or is 10, 20, 30, 40, 50, or about 60 seconds, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the interval is 30 seconds. In any of these aspects, following the heating interval, the sample is removed from the heater and tested for conductivity. In one aspect, when an increase in conductivity was detected, it was concluded that calcination of the foam had occurred. In a further aspect, if calcination had not yet occurred based on electrical conductivity measurements, the inductive field heating process could be repeated as needed. In another aspect, inductive field calcination is carried out in a non-oxidizing environment. In one aspect, the inductive field heater used for inductive field calcination can be equipped to allow flow of an inert gas through the heater during calcination. In another aspect, the inductive field heater used for inductive field calcination can be placed in a chamber such as, for example, a glove box or isolation chamber that is filled with an inert gas such as, for example, nitrogen, argon, or helium. In one aspect, following microwave radiation heat treatment to produce green foam, the coke samples can be placed in crucibles and covered in graphite and steel wool as previously described. In a further aspect, the vessel containing the crucibles and graphite is placed in a furnace, which has been programmed as follows:(a) the furnace is heated at a first rate until a first temperature is reached;(b) the heating rate is decreased to a second rate until a second temperature is reached;(c) the heating rate is decreased to a third rate until a third temperature is reached;(d) the temperature is held at the third temperature for a first time period;(e) the heating rate is decreased to a fourth rate until a fourth temperature is reached;(f) the temperature is held at the fourth temperature for a second time period; and(g) the furnace is turned off and its contents are allowed to cool for a third time period. In one aspect, the first rate is from about 300 to about 500° C. per hour, or is about 300, 325, 350, 375, 400, 425, 450, 475, or about 500° C. per hour, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the first rate is about 400° C. per hour. In another aspect, the first temperature is from about 450 to about 650° C., or is about 450, 475, 500, 525, 550, 575, 600, 625, or about 650° C., or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the first temperature is about 550° C. In another aspect, the second rate is from about 50 to about 150° C. per hour, or is about 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, or about 150° C. per hour, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the second rate is about 100° C. per hour. In another aspect, the second temperature is from about 600 to about 800° C., or is about 600, 625, 650, 675, 700, 725, 750, 775, or about 800° C., or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the second temperature is about 700° C. In yet another aspect, the third rate is from about 10 to about 90° C. per hour, or is about 10, 20, 30, 40, 50, 60, 70, 80, or about 90° C. per hour, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the third rate is about 50° C. per hour. In still another aspect, the furnace is held at the third temperature for a period of about 30 to about 90 minutes, or for about 30, 45, 60, 75, or about 90 minutes, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the furnace is held at the third temperature for about 60 minutes. In another aspect, the fourth rate is from about 15 to about 35° C. per hour, or is about 16, 20, 25, 30, or about 35° C. per hour, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the fourth rate is about 25° C. per hour. In yet another aspect, the fourth temperature is from about 800 to about 1350° C., or is about 800, 825, 850, 875, 900, 925, 950, 975, 1000, 1025, 1050, 1075, 1100, 1125, 1150, 1175, 1200, 1225, 1250, 1275, 1300, 1325, or 1350° C., or a combination of any of the foregoing values or a range encompassing any of the foregoing values. In one aspect, the fourth temperature is about 900° C. In one aspect, the second time period is from about 1 hour to about 3 hours, or is about 1 hour, 1.5 hours, 2 hours, 2.5 hours, or about 3 hours, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the second time period is 2 hours. In another aspect, the third time period is from about 8 to about 16 hours, or is about 8, 9, 10, 11, 12, 13, 14, 15, or about 16 hours, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the third time period is about 12 hours. In any of the above aspects, following calcination, samples can be assessed for conductivity using a voltmeter, with the presence of conductivity indicating successful calcination. Alternative Feedstocks In one aspect, alternative materials (i.e., not caking coals) can be used as source materials for carbon foams. In one aspect, a foaming pitch derived from non-caking coal as described previously can be used as a feedstock for a carbon foam. In one aspect, when foaming pitch is used as a feedstock, any particle size range can be used. In some aspects, a particle size range of 30-50 mesh is useful and can be prepared as described previously. In another aspect, a ratio of from about 10:1 to about 1:1 of pitch:flux can be used. In still another aspect, the ratio is about 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or about 1:1, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the ratio of pitch:flux is about 6:1. In another aspect, any flux agent already described can be useful herein. In one aspect, the flux agent can be composed of high fructose corn syrup and recycled coal volatiles as described previously. In another aspect, foaming pitch can be mixed with a conductive carbon compound as disclosed herein, prior to the formation of green foam. In any of the above aspects, the pitch and flux can be mixed by any method disclosed herein until the mixture is homogeneous. Following mixing, in one aspect, the mixture can be added to a crucible and converted to carbon foam. In one aspect, the mixture forms a carbon foam after 5 min at 20% power. In a further aspect, foams prepared from pitch feedstocks can be calcined in a non-oxidizing environment as previously described. Process Scale Up In one aspect, larger samples can be prepared. In a further aspect, preparation of larger samples can be useful for industrial scale up for testing and further applications. In one aspect, a sample containing coal powder, high fructose corn syrup, and graphite can be used to fill a container approximately 1 square foot in surface area. In another aspect, larger samples can be placed in larger microwave chambers to form the green foam phase. In some aspects, rather than having a rotating plate as in home microwave ovens, the microwave may have a rotating coil in order to effectively expose the sample consistently to microwave radiation. In any of these aspects, carbon foam samples can be successfully generated on a larger scale. In one aspect, a continuous carbon foam processing system can be employed to assist in the scale-up of the processes disclosed herein. In a further aspect, this device would supply energy to the foaming mixture to achieve foam formation and/or calcination. In one aspect, the energy can be microwave energy. In another aspect, the energy can be inductive field energy. In some aspects, the device can operate intermittently with mechanical pressure to compress the carbon foam as it is processed. Properties of Carbon Foams In any of the above aspects, density and electrical resistivity of low-volatile and/or high-volatile bituminous coal-based carbon foams can be assessed following foam formation. In one aspect, a low-volatile bituminous coal can have a density from about 1 to about 1.5 g/mL, or can have a density of about 1.1, 1.2, 1.3, 1.4, or about 1.5 g/mL or a combination of any of the foregoing values or a range encompassing any of the foregoing values. In one aspect, a carbon foam prepared from a low-volatile bituminous coal has a density of about 1.151 g/mL. In another aspect, a carbon foam prepared from a low-volatile bituminous coal has an electrical resistivity of from about 0.1 to about 0.5 Ω/ft2, or can have an electrical resistivity of about 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, or about 0.5 Ω/ft2, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, a carbon foam prepared from a low-volatile bituminous coal has an electrical resistivity of about 0.138 Ω/ft2. In still another aspect, a carbon foam prepared from a high-volatile bituminous coal can have a density of from about 0.9 to about 1.4 g/mL, or can have a density of about 0.9, 1, 1.1, 1.2, 1.3, or about 1.4 g/mL, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, carbon foams prepared from high-volatile bituminous coals have a density of about 1.028 g/mL. In another aspect, carbon foams prepared from high-volatile bituminous coals have an electrical resistivity of from about 0.1 to about 0.5 Ω/ft2, or of about 0.1, 0.2, 0.3, 0.4, or about 0.5 Ω/ft2, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, carbon foams prepared from high volatile bituminous coals have an electrical resistivity of about 0.247 Ω/ft2. Carbon foams as disclosed herein can be further characterized by additional methods. In one aspect, degree of anisotropy can be determined using polarized light microscopy. In another aspect, degree of anisotropy can be further characterized using a technique such as, for example, X-ray diffraction (XRD). In another aspect, XRD can be used to identify the properties of crystals formed in anisotropic regions of the carbon foams. In some aspects, crystal height can be from about 1.5 to about 2.1 nm, or can be about 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, or about 2.1 nm. In one aspect, crystal height is about 1.8 nm. In other aspects, crystal lateral dimension can be from about 3 to about 3.8 nm, or can be about 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, or about 3.8 nm. In one aspect, crystal lateral dimension is about 3.4 nm. In another aspect, spacing can be about 3.2 to about 4 Å, or can be about 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or about 4 Å. In one aspect, spacing is about 3.6 Å. In one aspect, when carbon foams have not yet been calcined, they display low anisotropy and low graphitization. In one aspect, a technique such as SEM-EDS can be used to reveal structural details as well as some elemental analysis of carbon foams disclosed herein. In a further aspect, the carbon foams may sometimes retain some mineral content. In a further aspect, the mineral content includes aluminum and silicon. In one aspect, aluminum and silicon content is less than about 1% by weight, or is about 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or about 1% by weight. In a further aspect, the mineral content includes sulfur. In one aspect, sulfur content is less than about 1% by weight, or is about 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or about 1% by weight. In still another aspect, the carbon foams disclosed herein incorporate cagelike structures. In another aspect, the cagelike structures are relatively large. In still another aspect, the cagelike structures are from about 200 to about 400 μm, or are about 200, 225, 250, 275, 300, 325, 350, 375, or about 400 μm. In one aspect, the cages are about 300 μm. In still another aspect, surface area and porosity can be determined using a technique such as, for example, nitrogen adsorption and desorption. In one aspect, nitrogen adsorption/desorption isotherms can be measured using an appropriate instrument. In a further aspect, using nitrogen adsorption and desorption data, surface area can be evaluated. In one aspect, nitrogen adsorption and desorption can be used to determine Brunauer-Emmett-Teller surface area. In a further aspect, surface area can be from about 2 to about 3 m2/g, or can be about 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or about 3 m2/g. In another aspect, surface area is about 2.65 m2/g. In another aspect, bulk density determined by this method can be from about 0.5 to about 1 g/cm2. In still another aspect, bulk density is about 0.5, 0.6, 0.7, 0.8, 0.9, or about 1 g/cm2. In still another aspect, bulk density is about 0.78 g/cm2. In still another aspect, average grain size distribution can be determined using a technique such as, for example, SEM. In one aspect, different starting coal particle sizes result in different average grain sizes for the carbon foams produced. In one aspect, a carbon foam made from 20-35 mesh coal particles (starting particle size from about 500-841 μm) produces carbon foams with a grain size of from about 40 μm to about 390 μm, or from about 40 μm to about 75 μm, or about 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, or about 390 μm. In yet another aspect, a carbon foam made from 60-100 mesh coal particles (starting particle size from about 149-250 μm) produces carbon foams with a grain size of from about 10 to about 110 μm, or from about 10 to about 50 μm, or about 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, or about 110 μm. In still another aspect, a carbon foam made from >100 mesh coal particles (starting particle size <149 μm) produces carbon foams with a grain size of from about 30 to about 175 μm, or about 75 to about 125 μm, or about 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, or about 175 μm. In yet another aspect, a carbon foam made from 40-60 mesh coal particles (starting particle size 250-400 μm) produces carbon foams with a grain size of from about 25 to about 240 μm, or from about 40 to about 150 μm, or about 25, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, or about 240 μm. Compositions In one aspect, disclosed herein are compositions including a conductive carbon material and a coal material. In another aspect, disclosed herein are compositions including a conductive carbon material, a coal material, and a carbohydrate-rich syrup. In still another aspect, disclosed herein are compositions including a conductive carbon material, a coal material, and a lignocellulosic waste material. In still another aspect, disclosed herein are compositions including a conductive carbon material, a coal material, and a coal tar distillate. In yet another aspect, disclosed herein are compositions including a conductive carbon material, a coal material, a coal tar distillate, and a solvent. In one aspect, the solvent is kerosene. In a further aspect, disclosed herein are compositions including a conductive carbon material, a coal material, and a solvent. In one aspect, the solvent is NMP. Carbon Foam Materials and Methods of Use In one aspect, disclosed herein are carbon foam materials prepared by the disclosed processes. In another aspect, disclosed herein are carbon foam composite materials prepared by the disclosed processes. In still another aspect, disclosed herein are methods of use of the carbon foam materials and carbon foam composite materials disclosed herein. In one aspect, the carbon foams produced by the processes disclosed herein are useful for various industrial uses. In a further aspect, the carbon foams can be mass produced to form sheets of insulation. In a further aspect, carbon foam insulation has the properties of a thermal insulator but does not burn and is thus useful as a building material. In some aspects, carbon foam insulation can be incorporated into firewalls on ships and in buildings. In another aspect, the carbon foams can be formed into bricks useful for lining high-temperature furnaces. In one aspect, carbon foam bricks are less expensive to produce than the refractory bricks currently used in high-temperature furnaces. In still another aspect, carbon foams as disclosed herein can absorb large amounts of energy during impact or crushing. In one aspect, carbon foams as disclosed herein may be useful in automotive applications to absorb energy from crashes, thereby reducing damage to automobiles and trucks while simultaneously lowering the likelihood of automobile occupant injury or death. In another aspect, the carbon foams disclosed herein can be used in military vehicle armor to prevent damage from improvised explosive devices. In another aspect, the foams disclosed herein are able to absorb energy from projectiles such as, for example, bullets. In a further aspect, the carbon foams can be wrapped with Kevlar® in order to reduce projectile penetration while simultaneously resisting impact. In some aspects, the wrapped carbon foams can be provided with a thin aluminum face plate and be incorporated into body armor. In one aspect, body armor prepared in this manner is lightweight and also resistant to being damaged by bullets. In another aspect, this arrangement of materials can be used to line baggage containers on commercial aircraft to prevent damage to the aircraft structure from explosives contained within luggage or fires starting in luggage items (e.g., from lithium ion batteries). In a similar aspect, cladding or armor for buildings in areas with high risk of terrorism can be constructed from these materials. In any of the above aspects, after calcination, the foams are open cell foams. In a further aspect, like other open cell foams, some cell boundaries have been broken, which allows air to occupy the cell interiors. In still another aspect, the foams are lightweight and have relatively low densities. Aspects The following listing of exemplary aspects supports and is supported by the disclosure provided herein. Aspect 1. A process for producing a carbon foam material, the process comprising: a heating step comprising heating a homogeneous mixture of a coal material and at least one additional agent in a microwave heating apparatus; wherein the homogeneous mixture of a coal material and at least one additional agent comprises: (a) a coal material present in an amount of from about 20 wt % to about 75 wt % based on the total weight of the mixture; and (b) at least one additional agent present in an amount of from about 25 wt % to about 80 wt % based on the total weight of the mixture; and wherein the additional agent is capable of absorbing microwave radiation. Aspect 2. The process of Aspect 1, wherein the heating step comprises heating the mixture to a temperature of from about 250° C. to about 700° C. for from about 1 minute to about 60 minutes. Aspect 3. The process of Aspect 1 or 2, wherein the coal material has a particle size of between about 10 mesh and about 400 mesh. Aspect 4. The process of Aspect 3, wherein the coal material has a particle size of between about 20 mesh and about 150 mesh. Aspect 5. The process of any of Aspects 1-4, wherein the coal material comprises a high-volatile or low-volatile sub-bituminous coal material. Aspect 6. The process of any of Aspects 1-5, wherein the coal material comprises pitch. Aspect 7. The process of any of Aspects 1-6, wherein the additional agent comprises a flux agent. Aspect 8. The process of Aspect 7, wherein the flux agent comprises a carbohydrate syrup. Aspect 9. The process of Aspect 8, wherein the carbohydrate syrup is high fructose corn syrup. Aspect 10. The process of Aspect 8, wherein the flux agent further comprises a secondary flux agent. Aspect 11. The process of Aspect 10, wherein the secondary flux agent comprises a volatile compound produced in a coal conversion process, a coal tar, a product of petroleum distillation, or a combination thereof. Aspect 12. The process of any of Aspects 1-11, wherein the additional agent comprises a lignocellulosic waste material. Aspect 13. The process of Aspect 12, wherein the lignocellulosic waste material comprises sodium lignosulfonate. Aspect 14. The process of any of Aspects 1-13, wherein the additional agent comprises a conductive carbon compound. Aspect 15 The process of Aspect 14, wherein the conductive carbon compound comprises a carbon fiber, a carbon nanofiber, a carbon nanotube, a carbon flake, carbon black, a needle coke, graphene, graphene oxide, graphite, or a combination thereof. Aspect 16. The process of Aspect 15, wherein the conductive carbon compound comprises graphite. Aspect 17. The process of any of Aspects 1-16, wherein the additional agent comprises a solvent. Aspect 18. The process of Aspect 17, wherein the solvent comprises N-methyl-2-pyrrolidone, kerosene, or a combination thereof. Aspect 19. The process of Aspect 18, wherein the solvent comprises N-methyl-2-pyrrolidone. Aspect 20. A process for calcining a carbon foam material, the process comprising: a. heating the carbon foam material to a temperature of from about 900° C. to about 1350° C. for a period of from about 10 seconds to about 3 hours; b. wherein calcining imparts electrical conductivity and mechanical stability to the carbon foam material. Aspect 21. The process of Aspect 20, wherein the carbon foam material is calcined in a furnace. Aspect 22. The process of Aspect 20 or 21, wherein heating is carried out for from about 1 hour to about 3 hours. Aspect 23. The process of Aspect 20, wherein the carbon foam material is calcined in a microwave heating apparatus. Aspect 24. The process of Aspect 23, wherein heating is carried out from about 1 minute to about 10 minutes. Aspect 25. The process of Aspect 20, wherein the carbon foam material is calcined in an inductive field heater. Aspect 26. The process of Aspect 25, wherein heating is carried out for from about 10 seconds to about 1 minute. Aspect 27. The process of any of Aspects 20-26, wherein the process further produces an sp2-hybridized carbon material. Aspect 28. The process of Aspect 27, wherein the sp2-hybridized carbon material comprises graphene, graphene oxide, graphite, or a combination thereof. Aspect 29. A carbon foam material produced by the process of Aspect 1. Aspect 30. A calcined carbon foam material produced by the process of Aspect 20. Aspect 31. A composite material comprising the calcined carbon foam of Aspect 30. Aspect 32. The carbon foam material of Aspect 29, wherein the carbon foam material has a resistivity of from about 0.1 to about 0.5 Ω/ft2. Aspect 33. The carbon foam material of Aspect 29 or 32, wherein the carbon foam material has a density of from about 0.5 to about 1.5 g/cc. Aspect 34. The carbon foam material of any of Aspects 29, 32, or 33 wherein the carbon foam material has a surface area of from about 2 to about 3 m2/g. Aspect 35. The carbon foam material of any of Aspects 29 or 32-34, wherein the carbon foam material has an average grain size of from about 10 to about 390 μm. Aspect 36. The carbon foam material of Aspect 35, wherein the carbon foam material has an average grain size of from about 25 to about 240 μm. Aspect 37. The calcined carbon foam material of Aspect 30, wherein the carbon foam material has a resistivity of from about 0.1 to about 0.5 Ω/ft2. Aspect 38. The calcined carbon foam material of Aspect 30 or 37, wherein the carbon foam material has a density of from about 0.5 to about 1.5 g/cc. Aspect 39. The calcined carbon foam material of any of Aspects 30, 37, or 38, wherein the carbon foam material has a surface area of from about 2 to about 3 m2/g. Aspect 40. The calcined carbon foam material of any of Aspects 30 or 37-39, wherein the carbon foam material has an average grain size of from about 10 to about 390 μm. Aspect 41. The calcined carbon foam material of Aspect 40, wherein the carbon foam material has an average grain size of from about 25 to about 240 μm. Aspect 42. An article comprising the carbon foam material of Aspect 29 or the calcined carbon foam material of Aspect 30. Aspect 43. An article comprising a carbon foam material, wherein the carbon foam material has a resistivity of from about 0.1 to about 0.5 Ω/ft2. Aspect 44. The article of Aspect 42 or 43, wherein the carbon foam material has a density of from about 0.5 to about 1.5 g/cc. Aspect 45. The article of any of Aspects 42-44, wherein the carbon foam material has a surface area of from about 2 to about 3 m2/g. Aspect 46. The article of any of Aspects 42-45, wherein the carbon foam material has an average grain size of from about 10 to about 390 μm. Aspect 47. The article of Aspect 46, wherein the carbon foam material has an average grain size of from about 25 to about 240 μm. From the foregoing, it will be seen that aspects herein are well adapted to attain all the ends and objects hereinabove set forth together with other advantages which are obvious and which are inherent to the structure. While specific elements and steps are discussed in connection to one another, it is understood that any element and/or steps provided herein is contemplated as being combinable with any other elements and/or steps regardless of explicit provision of the same while still being within the scope provided herein. It will be understood that certain features and subcombinations are of utility and may be employed without reference to other features and subcombinations. This is contemplated by and is within the scope of the claims. Since many possible aspects may be made without departing from the scope thereof, it is to be understood that all matter herein set forth or shown in the accompanying drawings and detailed description is to be interpreted as illustrative and not in a limiting sense. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only, and is not intended to be limiting. The skilled artisan will recognize many variants and adaptations of the aspects described herein. These variants and adaptations are intended to be included in the teachings of this disclosure and to be encompassed by the claims herein. Now having described the aspects of the present disclosure, in general, the following Examples describe some additional aspects of the present disclosure. While aspects of the present disclosure are described in connection with the following examples and the corresponding text and figures, there is no intent to limit aspects of the present disclosure to this description. On the contrary, the intent is to cover all alternatives, modifications, and equivalents included within the spirit and scope of the present disclosure. EXAMPLES The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices and/or methods claimed herein are made and evaluated, and are intended to be purely exemplary of the disclosure and are not intended to limit the scope of what the inventors regard as their disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in ° C. or is at ambient temperature, and pressure is at or near atmospheric. Example 1: Materials Low volatile bituminous coal samples were obtained from Rosebud Mining Corporation (Pennsylvania, USA). High volatile bituminous coal samples were obtained from Anker Energy (West Virginia, USA). Samples were ground and separated into size fractions using a RO-TAP® sieve shaker (W.S. Tyler, Ohio, USA) and stored in sealed containers until use. High fructose corn syrup was purchased from Mann Lake, Ltd. (Minnesota, USA). Water content was determined to be 21% by placing a measured sample in a drying oven at 110° C. For some experiments, Karo syrup (a corn syrup that is not considered “high fructose” was used). Analytical grade graphite powder was purchased from Alfa Aesar (Massachusetts, USA) and sized using a Coulter counter. Median size was 6 μm. Pam® non-stick cooking spray (Conagra Brands, Ill., USA) was used as a release agent for ceramic containers. Example 2: Coal Preparation Coal was provided in approximately 60 lb batches after having been processed at a standard coal cleaning plant. The coal was fed three times through a hammer mill to reduce the particle size to about 2 mm. The coal was then fed into a coal pulverizer, which reduced the particle size to about 60 mesh. The pulverized coal was then sifted through a 60 mesh sieve to remove larger particles that had not been sufficiently pulverized. In some experiments, coal particles of other sizes and size ranges (e.g., 20-35 mesh, 35-60 mesh, 60-100 mesh, and >100 mesh) was used. In these experiments, coal was prepared by the same method but used an appropriately sized sieve to retrieve coal particles of the desired size. Carbon foams produced with large and smaller mesh sized coal particles can be seen inFIG.11andFIG.12, respectively. In some experiments, a stack of sieve trays was assembled to separate the particles into desired ranges. A series of sieves was placed above a collection pan. Pulverized coal was poured on top of the top sieve and covered with a lid. The sieves were placed in a sieve shaker and shaken using orbital motion for 10 minutes. The sieves were then disassembled one at a time and the surfaces of the sieves were scraped with a rubber spatula to eliminate any blinding effects. The sieves were then re-stacked and placed back into the sieve shaker for an additional 10 minutes. Following this step, the different mesh sizes of coal particles were collected, weighed, and stored for further experiments. Example 3: Flux Agent Preparation In some experiments, high fructose corn syrup or another carbohydrate syrup was used without further processing as flux agent. In other experiments, a portion of the flux agent was prepared as follows: A 200 mL plastic container was weighed and labeled. Approximately 150 g of fructose or a carbohydrate syrup was added to the container. Recovered volatiles from a coal conversion process described in U.S. Pat. No. 8,226,816 and US Published Patent Application 2015/0083570 were obtained by collection from vacuum distillation step. These recovered volatiles included a mixture of hydrocarbons with boiling points ranging from about 80° C. to about 300° C. About 7.5 g of recovered volatiles were added to the fructose or carbohydrate syrup in the plastic container. The plastic container was then sealed and shaken vigorously by hand for 60 seconds to mix the components of the flux agent. No change was observed after an additional 60 seconds of shaking and the mixture was then considered homogeneous. Example 4: Foaming Mixture Preparation For experiments in which a flux agent was used, the following procedure was employed to prepare the foaming composition: A 250 mL glass beaker was labeled and weighed and 100 g of coal, prepared as described above, was added to the beaker. The flux agent container was shaken to ensure homogeneity and 30 g of flux agent mixture was added to the beaker with the coal. The contents of the beaker were stirred for stirred for several minutes, with additional flux material added as needed (in some experiments, an additional 20 g were added) to achieve an appropriate wetting level for the coal. The mixture was again stirred to ensure a homogeneous coal/flux mixture. In some experiments, the mixture was viscous enough that it could be kneaded by hand, using rubber gloves. When kneading was performed, the kneaded portion was added back to the remainder of the sample and stirring continued. A cycle of kneading and stirring was repeated several additional times. Process Scale-Up Foaming pitch can be prepared on a larger scale for industrial purposes or to enable numerous experiments to be conducted in parallel, according to the following steps. Lignite coal was ground and passed through a 60 mesh sieve. Although a 60 mesh sieve was used for testing, the particle size can be varied without departing from the processes disclosed herein. In particular, the particle size can be further optimized during scaling for commercial operations. Following grinding and sieving, a slurry was prepared by dispersing 15 pounds of ground coal in 42 pounds of condensed and recycled volatiles from previous experiments scaled up but otherwise described above. These recycled volatiles are referred to in the following process as a solvent. Three pounds of hydrogenated vegetable oil was added to the slurry to act as a hydrogen donor during the coal conversion reaction. The slurry was mixed via agitation and transferred into a stirred 10 gallon reaction vessel for coal digestion. Mixture homogeneity was maintained in the reactor vessel. Inside the vessel, the slurry was heated to about 120° C. and held there to allow vaporization of water and low boiling point volatiles present in the coal or solvent. These vapors were vented to a moisture collection vessel and removed from the reaction mixture. The contents of the moisture collection vessel were separately collected, weighed, and analyzed. The reactor was then isolated and temperature increased to 550° C. and held for 1 h. Pressure inside the reactor was maintained between 500-600 psig with venting to allow excess volatiles from the reactor to escape into an expansion tank. The vapors produced at 550° C. were passed through a water-cooled heat exchanger en route to the expansion tank, condensing the vapors to a volatile liquid mixture. Liquid volatiles recovered from this step were weighed, samples were removed for analysis, and the bulk components were added to the recycled solvent mixture for use in future experiments. Non-condensable gases produced by the reaction were further vented from the expansion tank to a scrubber. These primarily contained hydrogen sulfide. Without wishing to be bound by theory, it was believed that the hydrogen sulfide was produced by the removal of sulfur from coal during the conversion process. Once the reaction was complete, remaining pressure in the reactor was vented to the expansion tank and the remaining contents of the reactor, at this point a low-softening point mixture, were transferred into a larger volume holding tank (i.e., a flash vessel) to cool. The low-softening point mixture, containing reacted coal and mineral matter, remained in the flash vessel until the temperature reached 150° C. The mixture was then transferred into a centrifuge processing tank equipped with a gear pump to recycle the extract through a flow-driven centrifuge where ash is concentrated and collected within a rotating spindle. When ash removal was complete, the centrifuge spindle was removed and weighed for mass balance data. Enriched ash centrifuge tails, which form a cake-like residue of mineral matter and volatiles on the inside surface of the centrifuge spindle, were removed from the spindle and maintained for analysis and the spindle was cleaned. Depending on the specific characteristics of the coal used as a source material, the collected mineral matter can contain appreciable levels of rare earth elements (REEs) and, accordingly, can be considered an enriched rare earth elemental feedstock for further refining. It is to be understood that the disclosed procedure can be scaled to use a motor-driven scroll-type centrifuge for improved efficiency. Following centrifugation, de-ashed pitch was pumped into a vacuum distillation apparatus and distillation was carried out by increasing the temperature to 280° C. while maintaining a vacuum of approximately 50 torr. The vacuum distillation column was equipped with a low flow rate nitrogen sparge to facilitate the flow of volatiles from the pitch. Without wishing to be bound by theory, the nitrogen sparge is believed to additionally facilitate orientation of the various moieties in the carbon pitch as it forms. The distillation system was equipped with a set of distillate collection vessels and condensers in parallel to collect different fractions of potentially valuable distillation volatiles, which were weighed and analyzed. The pitch was drained from the distillation column as a liquid at elevated temperature and allowed to cool to room temperature, at which point it solidified. Foaming Pitch Preparation Foaming pitch was then prepared using a process similar to the process used to prepare green foam, with the chief difference being heating to a lower temperature. In this process, the pitch partially devolatilizes but retains a high enough volatile content to be fluid at elevated temperatures, enabling carbon particles to fuse into carbon foam. Furthermore, the system is operated at a pressure of about 700 torr. This slight vacuum increases the efficiency of volatile removal at the lower temperatures used, and provides for capture of the volatiles escaping the pitch to a vapor collection system. This prevents volatiles from condensing and refluxing when contacting the unheated surface of the vessel lid. Once pitch was produced, it was placed in a storage container and held at −5° C. for 12 h. This causes the pitch to become brittle and easily removable from the storage container, weighed, and transferred into a customized coking vessel. The lid for the coking vessel was bolted into place after checking the lid gasket and the vessel was insulated using high temperature insulation and connected to a volatile recovery system, a nitrogen feed, and a power source. A nitrogen purge was turned on at a flow rate of 20 psi in order to create an inert environment within the coking vessel as well as to facilitate the escape of volatiles to the condensation and recovery portion of the coking system. The vessel was heated from room temperature to 500° C. rapidly (i.e., over a period of about 3 h). The temperature was then maintained at 500° C. as the pitch continued to devolatilize. The coking vessel was allowed to cool for 12 h and disconnected from the power supply, nitrogen source, and volatile recovery system. Insulation was removed and top and bottom flanges were unbolted and removed. A chrome-plated steel plunger was used to push the foaming pitch out of the vessel and into a collection container, where it was inspected, weighed, and sampled for later analysis. The foaming pitch was then subjected to a second devolatilization step in the coking vessel at 525° C. for 8 h. Grinding and Sizing the Foaming Pitch Pieces of pitch removed from the coking vessel ranged in size from 0.5 cm to about 8 cm. Larger pieces were crushed with a hand-operated rock crusher. Smaller pieces were ground to the desired particle size using a mortar and pestle. A series of sieve trays was assembled to separate the pitch particles, with additional crushing as needed. The tray stack was shaken by hand to separate the material into the desired particle size ranges (e.g., 20-50 mesh, 50-100 mesh, and >100 mesh). Compacted particles were scraped off as needed and further crushing was carried out using either a rock crusher or mortar and pestle as described above. Example carbon foams produced using the foaming pitch as an additive are seen inFIGS.5-6. Example 5: General Procedure Carbon foam samples were prepared according to the following general procedure (FIG.18). Coal compositions as disclosed herein were placed into ceramic cups or other containers that had been previously coated with a release agent. Ceramic tiles were placed over the tops of the containers. Samples were placed in the microwave chamber and a power level and time increment were chosen. A typical time increment was from 1 to 5 minutes. After each heating cycle, the sample was removed from the microwave chamber and inspected. If the sample had risen during the heating cycle, it was compressed with a clean object having a flat surface (e.g., a beaker). Additional heating cycles were performed until the sample solidified and no more rising was observed. Some experiments were performed using high fructose corn syrup as a flux agent and some experiments used sodium lignosulfonate as a binding agent, with high fructose corn syrup flux samples being generally structurally stronger than sodium lignosulfonate flux samples. In some experiments, coal and flux mixtures were microwaved in a crucible that was placed inside a 1 L glass beaker covered with a 6-inch diameter watch glass, a configuration that allowed released volatile compounds to escape the beaker and avoid any pressure build up. The beaker glass did not respond to microwave radiation in the same manner as the coal mixture and remained cooler; thus escaped volatiles from the crucible condensed on the interior surface of the beaker during microwaving. Crucible loading was accomplished by placing a sufficient amount of material to cover the entire bottom of the crucible and roughly fill it without packing the mixture. The mixture was then compressed into the crucible with further kneading by hand. As needed, additional amounts of the mixture were added and kneaded into place, with addition and kneading repeated until the crucible was filled and the mixture was not further compressible. The flat edge of a paint scraper was used to press the mixture into the crucible with any excess material being scraped away across the surface. When the crucible was completely filled and compressed, it was weighed to determine the starting amount of material. Microwaved foam samples were observed following microwaving to find outwardly bulging portions. Without wishing to be bound by theory, it was believed that the bulging portion was formed as volatile components escaped from the foam. Thus, the carbon foam and the bulging portion were malleable and could be molded or shaped. It was thus concluded, without wishing to be bound by theory, that the carbon material was in a pseudo-fluid state while at higher temperature and did not form a solid foam structure until it had sufficiently cooled. Accordingly, it should be possible to mold or extrude a partially formed carbon foam into specific sizes and shapes without the need for expensive processing to form specific shapes for an end product. Samples thus formed (referred to herein as foaming/flux pitches) were then placed into ceramic crucibles for calcination. Without wishing to be bound by theory, it is believed that swelling or bulging is principally caused by rapid vaporization of light volatiles and/or moisture in the flux agent and that this swelling or bulging can be reduced by heating the sample at a slower rate during the initial stages of heating. It is further believed that swelling or bulging can be reduced by heating the sample to about 105° C. to drive off moisture and some low boiling point volatiles prior to the first microwave heating step. Example foams produced by this process can be seen inFIGS.1-4. Carbon Foam Production at Atmospheric Pressure using Low Volatile Bituminous Coal The starting material for one set of experiments was low volatile bituminous coal ground to a particle size of 80-100 mesh. The coal was combined with a flux agent at a 2:1 ratio by weight, where the flux mixture consisted of 95% fructose and 5% recovered distillation volatiles as described elsewhere in the Examples. The coal and flux agent were combined to a homogeneous mixture and pressed into a crucible, which was in turn placed into a 1 L beaker covered by a watch glass. The beaker containing the crucible was placed into an 1100 W microwave, which was operated for 5 min at power level 3, equivalent to about 330 W. The carbon foam that was produced expanded slightly above the level of the crucible and was pushed back down using a larger crucible. The carbon foam and crucible were heated to 600° C. and calcined at 900° C. as described herein. Example 6: Graphite-Assisted Foam Formation Samples containing high fructose corn syrup as an additional agent but lacking a conductive carbon compound were prepared as described above. Samples containing high fructose corn syrup as well as 1% by weight or 5% by weight graphite were also prepared. Samples containing 1% by weight graphite reached the required temperatures more easily and thus formed green foam more quickly, and a similar increase was also seen for samples containing 5% by weight graphite, regardless of whether high volatile or low volatile bituminous coal was used. Results were similar for different coal particle sizes (20-35 mesh, 35-60 mesh, 60-100 mesh, and >100 mesh) as well as for different microwave power levels, with the largest impact of increasing graphite concentration on foam formation time at low power levels. A 1000 W microwave was used for most experiments. Example 7: Foam Compositions Variables including coal particle size (as mesh size); coal type; weight percent of optional components including high fructose corn syrup, graphite powder, sodium lignosulfonate; and microwave power were evaluated to assess their effects on carbon formation. Results are presented below in Table 1: TABLE 1Foaming Blend Compositions and Microwave Foaming ResponsesMicro-TimeWeightwaveTimeto% HighWeight %PowertoFormWeightFructoseWeightWeight %Sodium(% ofFormCoalMeshCoal%Corn% FluxGraphiteLigno-TotalSolidTarSizeTypeCoalSyrupMixturePowdersulfonatePower)(min)(min)20-35786040000208520-35785940010206520-3578554005020363820-35785540050206020-357855430202010510020-357855440102010510020-35786040000502620-35785940010502320-3578554005050222520-357855400505017720-35785540050501820-3578554500050402520-357860400001001020-35785940010100820-357855400501005520-357855400501005420-35785540050100535-60786040000207935-60785940010206235-60785540050205635-60786040000503435-60785940010503035-60785540050502235-607865305001006NA35-60786530500100101335-60786530500100101335-6078653050010010NA35-60786040000100835-60785940010100735-60785540050100660-100786040000207460-100785940010205860-10078664005020506060-100785540050205060-100786040000501760-100785940010501660-100785540050501560-1007860002381003NA60-1007860002381003NA60-100785000455100NANA60-10078603505010031560-100786040000100760-100785940010100660-100785540050100660-10078504505010034>1007860400002070>1007859400102055>1007855400502048>1007860400005012>100785940010509>100785540050508>1007860400001005NA>1007860400001006>1007859400101005NA>1007859400101005>1007855400501004>1007855400501004NA20-35Kittanning60400002022020-35Kittanning59400102020020-35Kittanning55400502014020-35Kittanning6040000505520-35Kittanning5940010504820-35Kittanning5540050503420-35Kittanning65305001008NA20-35Kittanning65305001006NA20-35Kittanning65305001008NA20-35Kittanning65305001008NA20-35Kittanning65305001006820-35Kittanning60400001001820-35Kittanning59400101001620-35Kittanning55400501001235-60Kittanning60400002021635-60Kittanning59400102019235-60Kittanning55400502011835-60Kittanning6040000504935-60Kittanning5940010504135-60Kittanning5540050503035-60Kittanning65305001008835-60Kittanning65305001008835-60Kittanning653050010012NA35-60Kittanning65305001006NA35-60Kittanning653050010014NA35-60Kittanning60400001001735-60Kittanning59400101001535-60Kittanning55400501001060-100Kittanning60400002021260-100Kittanning59400102018060-100Kittanning55400502010460-100Kittanning6040000504060-100Kittanning5940010503460-100Kittanning5540050502660-100Kittanning65305001008NA60-100Kittanning65305001008NA60-100Kittanning653050010010NA60-100Kittanning65305001008NA60-100Kittanning653050010014NA60-100Kittanning653050010012NA60-100Kittanning60400001001760-100Kittanning59400101001560-100Kittanning554005010010>100Kittanning604000020202>100Kittanning594001020168>100Kittanning55400502098>100Kittanning60400005026>100Kittanning59400105024>100Kittanning55400505019>100Kittanning65305001006NA>100Kittanning65305001006NA>100Kittanning65305001006NA>100Kittanning65305001004NA>100Kittanning65305001006NA>100Kittanning604000010011>100Kittanning594001010010>100Kittanning55400501008 Mesh size refers to particle size of the coal as described previously. Coal type refers either to a low volatile bituminous clay (e.g., “Kittanning” in the table) or a high volatile bituminous clay (e.g., “78” in the table). Time to form solid indicates microwave time at the given power for the sample to form a foam. Flux mixture as used herein refers to a 95% high fructose corn syrup, 5% recovered coal volatile solvent mix. Sodium lignosulfonate mixture as used herein refers to a black liquor as described above. In some instances, a time to form coal tar is also reported. This indicates, in most cases, that additional microwave heating was performed and the sample turned into a coal tar-like substance. In several cases, experiments were replicated several times; data for each replicate is presented in Table 1 on a separate line. An example foam prepared using a sodium lignosulfonate mixture as binder can be seen inFIG.13. Example 8: Carbon Foam Formation in a Furnace Furnace Pyrolysis Initial calcination experiments were carried out on green, coke-like foams as follows. A custom steel box was fabricated (Northco Manufacturing, West Virginia, USA) and partially filled with 1-2 mm graphitized carbon chips (GrafTech International, Ltd., West Virginia, USA) for some experiments. In other experiments, a ceramic bowl was used in place of the steel box. Green foam pieces were placed in crucibles with appropriately-sized lids and buried with additional graphitized carbon chips and steel wool was added to the top of the box or bowl to serve as oxygen scavenger and ensure the atmosphere remained inert or reducing. The steel box or ceramic bowl (covered with a ceramic tile) was placed in a large muffle furnace. Without wishing to be bound by theory, it was believed that heating foam samples at higher temperatures in an oxidizing environment would lead to combustion of the carbon foams, resulting in production of ash rather than of stable carbon foams. In order to maintain consistent heating rates, inert gas flow presented problems. It was further believed that the graphite chips oxidized to carbon dioxide prior to any oxygen reaching the crucibles (i.e., the graphite chips acted as a sink for oxygen entering the system). The graphite chips also allowed volatiles or other gases escaping from the crucibles to exit the sample box or bowl and, ultimately, to escape the furnace. In initial experiments, two furnace heating steps were employed. The steel box or ceramic bowl was placed inside the furnace, which was programmed as follows:(a) the temperature was increased from room temperature at a rate of 200° C./hour to 400° C.;(b) the heating rate was decreased to 100° C./hour until the temperature reached 600° C.;(c) the furnace was held at 600° C. for 3 h;(d) the furnace was turned off and allowed to cool for 10 h. Once the furnace had cooled, the steel box or ceramic bowl was removed. The steel wool typically showed significant oxidation and fusion into a single mass. It was removed and discarded. Graphite chips were removed and retained for reuse. The carbon foam sample was removed from the crucible, inspected, and weighed. A typical sample with a starting weight of 27.2 g had a final weight of 21.6 g. Carbon foam samples were also tested for electrical conductivity using a voltmeter and typically found to be conductive. Furnace Calcination Following this initial step, a second heat treatment was performed to drive off additional volatile components, increase the carbon content of the foam, and increase the strength and crush resistance of the foam. For this calcination step, foam samples formed as described previously were placed back in their original crucibles and covered with the original lids. The crucibles were then placed back into the ceramic bowl or steel box and covered with graphite chips and steel wool as described previously. The steel box was closed or the ceramic bowl was re-covered with a ceramic tile and the whole assembly was placed back inside the furnace. The furnace was programmed for calcination as follows:(a) The furnace was heated at a rate of 500° C./h to 400° C.;(b) the heating rate was reduced to 100° C./h until a temperature of 550° C. was reached;(c) the heating rate was again reduced to 50° C./h until a temperature of 700° C. was reached;(d) the heating rate was again reduced to 25° C.\h until a temperature of 900° C. was reached;(e) the temperature was held at 900° C. for 1 h;(f) the furnace was turned off and allowed to slowly cool over a period of 12 h. After cooling, the container holding the samples was removed from the furnace and emptied as described above. Calcined carbon foam samples were removed from their crucibles and weighed and their electrical conductivity was determined. In later experiments, heating was accomplished in a single step by an initial quick ramp to 550° C. and then slower heating to 900° C. at a rate of 75° C. per hour. The samples were held at 900° C. for three hours and then allowed to cool to room temperature. Samples were retrieved from the steel box and examined. A typical piece of carbon foam contracts by about 30 vol % during calcination while becoming harder, stronger, and more electrically conductive. When heating was not uniform, due to the insulating nature of the foam, contraction caused internal strains which occasionally resulted in the formation of cracks. Microwave-Assisted Calcination An alternative, microwave-assisted calcination procedure for samples containing a conductive carbon compound was designed to address the issue of internal strains and cracks resulting from the initial calcination procedure described above. Non-calcined foam samples containing a conductive carbon compound were tested with a multimeter to determine conductivity. Samples were then heated in a microwave in 5 minute intervals until one hour of exposure time had been reached. After one hour, samples were re-evaluated for conductivity, with the presence of conductivity being an indicator that calcination had occurred. Microwave experiments were conducted in a microwave oven that had been purged with an inert gas to create a non-oxidizing atmosphere. Inductive Field Calcination Since graphite absorbs radio wave energy produced by inductive fields, an inductive heating calcination procedure was designed to avoid any risk of sparking due to high conductive carbon compound content in carbon foam samples. In a typical experiment, a carbon foam sample tested for conductivity using a multimeter and then placed between the coils of an inductive heater. After a heating interval of 30 seconds, the sample was removed and again tested for conductivity; an increase in conductivity was detected, indicating the suitability of the inductive heating method for calcination of carbon foam. Sample foams prepared by inductive field heating, as well as an apparatus used for inductive field calcination, can be seen inFIGS.14-15. Example 9: Foam Properties Density and electrical resistivity were assessed for selected foam samples. These values are presented in Table 2: TABLE 2Density and Electrical Resistivity of Carbon FoamsElectricalDensityResistivityDrySubmergedWet(Ω/ft2)WeightWeightWeightDensityStandardSample(g)(g)(g)(g/mL)MeanDeviationKittanning7.7933.42810.2071.1510.1380.025787.1133.45410.3791.0280.2470.049 Each sample had a coal size of 35-60 mesh, with 65 weight % coal and 35 weight % high fructose corn syrup. Coal types are as described in Example 4. The carbon foams disclosed herein were characterized by various methods. Polarized light microscopy images (seeFIGS.19-20, with and without a color tint) show that the foams are largely isotropic but are characterized by some pressure-induced anisotropy. X-ray diffraction (XRD) analysis showed that the carbon foams were composed largely of disorganized material with a small region of crystalline order from the anisotropic regions (seeFIG.21). Crystal height for these regions was 1.8 nm and crystal lateral dimension was 3.4 nm. An approximately 3.6 Å spacing was observed with a degree of graphitization being 0. SEM-EDS images reveal a cage-like structure; analysis showed some mineral matter detected, with aluminum and silicon content less than 1 wt % and sulfur content less than 1 wt % (FIG.22). N2adsorption/desorption isotherms were measured using a Micromeritics ASAP 2420 accelerated surface area and porosimetry system (FIG.23). Brunauer-Emmett-Teller (BET) surface area was then evaluated using the N2adsorption data. Surface area was found to be approximately 2.65 m2/g, with bulk density being about 0.78 g/cm2. The above experiments indicate the analyzed sample was isotropic and likely formed from coal or coal solvent extract. XRD analysis suggests this foam sample was not heat treated post-foaming. Cages observed by SEM-EDS were large (average size about 300 μm) and interconnected, and surface area and density were relatively low. Particle size distribution and pore size was also assessed using scanning electron microscopy (SEM) for carbon foam samples constructed using different mesh sizes of coal particles. Size distribution was measured for all SEM images with no overlapping areas. FIJI, an open source software package based on ImageJ and Origin scripts were used to measure the dimensions of grains or pores, depending on the sample, directly from SEM images. A carbon foam made from 20-35 mesh coal particles (starting particle size 500-841 μm) (seeFIG.24) shows a grain size ranging from about 40 to about 390 μm with the largest distribution of grains ranging in size from about 40 to about 75 μm (FIG.25). Example SEM images of external surfaces and internal surfaces/pores are shown inFIGS.26and27, respectively. Scale bars in SEM images were used as a basis for software measurement of dimensions of particle and/or pore size. When low magnification mode was used, SEM images cover approximately 3.5×2.5 mm of area. A carbon foam made from 60-100 mesh coal particles (starting particle size 149-250 μm) (seeFIG.28) shows a grain size ranging from about 10 to about 110 μm with the largest distribution of grains ranging in size from about 10 to about 50 μm (FIG.29). Example SEM images of external surfaces and internal surfaces/pores are shown inFIGS.30and31, respectively. A carbon foam made from >100 mesh coal particles (starting particle size <149 μm) (seeFIG.32) shows a grain size ranging from about 30 to about 175 μm with the largest distribution of grains ranging in size from about 75 to about 125 μm (FIG.33). Example SEM images of external surfaces and internal surfaces/pores are shown inFIGS.34and35, respectively. A carbon foam made from 40-60 mesh coal particles (starting particle size 250-400 μm) (seeFIG.36) shows a grain size ranging from about 25 to about 240 μm with the largest distribution of grains ranging in size from about 40 to about 150 μm (FIG.37). Example SEM images of external surfaces and internal surfaces/pores are shown inFIGS.38and39, respectively. Example 10: Single-Step Calcination with High-Volatile Bituminous Coal In some experiments, carbon foam was produced at atmospheric pressure using high volatile bituminous coal using a single heating step. With a higher volatile amount in the coal, a lower amount of flux agent was needed to create the pseudo-liquid state necessary to fuse particles together during microwave radiation. In these experiments, a coal to flux ratio of 4:1 was used, where the flux agent was high fructose corn syrup with no added carbon conversion process volatiles. Particle size range was generally from 30-50 mesh for these experiments, although other particle sizes were evaluated. It was observed that larger particle sizes led to more consistent mixing with less time and effort required. Process steps were generally similar to those previously described, but with some key differences. Coal Preparation High volatile bituminous coal was received in 60 pound plastic bags and processed through a hammer mill to reduce the particle size to approximately 2 mm. The coal was further ground using a mortar and pestle to achieve the desired size range of 30-50 mesh. Initially, 200 g of the 2 mm coal was ground and separated using an assembled stack of sieve trays. Coal outside the desired size range was collected and stored for future use. Foaming Mixture Preparation The flux agent used for these experiments was high fructose corn syrup without any added condensed volatiles. Furthermore, the coal to flux agent ratio was reduced compared to previous experiments based on the inherent volatile percentage of feedstock coal. 100 g of 30-50 mesh coal was added to a 250 mL beaker, followed by the addition of 25 g of high fructose corn syrup. The beaker contents were stirred until the foaming mixture became homogeneous. It was not necessary to knead the material by hand. The foaming mixture was then loaded into a crucible in the same manner as in previous experiments. Post-Microwave Radiation Heat Treatment to Calcination Temperatures Following microwave radiation to produce foam as described previously, the crucible containing the foam was covered with a ceramic lid and placed in a nonoxidizing environment by immersing the samples in graphite chips and covering with steel wool as previously described. Calcination was accomplished in a furnace programmed with the following temperature ramps:(a) the furnace was heated at 400° C./h from room temperature to 350° C.;(b) heating rate was reduced to 100° C./h until 550° C. was reached;(c) heating rate was reduced to 50° C./h until 700° C. was reached;(d) temperature was held at 700° C. for one hour;(e) heating rate was set at 25° C./h until a temperature of 900° C. was reached;(f) temperature was held at 900° C. for 2 h;(g) furnace was turned off and contents were allowed to cool for 12 h. Calcined carbon foam was removed and weighed. Samples were assessed for conductivity using a voltmeter and determined to be conductive, thus showing a single heating step to calcination temperatures was effective and that two steps were not required. Example foams produced using high-volatile bituminous coal are shown inFIGS.7-8. Example 11: Alternative Feedstocks Alternative feedstocks to caking coals were explored as source materials for carbon foam. In one series of experiments, a foaming pitch derived from non-caking coal prepared as described above was used as a feedstock. 90 g of foaming pitch with a particle size range of 30-50 mesh was weighed and transferred to a 250 mL beaker and 15 g of a flux agent composed of high fructose corn syrup and recycled coal volatiles as described previously was added. The contents were mixed for a period of time until the mixture was homogeneous. The foaming mixture was loaded into a crucible and converted into carbon foam using microwave radiation at 20% power for 5 min. The foam was covered with a ceramic lid and calcined in one step in a non-oxidizing environment as described previously. A thin layer of a graphene-type compound was found on the lid of the crucible after this experiment, showing that the method can provide an additional carbon species from vapors expelled during the heat treatment and calcination processes disclosed herein. Examples of graphene-type layers formed on carbon foams can be seen inFIGS.9-10. Example 12: Process Scale-Up In some experiments, larger samples having compositions similar to those described previously (i.e., containing coal powder, high fructose corn syrup, and graphite) but with a top surface area of approximately 1 square foot were prepared. Coal flux mixtures were prepared using a commercial mixer. A square sample container 1 foot on each side was constructed and a large-chamber microwave with rotating coil was obtained for these experiments. Several samples of this size were manufactured successfully using the heating protocols described previously. The container used for large-scale foam production as well as an example large piece of foam are seen inFIGS.16-17. It will be apparent to those skilled in the art that various modifications and variations can be made in the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims. | 134,147 |
11858819 | DETAILED DESCRIPTION OF THE INVENTION Reference will now be made in detail to certain aspects of the disclosed subject matter. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter. Throughout this document, values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of “about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement “about X to Y” has the same meaning as “about X to about Y,” unless indicated otherwise. Likewise, the statement “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z,” unless indicated otherwise. In this document, the terms “a,” “an,” or “the” are used to include one or more than one unless the context clearly dictates otherwise. The term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. The statement “at least one of A and B” or “at least one of A or B” has the same meaning as “A, B, or A and B.” In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section. In the methods described herein, the acts can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process. The term “about” as used herein can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range, and includes the exact stated value or range. The term “substantially” as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. The term “substantially free of” as used herein can mean having none or having a trivial amount of, such that the amount of material present does not affect the material properties of the composition including the material, such that about 0 wt % to about 5 wt % of the composition is the material, or about 0 wt % to about 1 wt %, or about 5 wt % or less, or less than, equal to, or greater than about 4.5 wt %, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt % or less, or about 0 wt %. Method of Producing a Syngas Composition. Various aspects of the present invention provide a method of producing a syngas composition. The method can include hydrolyzing a metal halide salt to form a hydrohalic acid and a hydroxide salt of the metal in the metal halide salt. The metal can include an alkaline earth metal or an alkali metal. The method can include reacting the hydrohalic acid with the metal carbonate salt, wherein the metal carbonate salt is a carbonate salt of the alkaline earth metal or alkali metal, to form CO2, water, and the metal halide salt. At least some of the metal halide salt formed from the reacting of the hydrohalic acid with the metal carbonate salt can be recycled as at least some of the metal halide salt in the hydrolyzing of the metal halide salt to form the hydrohalic acid and the hydroxide salt. The method can also include electrolytically converting the CO2and the water into the syngas composition including carbon monoxide and hydrogen. The metal carbonate salt can be any suitable metal carbonate salt. In some examples, the metal carbonate salt is BeCO3, MgCO3, CaCO3, SrCO3, BaCO3, RaCO3, Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, Fr2CO3, or a combination thereof. The metal carbonate salt can be CaCO3, MgCO3, or a combination thereof. The metal carbonate salt can be CaCO3. The metal carbonate salt can be from any suitable source, such as from a sorbent, a water source (e.g., salt water, fresh water, or ocean water), or a combination thereof. The metal carbonate salt can be CaCO3and the CaCO3can be produced from a CO2-capture sorbent, is a CaCO3precipitate formed from water softening, is natural limestone (e.g., as used in the cement industry, or another industry), or a combination thereof. The method can include hydrolyzing a metal halide salt to form a hydrohalic acid and a hydroxide salt of the metal in the metal halide salt. The metal can include an alkaline earth metal or an alkali metal, such as beryllium, magnesium, calcium, strontium, barium, radium, lithium, sodium, potassium, rubidium, cesium, francium, or a combination thereof. The alkaline earth metal or alkali metal can be magnesium, calcium, or a combination thereof. The alkaline earth metal or alkali metal can be calcium. The metal halide salt can be beryllium halide salt, a magnesium halide salt, a calcium halide salt, a strontium halide salt, a barium halide salt, a radium halide salt, a lithium halide salt, a sodium halide salt, a potassium halide salt, a rubidium halide salt, a cesium halide salt, a francium halide salt, or a combination thereof. The halide can be chloride and the metal halide salt can be beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, radium chloride, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, francium chloride, or a combination thereof. The metal halide salt can be CaCl2, MgCl2, or a combination thereof. The metal halide salt can be CaCl2. The hydrohalic acid can be HCl, HBr, HI, HF, or a combination thereof. The hydrohalic acid can be HCl. The hydroxide salt can be Be(OH)2, Mg(OH)2, Ca(OH)2, Sr(OH)2, Ba(OH)2, Ra(OH)2, LiOH, NaOH, KOH, RbOH, CsOH, FrOH, or a combination thereof. The hydroxide salt can be Ca(OH)2, Mg(OH)2, or a combination thereof. The hydroxide salt can be Ca(OH)2. In some aspects, the metal carbonate salt is CaCO3, the alkaline earth metal or alkali metal is calcium, the metal halide salt is CaCl2, the hydrohalic acid is HCl, and the hydroxide salt is Ca(OH)2. The hydrolyzing of the metal halide salt can be performed under any suitable conditions. The hydrolyzing of the metal halide salt can be performed at any suitable pressure, such as at a pressure of 0.1 MPa-100 Mpa, or 0.1 Mpa to 9 Mpa, or 1 Mpa to 9 Mpa, or 3 Mpa to 9 Mpa, or 5 Mpa to 7 Mpa, or less than, equal to, or greater than 0.1 Mpa, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 40, 50, 60, 70, 80, 90, or 100 Mpa. The hydrolyzing of the metal halide salt can be performed at any suitable temperature, such as a temperature of room temperature to 1000° C., or room temperature to 500° C., or 300° C. to 500° C., or 350° C. to 450° C., or less than, equal to, or greater than room temperature (e.g., about 20° C.), 25, 30, 35, 40, 45, 50, 60, 80, 100, 125, 150, 175, 200, 225, 250, 275, 300, 320, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 480, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1000° C. The hydrolyzing of the metal halide salt (i.e., in water) produces the hydrohalic acid. The hydrohalic acid can be produced in a phase that is distinct from the brine solution that includes the water and the metal halide salt. The acid/water phase can be a vaporous phase, a supercritical water phase, a gaseous phase, or a combination thereof, depending on the hydrolysis conditions used to form the hydrohalic acid. The hydrolyzing of the metal halide salt can produce the hydrohalic acid at any suitable concentration (e.g., in the distinct acid/water phase), such as at a molar content of 0.01% to 10%, or a molar content of 0.1% to 1%, or less than, equal to, or greater than 0.01%, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.8, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or 10% molar content. The reacting of the hydrohalic acid with the metal carbonate salt can be performed under any suitable conditions. The reacting of the hydrohalic acid with the metal carbonate salt can be performed in the same reactor with, and using the same conditions as, the hydrolysis of the metal halide salt to form the hydrohalic acid (e.g., a heated and pressurized reactor). The reacting of the hydrohalic acid with the metal carbonate salt can be performed in a separate reactor from the reacting of the hydrolysis of the metal halide salt to form the hydrohalic acid, such as by removing the hydrohalic acid from the reactor, cooling the hydrohalic acid, and performing the reacting of the hydrohalic acid with the metal carbonate salt under different conditions, such as room temperature/pressure conditions. The reacting of the hydrohalic acid with the metal carbonate salt can be performed at a pressure of 0.1 Mpa-100 Mpa, or 0.1 Mpa to 9 Mpa, or 1 Mpa to 9 Mpa, or 3 Mpa to 9 Mpa, or 5 Mpa to 7 Mpa, or less than, equal to, or greater than 0.1 Mpa, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 40, 50, 60, 70, 80, 90, or 100 Mpa. The reacting of the hydrohalic acid with the metal carbonate salt can be performed at a temperature of room temperature to 1000° C., or room temperature to 500° C., or 300° C. to 500° C., or 350° C. to 450° C., or less than, equal to, or greater than room temperature (e.g., about 20° C.), 25, 30, 35, 40, 45, 50, 60, 80, 100, 125, 150, 175, 200, 225, 250, 275, 300, 320, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 480, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1000° C. At least some of the metal halide salt formed from the reacting of the hydrohalic acid with the metal carbonate salt can be recycled as at least some of the metal halide salt in the hydrolyzing of the metal halide salt to form the hydrohalic acid and the hydroxide salt. The metal halide salt formed from the reacting of the hydrohalic acid with the metal carbonate salt can be any suitable proportion of the metal halide salt used in the hydrolyzing of the metal halide salt to form the hydrohalic acid and the hydroxide salt. For example, the metal halide salt formed from the reacting of the hydrohalic acid with the metal carbonate salt is 0.001 wt % to 100 wt % of the metal halide salt used in the hydrolyzing of the metal halide salt to form the hydrohalic acid and the hydroxide salt, or 80 wt % to 100 wt %, or less than, equal to, or greater than 0.001 wt %, 0.01, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or 99.999 wt %, or 100 wt %. Various aspects provide a method of treating CaCO3to form a syngas composition. The method can include hydrolyzing CaCl2to form HCl and Ca(OH)2. The method can include reacting the HCl with the CaCO3, to form CO2, water, and CaCl2, wherein at least some of the CaCl2) formed from the reacting of the HCl with the CaCO3is recycled as at least some of the CaCl2) in the hydrolyzing of the CaCl2) to form the HCl and the Ca(OH)2. The method can further include reacting a used CO2-capture sorbent with the Ca(OH)2, to form the CaCO3, wherein at least some of the Ca(OH)2formed in the hydrolysis of the CaCl2) to form the HCl and the Ca(OH)2is recycled as at least some of the Ca(OH)2used in the reacting of the used CO2-capture sorbent with the Ca(OH)2. The method can include reacting Ca(HCO3)2from a water source with the Ca(OH)2, to form the CaCO3, wherein at least some of the Ca(OH)2formed in the hydrolysis of the CaCl2) to form the HCl and the Ca(OH)2is recycled as at least some of the Ca(OH)2used in the reacting of the Ca(HCO3)2with the Ca(OH)2. The method can also include electrolytically converting the CO2and the water into a syngas composition including carbon monoxide and hydrogen The method of producing a syngas composition can be used to regenerate hydrated lime (Ca(OH)2), such as from the precipitates produced during lime softening of water. Lime softening is a common treatment for municipal and industrial water supplies. The method of producing a syngas composition can be used to produce hydrated lime or dolomitic lime (e.g., a mixture of Ca(OH)2and Mg(OH)2). This process is already performed at large scale using calcination to produce lime for cement, steelmaking, food processing, and many other industries. The method of producing a syngas composition can be used to process a source of CaCO3to convert it into a Ca(OH)2product. The method of producing a syngas composition can include reacting the hydrohalic acid with the metal carbonate salt, wherein the metal carbonate salt is a carbonate salt of the alkaline earth metal or alkali metal, to form CO2, water, and the metal halide salt. The method of producing a syngas composition can include electrolytically converting the CO2and the water produced by the reacting of the hydrohalic acid with the metal carbonate salt into the syngas composition including carbon monoxide and hydrogen. The water formed by the reacting of the hydrohalic acid with the metal carbonate salt can be or can include gaseous water. The water formed during the reacting of the hydrohalic acid can have a temperature of 100° C. to 500° C., or 100° C. to 150° C., or less than or equal to 500° C. and greater than or equal to 100° C., 110, 120, 130, 140, 150, 160, 180, 200, 250, 300, 350, 400, or 450° C. Any suitable proportion of the water formed by the reacting the hydrohalic acid with the metal carbonate salt can be gaseous water; for example, 50-100 wt % of the water formed during the reacting of the hydrohalic acid can be gaseous water, or 90-100 wt %, or less than or equal to 100 wt % and greater than or equal to 50, 55, 60, 65, 70, 75, 80, 85, or 95 wt %. The electrolytic conversion of the CO2can convert any suitable proportion of the CO2and the water to other products (such as carbon monoxide). For example, the electrolytic conversion of the CO2and the water into the syngas composition can convert 50% to 100% of the CO2, or 90% to 100% of the CO2, or less than or equal to 100 wt % and greater than or equal to 50, 55, 60, 65, 70, 75, 80, 85, or 95 wt % of the CO2. For example, the electrolytic conversion of the CO2and the water into the syngas composition can convert 50% to 100% of the water, or 90% to 100% of the water, or less than or equal to 100 wt % and greater than or equal to 50, 55, 60, 65, 70, 75, 80, 85, or 95 wt % of the water. The syngas composition includes carbon monoxide and hydrogen. Carbon monoxide can form any suitable proportion of the syngas composition, such as 15 mol % to 40 mol % of the syngas composition, or 30 mol % to 36 mol % of the syngas composition, or less than or equal to 40 mol % and greater than or equal to 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, or 39 mol %. Hydrogen can form any suitable proportion of the syngas composition, such as 30 mol % to 80 mol % of the syngas composition, or 60 mol % to 75 mol % of the syngas composition, or less than or equal to 80 mol % and greater than or equal to 30 mol %, 35, 40, 45, 50, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, or 79 mol %. The syngas composition can have any suitable molar ratio of hydrogen to carbon monoxide, such as 1:1 to 3.5:1, 1.9:1 to 2.1:1, or less than or equal to 3.5:1 and greater than or equal to 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 1.9:1, 2.0:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.6:1, 2.8:1, 2.9:1, 3:1, 3.1:1, 3.2:1, or 3.4:1. Any suitable proportion of the syngas composition can be CO2, such as 0 mol % to 20 mol %, or 0 mol % to 5 mol %, or less than or equal to 20 mol % or greater than or equal to 0 mol %, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, or 18 mol %. Any suitable proportion of the syngas composition can be water, such as 0 mol % to 33 mol %, or 0 mol % to 10 mol %, or less than or equal to 33 mol % and greater than or equal to 0 mol %, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, or 32 mol %. In various embodiments, the method can include supplementing the water from the reaction of the hydrohalic acid with the metal carbonate salt (e.g., HCl with CaCO3) with additional water to accomplish a desired molar ratio of hydrogen to carbon monoxide, such as by vaporizing a portion of the water entrained with the CaCO3. Electrolytically converting the CO2and the water into the syngas composition can include placing the CO2and/or the water into contact with an electrolytic cell. The electrolytic cell can be any suitable electrolytic cell that can convert the CO2, the water, or both, to carbon monoxide and hydrogen. The electrolytic cell can include a reverse fuel cell, a solid oxide electrolysis cell, and/or a molten carbonate electrolysis cell. The electrolytic cell can include a solid oxide electrolysis cell. The electrolytic cell can include an anode, cathode, and an electrolyte, wherein at least one of the anode, cathode, and the electrolyte includes yttria-stabilized zirconia (YSZ). The electrolytic cell can include a cathode including Ni. The electrolytic cell can include an anode including lithium strontium manganite (LSM). The electrolytic cell can include an electrolyte including yttria-stabilized zirconia (YSZ), a cathode including Ni-YSZ, and an anode including lithium strontium manganite (LSM)-YSZ cathode. The electrolytic cell can be a solid oxide electrolysis cell (SOEC) with yttria-stabilized zirconia (YSZ) electrolyte, Ni-YSZ cathode, and LSM-YSZ anode where LSM is Lanthanum Strontium Manganite. Such electrode assemblies can sandwich a YSZ electrolyte layer between the anode and cathode layers; this electrode structure can be formed into plates or tubes that can be used to create separate flow chambers for the CO, H2, CO2, and H2O gas mixture, and the 02 that is electrochemically separated. Electrolytically converting the CO2and the water into the syngas composition can include placing the CO2into contact with a first electrolytic cell that electrolytically converts the CO2to CO, and placing the water into contact with a second electrolytic cell that electrolytically converts the H2O to H2. Electrolytically converting the CO2and the water into the syngas composition can include placing the CO2and the water into contact with an electrolytic cell that electrolytically converts the CO2to CO and that electrolytically converts the H2O to H2(i.e., coelectrolysis). Electrolytically converting the CO2and the water into the syngas composition can include using (e.g., maintaining) the one or more electrolytic cells at a temperature of 500° C. to 1,000° C., or 700° C. to 800° C., or less than or equal to 1,000° C. and greater than or equal to 500° C., 550, 600, 650, 700, 720, 740, 760, 780, 800, 850, 900, or 950° C. The method of producing the syngas composition can include using the syngas composition as a starting material to form a product including ammonia, methanol, a liquid fuel, a lubricant, gasoline, an oxo alcohol, or a combination thereof. The method can include using the syngas composition as a starting material in a Fischer-Tropsch process to form one or more hydrocarbons. The method can be a method of making methanol, wherein the method further includes using the syngas composition as a starting material to form methanol. Forming the methanol can include reacting the CO and the hydrogen in the presence of a catalyst to form the methanol. The catalyst can be any suitable catalyst. For example, the catalyst can include Cr—Zn, Cu—Zr, and/or Cu—Zn. The catalyst can include a Cu—Zn catalyst. Forming the methanol can include reacting the CO and the hydrogen in the presence of the catalyst at any suitable temperature, such as a temperature of 20° C. to 500° C., or 200° C. to 300° C., or less than or equal to 500° C. and greater than or equal to 20° C., 40, 60, 80, 100, 120, 140, 160, 180, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 320, 340, 360, 380, 400, 450° C. Forming the methanol can include reacting the CO and the hydrogen in the presence of the catalyst at any suitable pressure, such as a pressure of 0.1 MPa to 40 MPa, 3 MPa to 10 MPa, or less than or equal to 40 MPa and greater than or equal to 0.1 MPa, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 20, 24, 26, 28, 30, 32, 34, 36, or 38 MPa. The method can include recycling at least some exothermic heat generated by the formation of the product from the starting material in the method. Recycling at least some exothermic heat generated by the formation of the product from the starting material in the method can include supplying at least part of the generated exothermic heat to the reaction of the hydrohalic acid with the metal carbonate salt to form the metal halide salt. Method of Regenerating a CO2-Capture Sorbent. The method of producing the syngas composition can be used to remove CO2from a used CO2-capture sorbent (e.g., a CO2-capture sorbent for air). The method can include reacting a used CO2-capture sorbent with the hydroxide salt to provide the metal carbonate salt that is a carbonate salt of the metal in the metal halide salt. The used CO2-capture sorbent can be any suitable used CO2-capture sorbent, such as formed from contacting CO2with any suitable CO2-capture sorbent. The used CO2-capture sorbent can be a used hydroxide-based, ammonia-based, and/or amine-based CO2-capture sorbent. In some examples, the used ammonia-based and/or amine-based CO2-capture sorbent can include an ammonium carbamate, an ammonium carbonate, an ammonium bicarbonate, or a combination thereof. The used CO2-capture sorbent can be derived from sorption of CO2by a hydroxide-based, ammonia-based (e.g., aqueous ammonia and/or ammonium bicarbonate), and/or amine-based CO2-capture sorbent (e.g., monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, methyldiethanolamine, piperazine). The CO2-capture sorbent can be a used hydroxide-based CO2-capture sorbent, such as Ca(HCO3)2(derived from Ca(OH)2), Mg(HCO3)2(derived from Mg(OH)2), K2CO3(derived from KOH), Na2CO3(derived from NaOH), or a combination thereof. The reacting of the used CO2-capture sorbent with the hydroxide salt to provide the metal carbonate salt can be performed under any suitable conditions. The reacting of the used CO2-capture sorbent with the hydroxide salt to provide the metal carbonate salt can be performed at a pressure of 0.01 MPa to 10 MPa, 0.05 MPa to 0.2 MPa, or less than, equal to, or greater than 0.01 MPa, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.25, 0.3, 0.4, 0.5, 0.6, 0.8, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, or 10 MPa. The reacting of the used CO2-capture sorbent with the hydroxide salt to provide the metal carbonate salt is performed at a temperature of room temperature to 350° C., or 50° C. to 150° C., or 90° C. to 110° C., or less than, equal to, or greater than room temperature 25, 30, 35, 40, 45, 50, 60, 70, 80, 85, 90, 95, 100, 105, 110, 115, 120, 120, 125, 150, 175, 200, 225, 250, 275, 300, 320, 340, or 350° C. The method can include contacting a CO2-capture sorbent with CO2to form the used CO2-capture sorbent. In other aspects, the CO2-capture sorbent is contacted with CO2to form the used CO2-capture sorbent prior to the onset of the method. The method can include contacting Ca(OH)2, Mg(OH)2, KOH, and/or NaOH with CO2to form the used CO2-capture sorbent. The reacting of the used CO2-capture sorbent with the hydroxide salt to form the metal carbonate salt can also form an unused CO2-capture sorbent, e.g., to regenerate the used CO2-capture sorbent. The unused CO2-capture sorbent can be Ca(OH)2, Mg(OH)2, KOH, and/or NaOH. The unused CO2-capture sorbent can be KOH and/or NaOH. The method can further include providing the unused CO2-capture sorbent for CO2capture. The method can further include contacting the regenerated CO2-capture sorbent with CO2to form a used CO2-capture sorbent, which can then again be regenerated using the method. In some aspects, none of the hydroxide salt formed in the hydrolysis of the metal halide salt to form the hydrohalic acid and the hydroxide salt is recycled as the hydroxide salt used in the reacting of the used CO2-capture sorbent with the hydroxide salt. In other aspects, at least some of the hydroxide salt of the metal formed in the hydrolysis of the metal halide salt to form the hydrohalic acid and the hydroxide salt can be recycled as at least some of the hydroxide salt used in the reacting of the used CO2-capture sorbent with the hydroxide salt. For example, the hydroxide salt of the metal formed in the hydrolysis of the metal halide salt can be 0.001 wt % to 100 wt % of the hydroxide salt used in the reacting of the used CO2-capture sorbent with the hydroxide salt, or 80 wt % to 100 wt %, or less than, equal to, or greater than 0.001 wt %, 0.01, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or 99.999 wt %, or 100 wt %. The method of regenerating a used CO2-capture sorbent can include hydrolyzing a metal halide salt to form a hydrohalic acid and a hydroxide salt of the metal in the metal halide salt, the metal including an alkaline earth metal or an alkali metal. The method can include reacting the used CO2-capture sorbent with the hydroxide salt, to form a carbonate salt of the metal in the metal halide salt. The method can also include reacting the hydrohalic acid with the carbonate salt, to form CO2and the metal halide salt, wherein at least some of the metal halide salt formed from the reacting of the hydrohalic acid with the carbonate salt is recycled as at least some of the metal halide salt in the hydrolyzing of the metal halide salt to form the hydrohalic acid and the hydroxide salt. The method of forming a syngas composition can include hydrolyzing CaCl2to form HCl and Ca(OH)2. The method can include reacting the used CO2-capture sorbent with the Ca(OH)2, to form CaCO3. The method can also include reacting the HCl with the CaCO3, to form CO2, water, and CaCl2), wherein at least some of the CaCl2) formed from the reacting of the HCl with the CaCO3is recycled as at least some of the CaCl2) in the hydrolyzing of the CaCl2) to form the HCl and the Ca(OH)2. The method can include electrolytically converting the CO2and the water into a syngas composition including carbon monoxide and hydrogen. The method of producing a syngas composition including regenerating a used CO2-capture sorbent can provide a lower-temperature and lower-energy alternative to high-temperature calcination for hydroxide-based CO2DAC solvents. Solvents like KOH and NaOH have high affinity for CO2, even at low partial pressure, and offer design advantages for the massive air contactors required for large-scale CO2removal from the atmosphere. For instance, being liquid, these capture solvents can be circulated over a variety of air contactor geometries while being regenerated at a central location, thereby using the full system capacity for continuous CO2capture. However, regeneration of these solvents requires decomposition of a carbonate (commonly CaCO3) which is an energy-intensive, high-temperature (900° C.) process using existing calcination techniques. This energy requirement is a significant drawback for hydroxide solvents since it results in additional emissions that must be offset by DAC system capacity to produce a net CO2reduction. Instead of high-temperature calcination, the present method of regenerating a CO2-capture sorbent can decompose carbonates using a regenerable acid produced from the hydrolysis of a chloride-based regeneration solution. A comparison of the process using CaCl2) brine to calcination regeneration is shown inFIG.1. The process of brine hydrolysis regeneration inFIG.1can integrate with DAC systems by using hydrochloric acid (HCl) to decompose carbonates, thus releasing captured CO2and recovering the precipitated hydroxide (e.g., Ca[OH]2) to regenerate soluble hydroxide solvents such as KOH and NaOH. Hydrolysis can occur at significantly lower temperatures than calcination (e.g., 400° versus 900° C.), and it can offer a feasible way to recycle thermal energy released from Ca(OH)2formation, thus lowering the quantity of input thermal energy. Chloride compounds in the regeneration solution are not consumed and can be continually recycled. Brine hydrolysis can be the source of HCl used for carbonate decomposition, and it has been observed experimentally. A plot of pressure versus concentration for CaCl2brine is shown inFIG.2, which is a plot of phase composition data for CaCl2brine near its critical point (see, Bischoff, J.; Rosenbauer, R.; Fournier, R. The Generation of HCl in the System CaCl2—H2O: Vapor-Liquid Relations from 380°-500° C.Geochimica et Cosmochimica Acta1996, 60 (1), 7-16). As the data show, HCl is produced in significant amounts during the dynamic equilibrium above CaCl2brine held at a moderate temperature of 400° C. The hydrolysis data shown inFIG.2also result in corresponding Ca(OH)2left behind in the brine, some of which precipitates because of its decreasing solubility with temperature. The hydrolysis data highlighted inFIG.2evaluated conditions over the temperature range of 380° to 500° C. but was a study of equilibrium conditions and, by definition, did not consider the kinetics of CaCl2hydrolysis. Referring to the brine hydrolysis regeneration process inFIG.1, the hydrolysis reactor contains a concentrated solution of CaCl2and H2O with an acid/water phase above it. The acid/water phase can include H2O with a fraction of HCl produced as a result of brine hydrolysis; the exact amount of HCl depends on the temperature, pressure, and brine composition within the reactor. The other component from CaCl2hydrolysis, Ca(OH)2, can remain in the brine and can precipitate because of its decreasing solubility with temperature. At equilibrium, the amount of CaCl2hydrolysis can be stable, but in the brine hydrolysis regeneration scheme, HCl-containing vapor can be reacted with CaCO3from causticization of a DAC solvent. This HCl consumption along with Ca(OH)2precipitation can shift the reaction toward continued hydrolysis. The decomposition of CaCO3can release a stream of captured CO2and can reproduce the CaCl2salt to complete the cycle. Some indication of the minimum theoretical energy requirements can be gained by considering their standard heat of reaction. Table 1 compares the reaction energies for brine hydrolysis regeneration and the existing method using calcination and lime slaking; these pathways correspond to the alternatives shown inFIG.1. Summing the reaction energies for both pathways gives the same net endothermic energy of +113 kJ/mol CO2, which is a thermodynamic necessity since all inputs and outputs at the process boundary are assumed to be identical. In practice, however, recovering energy between process steps is not always feasible. For instance, lime slaking is significantly exothermic, but the reaction does not proceed in the forward direction at the temperature needed for calcination (900° C.), and as a result, heat from this reaction cannot be used to offset the calcination energy requirement of +178 kJ/mol CO2(without the input of additional work). TABLE 1Comparison of Regeneration Pathway Energies.Existing Calcination RegenerationBrine Hydrolysis RegenerationReactionHeat of ReactionReactionHeat of ReactionCarbonate Calcination+178 kJ/mol CO2Carbonate Decomposition−15 kJ/mol CO2CaCO3→ CaO + CO2CaCO3+ 2HCl →CaCl2+ CO2+ H2OLime Slaking−65 kJ/mol CO2Brine Hydrolysis+128 kJ/mol CO2CaO + H2O → Ca(OH)2CaCl2+ 2H2O →2HCl + Ca(OH)2 In contrast to calcination regeneration, the reactions including brine hydrolysis regeneration in Table 1 can both proceed under the same conditions of temperature and pressure, and as a result, it is theoretically possible to reduce the regeneration energy requirement from +178 kJ/mol CO2to +113 kJ/mol CO2. Even if the steps of carbonate decomposition and brine hydrolysis are not combined in the same reactor, the full energy required by brine hydrolysis alone is still a significant savings compared to calcination (+128 kJ/mol CO2versus +178 kJ/mol CO2) and occurs at a much lower temperature (400° C. versus 900° C.). FIG.3presents a KOH solvent capture process using Ca causticization, a DAC process suitable for large-scale application. In the system, a KOH solvent contacts air and absorbs CO2. Spent CO2-rich solvent is then causticized using Ca(OH)2where the captured CO2is transferred from the solvent to an insoluble carbonate, CaCO3in this case. Causticization is mildly exothermic, but its primary utility is to transfer CO2from the liquid solution to a solid, thereby reducing sensible energy consumption during regeneration. At this point in the process, precipitated CaCO3can enter the brine hydrolysis regeneration stage where it is decomposed using HCl to release the captured CO2. The resulting CaCl2salt reforms the brine used for HCl and Ca(OH)2generation. Nominal conditions within the brine hydrolysis process have been estimated at 400° C. and 6 MPa based on the experimental data shown inFIG.2. While hydroxide-based solvents such as KOH and NaOH have desirable capture and engineering properties, their high regeneration energy requirements (greater than 178 kJ/mol CO2at 900° C.) necessitates the development of improved alternatives. The method of the present invention provides a practical means to approach the theoretical limit of regeneration energy (113 kJ/mol CO2) at a significantly lower temperature (400° C.), thereby providing improved CO2separation performance over the options available today. Method of Removing CO2from Water. The method of producing the syngas composition can be used to remove CO2from water. For example, the method can further include reacting a bicarbonate salt such as NaHCO3, Mg(HCO3)2, Ca(HCO3)2, KHCO3, or a combination thereof, taken from any suitable water source, with the hydroxide salt to provide the metal carbonate salt that is a carbonate salt of the metal in the metal halide salt. The method can be a method of softening water. The water source can be a natural water source, such as salt water, ocean water, brackish water, fresh water, a stream, a pond, a lake, a river, or a combination thereof. The bicarbonate salt can be Ca(HCO3)2. In some aspects, none of the hydroxide salt of the metal formed in the hydrolysis of the metal halide salt to form the hydrohalic acid and the hydroxide salt is recycled as at least some of the hydroxide salt used in the reacting of the bicarbonate salt with the hydroxide salt. In other aspects, at least some of the hydroxide salt of the metal formed in the hydrolysis of the metal halide salt to form the hydrohalic acid and the hydroxide salt is recycled as at least some of the hydroxide salt used in the reacting of the bicarbonate salt with the hydroxide salt. For example, the hydroxide salt of the metal formed in the hydrolysis of the metal halide salt is 0.001 wt % to 100 wt % of the hydroxide salt used in the reacting of the bicarbonate salt with the hydroxide salt, or 80 wt % to 100 wt %, or less than, equal to, or greater than 0.001 wt %, 0.01, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or 99.999 wt %, or 100 wt %. The method of producing the syngas composition including removing CO2from water can include hydrolyzing a metal halide salt to form a hydrohalic acid and a hydroxide salt of the metal in the metal halide salt, the metal including an alkaline earth metal or an alkali metal. The method can include reacting a bicarbonate salt from a water source with the hydroxide salt, to form a carbonate salt of the metal in the metal halide salt. The method can also include reacting the hydrohalic acid with the carbonate salt, to form CO2and the metal halide salt, wherein at least some of the metal halide salt formed from the reacting of the hydrohalic acid with the carbonate salt is recycled as at least some of the metal halide salt in the hydrolyzing of the metal halide salt to form the hydrohalic acid and the hydroxide salt. The method of producing the syngas composition including removing CO2from water can include hydrolyzing CaCl2) to form HCl and Ca(OH)2. The method can include reacting Ca(HCO3)2from a water source with the Ca(OH)2, to form CaCO3. The method can include reacting the HCl with the CaCO3, to form CO2, water, and CaCl2), wherein at least some of the CaCl2) formed from the reacting of the HCl with the CaCO3is recycled as at least some of the CaCl2) in the hydrolyzing of the CaCl2) to form the HCl and the Ca(OH)2. The method can also include electrolytically converting the CO2and the water into the syngas composition including carbon monoxide and hydrogen. An example of the method of removing CO2from water is shown inFIG.4, which illustrates a method for removing CO2from the ocean. Advantageously, the method leverages two advantages of CaCl2) splitting compared to a NaCl-based process, resulting in a transformational improvement in ocean CO2removal. Firstly, the Ca and Cl constituents of the CaCl2) brine can be recycled, and when regenerated, the brine is already concentrated. This is unlike a NaCl-based process where the split NaOH and HCl constituents are released with the treated seawater and replacement NaCl brine must be reconcentrated. Secondly, the proposed method of CaCl2) splitting is based on the hydrolysis of CaCl2) brine, a thermochemical process where appreciable quantities of HCl are produced in the acid/water phase above a heated CaCl2) brine pool. Compared to electrochemical- and/or membrane-based salt-splitting approaches, brine hydrolysis is potentially more robust and lower cost to operate. In various aspects, the method can lower the cost of ocean CO2removal to an estimated cost of $62/ton CO2or less. Aspects of the method can address the high energy costs needed to drive ocean CO2removal. Input energy is required to convert the dominant form of CO2in the oceans, bicarbonate ion (HCO3−), to form CO2gas that can be separated for utilization or sequestration. Conceptually, this process can be shown as HCO3−(aq)→CO2(g)+OH−(aq), which has a reaction heat of +66 kJ/mol CO2. Unfortunately, real processes have not achieved this minimum level of energy consumption, and state-of-the-art approaches are estimated to require many times this amount of energy to complete the task of CO2removal. Excessive energy consumption hinders ocean CO2removal by increasing operating costs and creating additional CO2emissions that need to be offset. The method of the present invention of removing CO2from water can provide a thermochemical cycle to achieve production of CO2from bicarbonate while enabling a lower cost of energy consumption compared to what is possible today, making the concept of ocean CO2removal a more feasible tool for carbon management. Various aspects of the method of producing the syngas composition including removing CO2from water include a process of hydrolytic softening based on salt splitting, but instead of NaCl the targeted salt can be CaCl2), as shown inFIG.4. Using CaCl2) can allow for a thermochemical approach to separate the salt into acid and base, thus switching the primary form of energy input from electricity to heat. The use of CaCl2) can also avoid the need to concentrate the brine prior to splitting which is an energy-intensive requirement for some NaCl-based approaches. Hydrated lime, Ca(OH)2, is used in Step 1 ofFIG.4to remove bicarbonate ions in seawater using the familiar chemistry of lime softening: at elevated pH, bicarbonate ions are reduced to carbonate which forms solid precipitates of CaCO3. The alkalinity of seawater is approximately 200 ppm (as CaCO3), and cold lime softening can be expected to achieve a reduction to around 50 ppm with near stoichiometric utilization of Ca(OH)2. The precipitates formed in Step 1 can be allowed to settle by gravity and are collected as a dense slurry. Softened seawater exits the process; its elevated pH to be dissipated by absorbing additional CO2from the atmosphere and mixing with untreated seawater. These mixing processes can be accelerated by mechanical means, such as to prevent harm to the local environment. The CaCO3slurry produced from the seawater softening process inFIG.4can be collected and sent to a reactor where it is mixed with aqueous HCl from brine hydrolysis. The resulting spontaneous reaction (−15 kJ/mol CO2) decomposes the CaCO3to liberate CO2gas and reform the CaCl2) brine. In order to control the concentration of the resulting CaCl2) brine, the density of the incoming CaCO3slurry can be controlled along with the concentration of the HCl solution leaving the brine hydrolysis step. Advantageously, as compared to an a NaCl-based process, the need for brine concentration before salt splitting is avoided. With a NaCl process, the split constituents of HCl and NaOH are lost to the treated seawater, and new concentrate must be continually reformed. The CO2released during Step 2 can include associated water vapor but can otherwise be of high purity. The CaCO3slurry can act as an effective scrubbing solution for vapor-phase HCl to prevent its contamination of the CO2product. The reaction between aqueous HCl and slurry CaCO3can be conducted under pressure to produce a pressurized CO2product, thus saving gas compression energy input. Brine hydrolysis can be a driving process behind hydrolytic softening, as shown inFIG.4. In Step 3, the concentrated CaCl2) brine, at a volume flow roughly 0.025% that of the seawater, can be hydrolyzed to form Ca(OH)2for softening and HCl to decompose the CaCO3precipitate. As the data inFIG.2show, HCl is produced in significant amounts (approximately 3000 ppm) during the dynamic equilibrium above CaCl2) brine held at a moderate temperature of 400° C. The hydrolysis data shown inFIG.2also result in corresponding Ca(OH)2left behind in the brine, some of which can precipitate because of its decreasing solubility with temperature. In addition to the hypothesized energy savings with brine hydrolysis, other potential advantages have been identified over electrochemical approaches to salt splitting. For instance, the process chemistry is robust and can be tolerant of the other dissolved species found in seawater. Any impurities that accumulate in the process can be kept in check with a periodic blowdown of the excess seawater Ca that precipitates in addition to the Ca added from the hydrated lime. Finally, unlike electrochemical processes, there are no concerns of catalyst or membrane fouling with hydrolytic softening. Compared to a NaCl-based process, the hydrolytic softening method described herein can be less disruptive to ocean life since it does not acidify the water which could harm sensitive organisms. As a result, hydrolytic softening can present a relatively lower environmental risk and should face fewer restrictions on its application. Regarding offshore processing costs, the simple reactor needs of hydrolytic softening make it more likely that cost projections can be met compared to a more complex process based on EDBM that requires large membrane surfaces that must be kept clean for optimal efficiency. In contrast, a floating reactor for hydrolytic softening only needs to separate seawater undergoing treatment from its surroundings and provide a collection basin (such as the ocean floor) for the precipitated carbonates. As with environmental concerns, hydrolytic softening appears to present less technical risk regarding ocean process development compared to state-of-the-art alternatives, and this feature should translate into a shorter time to market. The method of hydrolytic water softening can be used for various purposes including ocean CO2removal and treatment of industrial waste brines. The application of treating waste brines to make them easier to recycle or to recover valuable products therefrom can include treating produced water from oil and gas development, or displaced brine from geologic CO2sequestration. Such processes could be powered by natural gas in remote areas. EXAMPLES Various aspects of the present invention can be better understood by reference to the following Examples which are offered by way of illustration. The present invention is not limited to the Examples given herein. Part I. Treatment of Metal Carbonate Salt. The reactor used in Examples 1 and 3 can decompose Ca and Mg carbonates (i.e., CaCO3and MgCO3) as an alternative to conventional calcination (i.e., the direct thermal decomposition of these compounds. The reactor uses aqueous solutions of the corresponding chloride salts (i.e., CaCl2) and MgCl2) as a reaction intermediary to achieve carbonate decomposition at lower temperatures than those needed for direct thermal decomposition. Furthermore, the reactor converts the resulting oxide (CaO and MgO) into the corresponding hydroxide (Ca(OH)2or Mg(OH)2), which is an exothermic reaction. This release of energy has the potential to offset the energy required for carbonate decomposition, a task that is virtually impossible to achieve with conventional calcination. The reactor is illustrated inFIG.5, which shows the cross section of the reactor for the decomposition of CaCO3from CO2-capture processes, water softening processes, and/or natural limestone. Within the sealed reactor a pool of concentrated liquid CaCl2) brine resides at the bottom with a vapor phase above it. The vapor phase will consist of H2O with a small fraction of HCl gas produced as a result of CaCl2salt hydrolysis; the exact amount of HCl depends on the temperature, pressure and brine concentration within the reactor. The other component of CaCl2) hydrolysis, CaO, remains in the brine and is converted to the hydroxide Ca(OH)2, which can precipitate due to its low solubility. At equilibrium the degree of CaCl2hydrolysis is fixed, but in the reactor shown, solid CaCO3is suspended in the vapor phase which promotes continual hydrolysis of the salt by consuming HCl gas to reproduce CaCl2salt. CO2gas is produced during this process which can be released from the reactor along with some amount of H2O vapor. Provided the CaCO3bed depth is maintained, HCl vapor can be scrubbed from the gases exiting the reactor. Conventional calcining of CaCO3can be represented by Reaction 1 which requires a 900° C. or higher temperature. In comparison, the proposed process using hydrolyzed CaCl2) can be imagined to consist of the three steps shown in Reactions 2-4, where Reaction 2 is salt hydrolysis, Reaction 3 is the acidic decomposition of the carbonate, and Reaction 4 is hydroxide formation. Reactions 2 and 3 equate to the thermal decomposition of Reaction 1 and sum to the same theoretical heat of reaction, 178 kJ/mol CO2. However, by incorporating exothermic hydroxide formation, Reaction 4, the overall alternative process has a reduced theoretical energy requirement of 112 kJ/mol CO2. In addition to this 37% reduction in theoretical energy use, the alternative process has the potential to lower the required heat source temperature since Reaction 2 has been shown in the literature to occur at more moderate temperatures of 400° C.-500° C. CaCO3→CaO+CO2(+178 kJ/mol CO2) (Reaction 1) CaCl2+H2O→CaO+2HCl (+113 kJ/mol CO2) (Reaction 2) CaCO3+2HCl→CaCl2)+CO2+H2O (+65 kJ/mol CO2) (Reaction 3) CaO+H2O→Ca(OH)2(−66 kJ/mol CO2) (Reaction 4) Reactor pressure is another parameter for the process. The pressure can be selected in accordance with the temperature to maintain a distinct brine phase and another phase that includes water and the produced acid (e.g., supercritical water, such as above the brine stage), since these are required for the desired separations to take place. At the temperatures under consideration, the low pressure extreme results in solidified chloride salt in an atmosphere of H2O and HCl vapors. At the other extreme where pressure is too high, a dense phase liquid is formed with no distinct separation of hydrolysis products or CO2. In this case CO2separation would be infeasible and the solid carbonate reactant (e.g. CaCO3) and hydroxide product (e.g. Ca(OH)2) would be mixed. Precipitation of the hydroxide on the carbonate may also block complete conversion and decrease the efficiency of sorbent recycling. The reactor operating pressure can also be used to advantage for the production of pressurized CO2that does not require any, or as much, compression for pipeline transport or geologic sequestration. The other streams entering and exiting the reactor are solids (e.g., the carbonate and hydroxide). Conveying these materials through a pressure gradient may pose engineering challenges but since the materials are incompressible, these streams should not require excessive compression energy. Example 1. Regeneration Solution for CO2Direct Air Capture Solvents A laboratory-scale apparatus is used to generate the data necessary to identify the preferred regeneration solution composition from a selected set of brine chemistries, identify effective hydrolysis conditions, and provide a basis for modeling the mass and energy flows with an integrated DAC process. Capture of CO2from the atmosphere using hydroxide-based solvents like KOH and causticizing them to form CaCO3has been demonstrated elsewhere and it is not necessary to include these steps as part of this evaluation. Key processes include hydrolysis of the chloride-based brine to form HCl and precipitated Ca(OH)2, decomposition of CaCO3under hydrolysis temperature and pressure conditions, and recovery of CO2gas. The laboratory apparatus is diagrammed inFIG.6. The apparatus includes a heated tube reactor with provisions for makeup liquid injection and an off-gas conditioning and measurement train. The reactor serves as a vessel for brine hydrolysis and as the reaction chamber for carbonate decomposition by fitting a solids basket above the liquid brine. The tubular reactor is fitted with a reacting solids basket, temperature and pressure transducers, and a vapor extraction probe. An off-gas analysis train is assembled to depressurize the vapors, allow for composition analysis, and totalize gas production. Individual test series can have slight variations in setup and operating protocols depending on their specific objective, but all tests follow the same overall process. Prior to testing, the reactor is loaded with a predetermined quantity and composition of CaCl2) as brine or solid, and for selected cases, CaCO3(without and with impurities). After heating to the test condition, vapor is extracted and its composition and flow rate recorded as a function of time. Condensed vapor samples for subsequent analysis can also be collected. The reactor operates in an open circuit mode; i.e., water vapor that would normally be recycled within the reactor is vented, and as a result, extended tests can require the addition of makeup water using a high-pressure pump. Following cooldown, the reactor is opened, and residual liquid and solid samples are collected for composition and other needed analysis. Testing includes several evaluation stages, eventually leading to semicontinuous tests of the regeneration method. Initial tests to evaluate brine hydrolysis and carbonate decomposition are batch-operated without the addition of material inputs. Parameters including temperature over a range of 300° to 500° C. and brine composition are evaluated for their effect on hydrolysis and HCl formation. Hydrolysis is evaluated by analysis of the off-gas for HCl and the post-test analysis of recovered reactor liquids and precipitated solids. Operating pressure is constrained by temperature and brine composition and is determined for each test. Brine composition has been shown to have an effect on hydrolysis when comparing synthetic versus natural seawater, and is evaluated here in more depth by testing up to five brine chemistries to identify the preferred solution composition. All solutions are chloride-based, and one is aqueous CaCl2. Following the hydrolysis evaluation, carbonate (i.e., CaCO3) decomposition is evaluated at conditions suitable for brine hydrolysis to determine if this process can be incorporated within the hydrolysis reactor for simplified reactant transport and potential energy integration. Off-gas analysis is used to estimate the rate of conversion, and post-test sample recovery is used to determine conversion extent. Testing then advances to longer-duration semicontinuous runs to evaluate mechanisms necessary for successful cycle operation. Key mechanisms include the cycling of HCl and CaCl2, the precipitation and separation of Ca(OH)2, the decomposition of CaCO3in a physical form it is likely to be in after causticization (i.e., precipitated from solution), the extraction of CO2product, and the ability to pass impurity species from other parts of the DAC process (e.g., KOH/K2CO3). This is semicontinuous, where CaCO3solids are charged at the beginning of a run and product Ca(OH)2are recovered after, but CO2product vapors are withdrawn continuously, and makeup brine water is added as needed to sustain operation. Before testing, the reactor is charged with a larger quantity of the target carbonate to allow for longer, semicontinuous evaluation of regeneration cycle processes, including the precipitation and separation of Ca(OH)2, the decomposition of CaCO3in a physical form it is likely to be in after causticization, and extraction of CO2and any associated vapors. Testing can identify a baseline condition that can serve as the basis for high-level process integration modeling. Data collection includes a combination of operational data logging and posttest analysis of recovered samples. Data logging includes reactor temperature(s) and pressure and analysis of the off-gas composition and flow rate. Recovered samples from each test include residual brine liquid, precipitated solids in the brine, and residual solids left in the carbonate loading basket. Liquids undergo analysis for pH and dissolved species determination. Solids are evaluated for their chemical makeup using X-ray fluorescence and, as needed, X-ray diffraction for mineral phase identification and inspection using a scanning electron microscope. The regeneration process is evaluated over a range of temperatures from 300° C. to 500° C. Below this range, hydrolysis diminishes because of reduced HCl vapor pressure, and above it, Ca(OH)2formation is not favored. Operating pressure is constrained by temperature and brine composition and will be determined individually for each test. Using available data, a typical operating pressure is expected to be 6 MPa. Input solids include a target carbonate compound, CaCO3, which is representative of the final capture product for DAC systems utilizing Ca causticization. Initial batch conversion tests use a purchased CaCO3reagent for test-to-test consistency, but the semicontinuous tests use CaCO3precipitated from a simulated causticization process. This precipitated material includes or is spiked with process impurities such as unconverted Ca(OH)2and carryover KOH/K2CO3to determine their fate and demonstrate that a manageable steady state can be achieved. Ambient pollutant impurities, specifically SO2and NOR, are not be evaluated experimentally, but they will be treated using modeling to identify their likely fate and explore management options. Chemical process modeling is used to supplement the results and extrapolate performance for a full-scale DAC. In order to estimate the potential performance of a full-scale DAC system, process modeling software Aspen Plus is used alongside experimental data to produce a complete analysis. The proposed effort is directly relevant to the development of improved DAC systems by addressing a key barrier to commercialization for solvent DAC, i.e., the regeneration energy it requires. Cuts in regeneration energy compared to high-temperature calcination result in fewer emissions that must be offset to achieve net carbon reduction, and lowering the maximum heat source temperature expands the pool of candidate energy sources that can be applied to power large-scale DAC. Even if this approach may not result in the lowest specific separation energy or the lowest regeneration temperature compared to sorbent- or membrane-based approaches, it will still be impactful because of the engineering advantages solvents offer to the design of large-scale air contactors, in particular the ability to decouple CO2capture from regeneration. Therefore, feasible methods to reduce the energy consumption of DAC solvents can be used to implement large-scale air contactors based on solvents in the near term, but the same may not be true for sorbent- or membrane-based systems. Example 1 Supporting Data The process of hydrolyzing CaCl2) to form HCl and Ca(OH)2was investigated experimentally to demonstrate the potential energy savings of brine hydrolysis regeneration over the conventional approach based on high-temperature calcination. The apparatus diagrammed inFIG.6was used to determine the degree of CaCl2) hydrolysis as a function of temperature, and to experimentally determine the standard heat of reaction, which has a theoretical value of +128 kJ/mol CO2as shown in Table 1 for the brine hydrolysis reaction itself. For the experiments, approximately 20 g of hydrated CaCl2) was loaded into the vertical tube reactor ofFIG.6and heated to temperatures over the approximate range of 250° C. to 490° C. Reactor pressure was maintained at approximately 0.1 MPa absolute, and the salt was exposed to a steam atmosphere generated from the vaporization of makeup water pumped into the heated cabinet. Steam flow was maintained by the water makeup pump and equated to a volume flow rate of approximately 3.7 Lpm at the exit conditions of the heated cabinet (i.e., 0.1 MPa and 191° C.). Hydrolysis extent was monitored by condensing the steam atmosphere exiting the reactor cabinet, and measuring condensate pH, which was correlated to HCl concentration. Periodic samples of this condensate were also collected and analyzed for calcium and chloride ions to provide confirmation of its composition. Summary data for the CaCl2) hydrolysis experiments are presented in Table 2 and in the Arrhenius plot ofFIG.7. Within experimental variability, the data clearly show a linear trend with a curve-fit slope of −7683 degrees Kelvin. Given that the slope of an Arrhenius plot is equal to the negative value of activation energy divided by the universal gas constant (8.31451 J/mol/K), the experimentally-determined activation energy was +127.8 kJ/mol Ca (or per mole CO2if discussing the entire regeneration process). This value is virtually identical to the theoretical value of CaCl2brine hydrolysis presented in Table 1, and it provides evidence of the reduced activation energy requirement of this method compared to calcination regeneration. TABLE 2Summary Data from CaCl2Hydrolysis Experiments.ReactorReactorMeasured HClPressure,Temperature,Content in GasMPa Absolute° C.Phase, ppmv0.1253430.12901040.13503100.13513310.13824640.143511400.14875160 Example 2. Energy Estimation for DAC Regeneration Solution The state point data table applicable to various solvent materials is provided in Table 3. The entries for the pure solvent, working solution, and absorption fields in Table 3 are based on a DAC system using KOH capture solvent and Ca causticization as shown inFIG.3. Improvements from using the regeneration solution and brine hydrolysis regeneration appear under the desorption field; these values are estimated based on the minimum-pressure CaCl2hydrolysis condition presented inFIG.2. However, it is important to note that those data were not gathered to optimize HCl production and that a wider range of temperature conditions (300° to 500° C.) and multiple brine compositions are evaluated in Example 1 to optimize DAC system integration. TABLE 3Preliminary state point data table.Measured/EstimatedUnitsPerformancePure SolventaMolecular Weightmol−156.1Normal Boiling PointC.1327°Normal Freezing PointC.405°Vapor Pressure at 15° C.bar0Working SolutionbConcentrationkg/kg0.10Specific Gravity—1.09(15° C./15° C.)Specific Heat Capacity atkJ/kg · K3.88STPViscosity at STPcP1.25Surface Tension at STPdyn/cm76.5CO2Mass Transfer Rate,m/s0.0013[KL]CO2Reaction Rate—75% over 5 sThermal ConductivityW/(m · K)0.616AbsorptionbPressurebar1TemperatureC.15Equilibrium CO2Loadinggmol CO2/kg0.46Heat of AbsorptionkJ/kg CO22180Solution ViscositycP1.25DesorptionPressurebar<50cTemperatureC.300 to 350cEquilibrium CO2Loadinggmol CO2/kg0.002dHeat of DesorptionkJ/kg CO23800 to 5700eaMeasured property data based on KOH as the pure solvent;bReported data based on CO2DAC with a 2M KOH solution;cProjected values from extension of reported data;dProjected loading assuming an optimized CaCO3conversion of 99.5%;eProjected range based on similar low and high heat recuperation assumptions used for solvent DAC analysis. The heat of desorption value in Table 3 represents an approximately 35% energy savings compared to conventional CaCO3calcination. For further comparison, recent analyses for solid DAC sorbents gave a range of 3400 to 4800 kJ/kg CO2for regeneration energy. The corresponding regeneration temperature for that sorbent analysis was assumed to be 67° to 100° C., but many engineering issues need to be overcome to realize the large-scale application of potential. The data presented in Table 3 demonstrates that brine hydrolysis regeneration can combine the desirable CO2capture and system engineering characteristics of solvent DAC with the lower energy input requirements more typical of solid sorbent processes. Example 3. Hydrolytic Softening of Ocean Water for Carbon Dioxide Removal Laboratory testing is used to identify effective hydrolysis conditions and provide a basis for modeling the mass and energy flows for an integrated hydrolytic softening process, as illustrated inFIG.4. Parametric brine hydrolysis testing is performed where data will be generated regarding the extent of hydrolysis conversion at various conditions of temperature, brine composition, and vapor extraction rate. Hydrolytic lime product testing is performed, and favorable hydrolysis conditions identified during the parametric tests are repeated for extended durations to produce larger quantities of the precipitated solids (referred to as hydrolytic lime) for subsequent softening effectiveness testing. The laboratory apparatus is diagrammed inFIG.6; it is based around a high-temperature (1000° C. maximum) vertical tube reactor system. The apparatus includes a heated tube reactor with provisions for makeup liquid injection and an off-gas conditioning and measurement train. For each semi-batch evaluation test, the reactor is loaded with a predetermined quantity and composition of brine. After heating to the test condition, vapor is extracted and its composition and flow rate recorded as a function of time. Composition data is determined using an online Fourier transform infrared gas analyzer that includes a calibration for HCl. The gas is also passed through an absorbing impinger solution to capture the acid gas and allow determination of a total acid quantity. For these tests, the reactor operates in an open circuit mode; i.e., water vapor that would normally be recycled within the reactor will be vented, and as a result, extended tests may require the addition of makeup water using a high-pressure pump. Following cooldown, the reactor is opened, and residual liquid and solid samples are collected for yield determination and composition analysis. Data collection includes a combination of operational data logging and posttest analysis of recovered samples. Data logging includes reactor temperature(s) and pressure and analysis of the off-gas composition and flow rate. Recovered samples from each test include residual brine liquid and precipitated solids in the brine. Liquids undergo analysis for pH and dissolved species determination. Solids are evaluated for their chemical makeup using X-ray fluorescence and, as needed, X-ray diffraction for mineral phase identification and inspection using a scanning electron microscope. Parametric Brine Hydrolysis Testing. Parameters including temperature and brine composition are evaluated for their effect on hydrolysis and HCl formation. Operating pressure is constrained to a feasible range bounded by too little HCl production at high pressure and crystallization of the brine if pressure is too low; this range is a function of temperature and brine composition and is determined for each test. The temperature range evaluated is 300° to 500° C., but the test range is also adapted based on test feedback in order to minimize the needed heat source temperature. Brine composition has an effect on hydrolysis when comparing synthetic versus natural seawater; as a result, pure CaCl2brine along with brine containing Mg, an expected impurity from seawater, are evaluated. Hydrolytic Lime Product Testing. Precipitated solids that form in the hydrolysis reactor represent the material that can be used for seawater softening in a full-scale ocean CO2removal system. Favorable test conditions can be repeated and extended in time by injecting makeup solution to achieve a quasi steady-state condition. These extended runs can be used to produce sufficient quantity of hydrolytic lime product (up to gram-size quantities) for detailed composition analysis and for softening effectiveness tests using synthetic seawater solutions. These latter tests can substantiate the stoichiometry of water softening using base material from brine hydrolysis. The target base material is Ca(OH)2, but could potentially include CaO, CaClOH, and unconverted CaCl2). Hydrolysis data generated is used to validate a process simulation of brine hydrolysis in Aspen Plus; this unit operation model is, in turn, used to develop a complete process for efficiently extracting HCl and Ca(OH)2products. The overall process separates HCl while recycling as much H2O as feasible to avoid wasting energy on excessive water vaporization. Another design consideration for the process is a means to recycle sensible heat between the hot products and incoming brine. In order to estimate the potential performance of a full-scale hydrolytic softening system for seawater, process modeling software Aspen Plus is used alongside experimental data to produce a complete analysis. But the specific energy consumption (i.e., kJ/kg CO2) is difficult to measure accurately an apparatus of this size. For this and other similar scenarios, chemical process models calibrated with measured experimental data is used to estimate the needed parameters. Estimates from techno-economic modeling are used to determine if a $100/ton levelized cost of CO2removal can be met. Example 3 Supporting Data In order to demonstrate the feasibility of applying hydrolytic softening for carbon dioxide removal from the ocean, laboratory experiments were used to measure carbonate precipitation using Ca(OH)2as the softening reagent, and to show the potential for the complete recovery of calcium that is necessary to perpetuate a cycle of regeneration and reuse. These tests used three material streams to simulate the process of carbon dioxide removal from the ocean, 1) artificial seawater, 2) softening reagent solution, and 3) seed particles to serve as nucleation sites for certain tests. Artificial seawater prepared according to ASTM D1141-98 standards (dry solids supplied by Lake Products Company, Florissant, MO), was used as the seawater source. The softening reagent solution was prepared by forming a saturated solution of Ca(OH)2in distilled water. Seed particles were composed of powdered CaCO3having a mean particle diameter of 48 μm. For tests that used seeds, they were added at a nominal loading of 10 g/L, which provided approximately 0.6 m2/L of nucleation surface area. The test procedure consisted of adjusting the pH of each seawater sample using saturated Ca(OH)2solution, adding or withholding seed particles, and agitating the solution for 24 hours of contact time. At the conclusion of 24 hours, each seawater sample was filtered to remove precipitates and the liquid was analyzed for alkalinity, calcium, and magnesium. These data are summarized in Table 4. TABLE 4Summary Data for Seawater Softening Tests.CalculatedRecoveredStartingEndingCO2Ca to CapH AfterAlkalinity,EndingEndingEquivalentAdded asSeedsCa(OH)2mg/L (asCa,Mg,Removal,Ca(OH)2,TestPresentAdditionCaCO3)mg/Lmg/L%mol/mol1No8.2113859313200.0NA2No8.9191.4566132034.32.253No9.4241.7550132073.61.874No9.8442.1531128079.11.965No10.0948.9548124079.81.546No10.1741.7581121082.51.117Yes8.14110565127020.7NA8Yes8.86105570131023.72.069Yes9.2838.7542131073.42.0410Yes9.6139.1557131081.91.5611Yes9.8241.7560130079.41.3912Yes10.0641.2589129083.51.04 Test 1 in Table 4 represents the starting seawater solution and served as the basis to calculate carbon dioxide removal and to determine the amount of recovered calcium. Carbon dioxide removal results are also plotted inFIG.8, and they indicate the potential for high efficiency, up to 73%, at adjusted pH values in the range of 9.0 to 9.5. The corresponding magnesium data in Table 4 confirm that carbon dioxide removal within this pH range occurred before any significant co-precipitation of magnesium hydroxide. Within the pH range of approximately 9.0 to 9.5, the calcium carbonate saturation index (as calcite) approaches a maximum, but supersaturation of the unproductive and competitive precipitant magnesium hydroxide (as brucite) does not occur. This preferred range of pH adjustment for ocean carbon dioxide removal is highlighted inFIG.9, which is a plot of calculated saturation index values for calcite and brucite. One aspect of hydrolytic softening is to operate as a closed cycle without net input of calcium. To make cyclic operation possible, the calcium used for pH adjustment as Ca(OH)2needs to be recovered as CaCO3precipitate, and recycled using the process of brine hydrolysis regeneration. To confirm that cyclic operation is possible, the experimental calcium recovery values from Table 4 are plotted inFIG.10. Over the adjusted pH range of interest for seawater, 9.0 to 9.5, the recovery ratio has a value near two, meaning that nearly double the calcium needed for cyclic operation could potentially be recovered. This calcium recovery excess is an important operating characteristic since it will allow optimization of the precipitation stage in terms of residence time and circulation rate, and will ultimately lead to a lower cost of implementation. Example 4. Economic Analysis of Hydrolytic Softening of Ocean Water for Carbon Dioxide Removal The key advantage offered by the proposed technology is a reduction in the energy cost required for ocean CO2removal. Energy cost savings are achieved by eliminating the need to concentrate brine prior to salt splitting and by incorporating a unique thermochemical approach for splitting. The impact of reduced energy consumption is manifested in the estimated performance metrics summarized in Table 5. TABLE 5Summary of performance metrics.Performance MetricTargetEstimated ValueLevelized Cost of<$100/ton CO2$62/ton of net CO2CO2CaptureremovedSecond-Law Efficiency>10%27%Embodied Emissions<5%0.9%(as % of life cyclecaptured emissions) The second-law efficiency determination was based on the minimum heat of reaction for bicarbonate ion conversion to CO2(HCO3−(aq)→CO2(g)+OH−(aq)), which is +66 kJ/mol CO2at reference conditions. Energy consumption for hydrolytic softening was estimated to include two parts: the sensible energy needed to reach hydrolysis conditions (assumed to be 400° C.) from the reference state and the reaction energy for hydrolysis. Sensible energy consumption was estimated to be +35 kJ/mol CO2using a simple Aspen Plus model of the recuperative heating of a CaCl2) brine from 20° to 400° C. with a 50° C. heat exchanger temperature approach limit. Hydrolysis energy was estimated to be +214 kJ/mol CO2by setting a 60% thermal efficiency target for CaCl2) hydrolysis, Reaction 5 below, which has a theoretical reaction heat of +128 kJ/mol CO2. Combined, these estimates result in a preliminary value of +249 kJ/mol CO2for hydrolytic softening; this compared to the minimum energy for CO2removal at the reference state results in a second-law efficiency estimate of 27%. CaCl2)+2H2O→Ca(OH)2+2HCl (Reaction 5) Embodied emissions were based on a nominal 1-million-ton CO2per year capture facility. An embodied emission factor of 14.6 g CO2/kWhe developed for coal-fired power plants was used to estimate these emissions. The factor was converted to a thermal basis of 3.8 g CO2/kWhth (assuming 45% thermal efficiency and a capacity factor of 1) and scaled for the estimated system firing rate of 163 MWth. The result was an estimate of 5890 tons CO2/yr of embodied emissions for the lifetime of the project (20 years); this value was 0.9% of the estimated net CO2captured for this scenario, or 644,000 tons CO2/year. Techno-Economic Analysis. A preliminary cost model has been developed for a hydrolytic softening process sized for the nominal removal of 1 million tons of CO2from the ocean per year. It was estimated that with the reduced energy requirements of this concept and its use of thermal energy, a cost of $62/ton CO2, appears achievable for ocean CO2removal, significantly below a $100/ton performance target.FIG.11illustrates process flow values used for the techno-economic assessment. Table 6 illustrates the preliminary techno-economic analysis for a hydrolytic ocean CO2removal system with 1 million tons CO2per year nominal capacity. TABLE 6Preliminary Techno-Economic Analysis for a Hydrolytic OceanCO2Removal System with 1 million tons CO2per year Nominal Capacity.ItemBasisEstimated ValueOcean Softening Reservoir$35/m3of estimated retention$110,000,000CapitalvolumeBrine Hydrolysis and Carbonate$840/kWth of estimated heat$137,000,000Decomposition Capitalinput rateSystem Ca(OH)2ConsumptionAssumed 1:1 molar ratio of2.07 × 1010mol/yrCa(OH)2to CO2gas capturedSystem Energy ConsumptionBrine hydrolysis energy163MWthrequired for needed HCl rateassuming 60% thermalefficiencyAnnual Energy CostNatural gas at $3.43/MMBtu$16,700,000/yrNominal CO2Removed fromInput specification1,000,000ton CO2/yrthe OceanAnnual CO2Emissions fromEmissions factor of 227 g356,000ton CO2/yrEnergy ConsumptionCO2/kWth for natural gasNet Annual CO2CaptureDifference between capture644,000ton CO2/yrand energy emissionsLevelized Cost of Net CO2Assumed a 20-year project life,$62/ton CO2Removal7% annual discount rate, andzero end of life value Carbonate removal rate. Determination assumed an incoming concentration of 200 ppm in seawater and a softened concentration of 50 ppm (both values given as CaCO3). This range is typical of conventional softener performance and results in a seawater throughput of nearly 1.6 million m3/hr for a nominal 1 million tons of CO2/year. The net CO2emissions were somewhat lower in Table 6 to account for CO2associated with energy production. Hydrated lime and HCl consumption. Determined from the stoichiometric ratio of 1 mole Ca(OH)2and HCl to separate and release 1 mole of CO2gas. In reality it is likely that closer to 2 moles of CaCO3will precipitate per mole of added Ca(OH)2because of Ca(HCO3)2existing in seawater, but the production of CO2gas will be constrained by HCl availability. Brine hydrolysis energy consumption was estimated using a hydrolysis efficiency target of 60% and a reasonable sensible heat recuperation assumption of 3800 to 5700 kJ/kg CO2. The energy basis for hydrolysis was estimated to be +249 kJ/mol CaCl2. These assumptions resulted in a plant heat input rate of 163 MWth for the 1-million-ton/year CO2removal rate. Power cost was assumed to be dominated by the thermal energy for brine hydrolysis. Natural gas at $3.43/MMBtu and with a carbon intensity of 227 g CO2/kWth was the energy source. To account for the CO2released from gas consumption, these emissions were deducted from the plant's nominal 1-million-ton/year capacity and the resulting cost of CO2removal was normalized on a net CO2removal basis to result in an annual cost of $16,700,000 or roughly $26 per ton of net CO2. Capital cost for solids regeneration. Capital for Steps 2 and 3 inFIG.11was estimated by scaling the costs for a modern supercritical coal-fired power plant, an engineered system perceived to have similarities to the eventual brine hydrolysis process in terms of operating temperatures and pressures and that incorporates a similar variety of unit operations (e.g., large-scale heat generation and heat transfer, emission control, solids collection and transport, and the like). Assumed cost on an electrical output basis was $2100/kWe or $840/kWth on a thermal input basis. Capital cost for ocean softening. Capital for Step 1 inFIG.11is based on what are assumed to be existing analog structures to the floating reservoir envisioned for softening, i.e., floating cages used for large-scale ocean-based aquaculture. The key cost driver for the softener infrastructure is based on the retention time needed for lime mixing and settling of the precipitated carbonates. A typical retention time value of 2 hours was assumed; at the nominal seawater throughput this sizing criteria resulted in a 3.1 million m3enclosed volume capacity. This volume is roughly one order of magnitude larger than the largest aquaculture systems in use today, suggesting that an ocean CO2removal system would require multiple units or the development of larger systems. Costs were assumed using $35/m3of enclosed volume based on a survey of aquaculture cage designs. Part II. Method of Making Syngas Example 5. Hypothetical Integrated Process for Making Carbon-Neutral Offshore Methanol This Part describes a hypothetical integrated process for making carbon-neutral offshore methanol (C-NOM) where the feedstocks of atmospheric CO2and H2O are harvested from the surface layer of the ocean and renewable offshore power drives methanol synthesis. C-NOM is based on integrating 1) electric methanol synthesis (i.e., to produce “e-methanol”) with 2) hydrolytic softening for the direct ocean capture of CO2. Among proposed e-methanol routes, C-NOM is believed to offer significant scaling potential since it largely avoids land- or freshwater-use competition by operating and harvesting feedstock molecules offshore. The integrated C-NOM production process leverages complementary features of hydrolytic softening and e-methanol synthesis to reach an $800/tMeOH production target. Deployment of C-NOM will benefit energy and chemical product decarbonization, while increasing the resilience of local ecosystems and supporting a highly skilled workforce. Objectives of this Phase 1 project are to evaluate the integration of hydrolytic softening and e-methanol synthesis in detail to identify an optimal configuration that results in a $800/tMeOH or lower production cost and to develop the plans necessary for future Phase 2 testing. The team will prepare the conceptual design for an integrated, laboratory-scale C-NOM system; perform preliminary techno-economic and life cycle analyses; prepare a technology maturation plan and technology gap analysis; complete an initial environmental health and safety analysis; and evaluate the societal considerations and impacts of the technology. Description of Proposed Technology and Applicability to Objectives and Success Metrics. The objective of is to produce carbon-neutral methanol using carbon-free hydrogen and atmospheric carbon dioxide provided by direct capture from the atmosphere while targeting a production cost of $800/tMeOH or less. The proposed process for C-NOM aligns with that objective by producing methanol using 1) hydrogen made carbon-free using a combination of low-carbon renewable power input and by sequestering a stream of negative emissions CO2to offset the remaining carbon footprint and 2) atmospheric CO2absorbed in the surface layer of the ocean and removed using a direct ocean capture (DOC) process. C-NOM is predicted to reach the $800/tMeOH production target by integrating the material and energy needs of e-methanol synthesis with hydrolytic softening DOC. Process Description and Chemistry. A process diagram for C-NOM is presented inFIG.12with the reactions for each process step summarized in Table 7. C-NOM production begins with the precipitation softening of seawater, where absorbed atmospheric CO2, present primarily as bicarbonate in the ocean (—HCO3), is captured as calcium carbonate (CaCO3) from the addition of hydrated lime (Ca[OH]2). This step removes CO2(as bicarbonate) from the water and replaces it with hydroxide ion (—OH) which primes the seawater to reabsorb more atmospheric CO2. The next steps inFIG.12are hydrolytic lime regeneration and carbonate dissolution. In lime regeneration, calcium chloride (CaCl2)) produced within the carbonate dissolution step is hydrolyzed at 500° C. to form hydrochloric acid (HCl) and dissolved calcium hydroxide. The latter product is used for precipitation softening while the hydrochloric acid is used in the carbonate dissolution step to dissolve the calcium carbonate precipitates, releasing CO2gas and forming the intermediate neutralization salt, calcium chloride. Dissolution releases CO2gas in an atmosphere of water vapor that is evaporated from excess seawater carried in with the precipitates. This mixed CO2and H2O gas stream is used directly in the next step, regenerative fuel cell (RFC) coelectrolysis, where gas-phase electrolysis of both H2O and CO2produces a chemical synthesis gas consisting of H2and CO. These synthesis gas constituents are the feedstock molecules needed for the final step of catalytic methanol synthesis. TABLE 7Process Chemistry for C-NOM Production.StepGoverning ReactionPrecipitation Softening—HCO3+ Ca(OH)2→ CaCO3+ H2O + —OHHydrolytic LimeCaCl2+ 2H2O → Ca(OH)2+ 2HClRegenerationCarbonate DissolutionCaCO3+ 2HCl → CaCl2+ H2O + CO2Regenerative Fuel CellCO2+ H2O → CO + 2H2+ O2CoelectrolysisMethanol SynthesisCO + 2H2→ CH3OH The overall process shown inFIG.12can be powered by a combination of 500° C. heat and electricity, or electricity alone by electrifying the heat demand of hydrolytic lime regeneration. Power generation introduces a source of upstream CO2emissions, and to offset them, the hydrolytic softening process is sized to collect an excess of CO2that is compressed and sent for geologic sequestration. An illustrative implementation of C-NOM is shown inFIG.13where the first step of precipitation softening takes place inside a neutrally buoyant softening enclosure floating in the water column. This structure would allow for contacting large volumes of seawater while retaining calcium carbonate precipitates that sink to the bottom. The remaining process steps of hydrolytic lime regeneration and e-methanol synthesis would take place at the surface on a floating or fixed platform. Hydrolytic Softening. Hydrolytic softening is described herein at Part I. Experimental results included measuring the reaction heat of CaCl2hydrolysis, confirming the composition of the hydrolysis products, and demonstrating the effectiveness of hydrolytic lime for seawater softening. Experimental data from Part I have been used to develop a process model for hydrolytic softening, which was used to extrapolate the mass and energy balance of C-NOM shown inFIG.13. Hydrolytic lime regeneration inFIGS.12and13is differentiated from the common practice of producing hydrated lime through high-temperature calcination of calcium carbonate at ˜900° C., followed by slaking of the calcium oxide (CaO) with water. The key difference between hydrolytic lime regeneration and conventional calcination/slaking is that CaCl2hydrolysis yields hydrated lime directly, instead of the calcium oxide intermediary formed during calcination. This eliminates the need for slaking and saves energy by reducing the quantity of 500° C. heat by 28% compared to the amount of 900° C. heat required during calcination, i.e., 128 kJ/mol Ca(OH)2for the former versus 179 kJ/mol for the latter. e-Methanol Synthesis. The next C-NOM process step is coelectrolysis of the CO2and H2O vapor stream from carbonate dissolution to produce a synthesis gas mixture of CO and H2at the proper H2:CO ratio for methanol synthesis (2:1). The RFC is a solid oxide electrolyzer that operates at 700° to 800° C., and it offers key benefits for this application, including 1) high conversion efficiency for electricity to synthesis gas (>80%), 2) low-cost ceramic materials as catalysts, and 3) reliable operation up to 6000 hours or more. Steam production is commonly a cost-prohibitive step for applying RFC technology since it uses gas-phase steam electrolysis. However, in this application, excess ocean water is evaporated during the hydrolysis and dissolution steps of hydrolytic softening which effectively integrates the energy burden of raising steam into the overall process, making RFC a complementary fit. The final step of catalytic methanol synthesis is the most technically mature of the three key processes proposed for C-NOM. High-selectivity Cu—Zn catalysts have been developed, and the life cycle costs of their use are well understood. Additionally, reactor designs have been developed that allow efficient recovery of the exothermic heat of reaction in the form of 200°-250° C. steam that will be used to thermally integrate methanol synthesis with hydrolytic lime regeneration as shown inFIG.12. Potential Advantages. Utilization of hybrid systems for generating carbon free hydrogen with improved long-term stability. The C-NOM approach is based on high-efficiency RFC technology that has been demonstrated for extended operating periods. Consolidation of process operations to achieve reductions in cost. The preliminary techno-economic analysis (TEA) predicts C-NOM to reach the $800/tMeOH production target, partly by consolidating H2O electrolysis and CO2reduction into a single, high-efficiency step. Reduction of auxiliary power by utilizing process schemes that allow heat integration. Each step of the C-NOM process has complementary thermal energy requirements with the key opportunity for thermal energy recovery being between the exothermic process of methanol synthesis and the endothermic process of hydrolytic lime regeneration. Preliminary Conceptual Design of the Laboratory Validation System. Under a future Phase 2 project, an integrated system for C-NOM production will be designed and operated at laboratory scale, including all steps shown inFIG.12with the exception of CO2compression. It is anticipated that the scale of the system will be based on a methanol production rate of ˜1 tMeOH/yr or roughly 170 kg of methanol during the 2-month validation test. This production rate is 0.1% of the heat and mass balance values shown inFIG.13, implying a 1 to 2 kWe RFC stack will be needed along with a seawater circulation rate of ˜9 t/hr or 40 gpm. State point data table values for the preliminary conceptual design are included as one of the scenarios in Table 10. A system of this scale can be used to demonstrate CO2capture and conversion to methanol; however, validating thermal efficiency claims will be challenging. As an alternative, it is proposed to limit experimental validation to conversion rates, extended term performance, and measured energy requirements, but then evaluate thermal efficiency with complementary process modeling using Aspen Plus or a similar modeling tool. Technology Competitive Assessment. Two pathways are available for producing carbon-neutral methanol: 1) converting biomass feedstocks into bio-methanol and 2) creating e-methanol using negative emission CO2and supplying energy from low-carbon power sources. Most carbon-neutral methanol produced today is bio-methanol, and the technology could be considered mature. As with other biomass-based energy sources, the maximum potential of bio-methanol is limited by the cost, availability, and distribution of feedstocks (e.g., municipal, agricultural, or forest wastes) and by competition for the resources needed to produce them (e.g., arable land and water). Without breakthroughs in the production of convertible biomass like, perhaps, offshore algae farming, this route to carbon-neutral methanol will face fundamental limitations to the amount of fossil methanol it could displace. E-methanol routes, on the other hand, can potentially avoid some of the fundamental limitations faced by bio-methanol production to result in greater displacement of fossil methanol. Among the e-methanol routes, C-NOM is believed to offer significant scaling potential since it largely avoids land- or water-use competition. Water use is a criticism of direct air capture plants since the processes can lose moisture to the atmosphere under dry conditions. In addition, methanol synthesis is a water consumer since each metric ton of methanol requires 1.4 tCO2and 1.1 tH2O. C-NOM negates water as a constraint since H2O is harvested along with the precipitates of calcium carbonate from the ocean. Relevance of the Proposed Technology. The C-NOM process is an integrated process that harvests carbon-neutral CO2and uses it to synthesize methanol with carbon-free hydrogen. The experimental data in Part I shows the concept for CO2capture to be technically viable. The oceans represent a mostly untapped resource for renewable power generation, and C-NOM can be a complementary fit to concentrate, store, and economically transport that energy to shore. Adequacy of the Preliminary TEA and LCA to Meet Objectives. Preliminary mass and energy balance values for a reference plant size of 1000 tMeOH/yr are presented inFIG.13. These estimates are based on 1) experimentally based process modeling of hydrolytic softening from Part I; 2) RFC performance on advertised specifications; and 3) methanol synthesis performance from selected references on small-scale, syngas-based methanol from biomass and stranded natural gas resources. Preliminary TEA results are shown in Table 8 along with calculation assumptions. As shown, the more carbon intense national grid scenario results in increased costs associated with offsetting energy emissions and hydrolytic softening plant size. As a result, production costs for the national grid scenario were higher than the $800/tMeOH target for both required power cost assumptions. However, the reduced carbon intensity of renewable power resulted in a lower power input and a smaller hydrolytic softening unit, leading to production values that reach the target. TABLE 8Preliminary TEA Results for 1000-tMeOH/yr C-NOM Reference Plant.National GridRenewable PowerCarbon Intensity,Carbon Intensity,CalculationTEA Parameter450 kg CO2e/MWh23 kg/CO2e/MWhAssumptionsLevelized Inputs, $/tMeOHTotal Input Energy$746 to $1344$282 to $507Combined thermal andBasis, MWe($25 to $45/MWh)($25 to $45/MWh)electrical powerrequirements assuming85% plant capacityfactorSequestration Charge$133$3Assumed $10/tCO2for Negative EmissionsCO2Hydrolytic Softening$676$75$650/tCO2/yr capacity,Capital*based on TEA modelingunder previous ARPA-EprojectRFC Capital*$190$190$2300/kW of inputpowerMethanol Synthesis$78$78$1100/tMeOH/yr forCapital*small-scale productionFixed Operations and$333$1212.5% of total capital perMaintenanceyearLevelized Outputs, $/tMeOHPreliminary Levelized$2750$974$45/MWh power cost,Cost of C-NOMDOE cost target forProduction, $/tMeOHfloating offshore wind$2160$748$25/MWh power cost,cost today for optimallysited wind resources*First-year capital charges determined using a 0.071 capital recovery factor that assumed a 25-year life at 5% discount rate. Complementary to the preliminary TEA, results of a preliminary cradle-to-gate life cycle analysis (LCA) for the mass and energy streams of C-NOM are summarized in Table 9. Both scenarios in Table 9 produce the same quantity of carbon-neutral MeOH product, and as the carbon intensity of the energy source decreases from left to right, so does the input power requirement and the magnitude of the CO2sequestration stream. TABLE 9Preliminary LCA Results for 1000-tMeOH/yr C-NOM Reference Plant.Combined HeatCombined Heatand Electricityand Electricityfrom Nationalfrom Renewables,Grid, 450 kg23 kgUnitsCO2e/MWhCO2e/MWhMethanol ProductiontMeOH/yr10001000Total Power InputMW3.961.46CO2e in MethanoltCO2e/yr13701370Total Power EmissionstCO2e/yr13,300250Negative CO2UptaketCO2/yr14,6001620CO2to SequestrationtCO2/yr13,300250 Thoroughness and Completeness of the State Point Data Table. Preliminary state point data tables have been completed for the carbon capture process in Table 10 and the conversion of CO2to methanol in Table 11. Table 10 compares three system sizes, the first is based on the measured performance of the small laboratory proof-of-concept testing for hydrolytic lime regeneration from Part I. The other two scenarios are estimates for continuous processes scaled up to the planned size of the Phase 2 laboratory validation system and a full-scale 1000-tMeOH/yr system. Calculation notes for Table 10 include the following items: Scale. Measured value based on laboratory-scale, hydrolysis proof-of-concept reactor with an equivalent capacity of roughly 0.6 g/hr of CO2. Projected performance range based on the capacity needed to produce 1 t/yr (validation scale) and 1000 t/yr (full-scale) of carbon-neutral methanol assuming both low carbon (23 kg CO2e/MWh) and high carbon (450 kg CO2e/MWh) energy. Total Thermal Energy Requirements. Measured performance is based on the measured reaction heat of 128 kJ/mol CO2. Projected heat values includes estimates for the sensible heat loss in a continuous system. Required Temperature of Thermal Energy. Measured value range based on experiments; projected performance assumes operation at the maximum end of the range. Total Electricity Energy Requirements. Electrical energy measurements were not meaningful at the scale of the proof-of-concept tests. Proposed electrical use is based on a process model developed for hydrolytic softening. Volumetric Productivity. Values were based on the quantity of CO2removed per unit volume of seawater for the duration of the softener residence time. Measured value represents maximum capture at a long residence time while the projected values are based on optimal throughput, i.e., less capture efficiency but shorter residence time. Carbon Capture Efficiency. Efficiency was determined by comparing the measured quantity of CO2precipitated as carbonate from seawater to the total amount of CO2in seawater as either carbonate or bicarbonate ions. The measured lab-scale trend was used as the basis for both the measured and the projected values. Pressure Drop. Estimate to flow the desired quantity of seawater through a full-scale softening vessel. This value was not applicable to the laboratory system since it was a batch operation. CO2Storage Option. This parameter is only relevant to the full-scale projected performance where geologic sequestration was assumed. Distance to CO2Storage Option. This parameter is only relevant to the full-scale projected performance where it was assumed that initial deployments of the technology would take place on repurposed oil and gas platforms proximate to a sequestration well. TABLE 10State Point Data for CO2Capture System.ProjectedProjectedMeasuredPhase 2Full-Proof ofLaboratoryScaleUnitsConceptValidationPerformanceOverall ProcessScaletonne0.0051.6 to 151620 to 14,600CO2(net)/yearTotal ThermalGJ/tonne2.933.063.06EnergyCO2(net)RequirementsRequired° C.475-500500500Temperature ofThermal EnergyTotal ElectricityGJ/tonneNA2.092.09EnergyCO2(net)RequirementsVolumetricgmol2.35.95.9ProductivityCO2(net)/m3capturemedia/hrCarbon Capture%76%50%50%Efficiency (singlepass)Pressure DropPaNA104,000104,000Proposed/estimatedCO2Storage Option—NANAGeologicsequestrationDistance to CO2milesNANAWithin 10-mileStorage Optionradius TABLE 11SPDT for Methanol Synthesis Portion of C-NOM.Measured/CurrentProjected/TargetUnitsPerformancePerformanceSynthesis PathwayStepsStep 1mol−1CO2+ 2H2O = CO + 2H2+ 1.5O2Step 2mol−1CO + 2H2= CH3OHReactionThermodynamicsReactionStep 1: electrochemicalStep 2: thermochemicalΔH0rxnkJ/molStep 1: +767 CO2Step 2: −90.7 CH3OHΔG0rxnkJ/molStep 1: +714 CO2Step 2: −24.3 CH3OHConditionsCO2SourceBiomass feedstockAtmospheric CO2for bio-methanoltaken from the oceanCatalystStep 2: Cu—ZnStep 2: Cu—ZnPressurebarStep 1: 1Step 1: 1Step 2: ~55Step 2: ~55CO2Partial PressurebarStep 1: ~0.33Step 1: ~0.33Step 2: ~6Step 2: ~6Temperature° C.Step 1: ~750-850Step 1: ~750-850Step 2: ~230-300Step 2: ~230-300PerformanceNominal Residencesec<1<1TimeSelectivity to Desired%99.599.5ProductProduct CompositionDesired Productmol %CH3OHCH3OHUnwanted By-mol %H2OH2OProduct The state point data table (SPDT) for the production of value-added methanol from captured CO2is presented in Table 11. Measured and projected values are based on literature sources for the individual processes of RFC coelectrolysis and methanol synthesis. The results are similar since advancements within the process steps are not targeted; instead, the novelty of the proposed project is in integrating these processes together with negative emission CO2. Quality and Completeness of the Market Assessment and CO2Mitigation Potential. Methanol is in many ways an ideal energy carrier to integrate with existing U.S. infrastructure since it is already a widely produced chemical with an established market that includes major uses as a fuel and chemical feedstock. The existing U.S. market size for methanol is over 8 Mt MeOH/yr, and between 2020 and 2022, prices ranged from $400 to $660/t MeOH. TEA projections of ˜$800/tMeOH production cost for C-NOM is above the recent commodity price range; however, C-NOM would sell at a premium since it would qualify for renewable credits and other carbon-free incentives and mandates. Growth in the North American renewable methanol market is estimated to have a CAGR (compound annual growth rate) of between 4% and 8%. Most renewable methanol today is derived from biomass sources, which are anticipated to face constraints in resource availability that will drive demand for noncompetitive methanol production routes like the proposed C-NOM concept. Transportation costs for C-NOM will impact the revenue potential of the product, but existing transport networks in the Gulf of Mexico region can be leveraged for efficient methanol transport to this market, which is 65% of the U.S. total. C-NOM development off either the U.S. West or East Coasts may not have equivalent infrastructure to leverage, but these locations could be uniquely positioned to service important export markets. For instance, the majority of the world's methanol production is consumed in southeast Asia, and carbon-neutral fuel incentives are currently driving demand in the EU. Beyond exports, offshore production might also serve the growing demand for carbon-neutral transportation fuel in the shipping industry, a goal of the U.S.-Norway Green Shipping Challenge announced at COP 27 on Nov. 7, 2022. Each metric ton of fossil-based methanol displaced by carbon-neutral methanol would prevent not only the direct emission of 1.37 tCO2from methanol combustion, but also another ˜1.9 tCO2e from producing 1 metric ton of methanol from natural gas, currently the dominant method of production in the U.S. Therefore, each GW of offshore wind production dedicated to methanol production could result in approximately 0.44 Mt MeOH/yr (assuming 55% annual wind capacity factor) or nearly 5% of current (2020) U.S. conventional methanol production capacity to avert nearly 1.4 MtCO2e in associated emissions. For context, the U.S. Bureau of Ocean Energy Management recently estimated the technical potential for offshore wind power in the Gulf of Mexico to be over 500 GW. Degree that Captured CO2is Utilized in the Product. Results of the preliminary LCA have been used to evaluate the carbon flows predicted for C-NOM, and Table 12 is a results summary. Like the preliminary LCA, carbon utilization increases as the amount of energy-related emissions decrease from left to right. TABLE 12Carbon Flow Summaries for Various Energy Sources.Combined HeatCombined Heatand Electricityand Electricityfrom National Grid,from Renewables,450 kg CO2e/MWh23 kg CO2e/MWhTotal C Uptake100%100%C to Sequestration91%15%C to Methanol9%85% The terms and expressions that have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the aspects of the present invention. Thus, it should be understood that although the present invention has been specifically disclosed by specific aspects and optional features, modification and variation of the concepts herein disclosed may be resorted to by those of ordinary skill in the art, and that such modifications and variations are considered to be within the scope of aspects of the present invention. Exemplary Aspects. The following exemplary aspects are provided, the numbering of which is not to be construed as designating levels of importance: Aspect 1 provides a method of forming a syngas composition, the method comprising:hydrolyzing a metal halide salt to form a hydrohalic acid and a hydroxide salt of the metal in the metal halide salt, the metal comprising an alkaline earth metal or an alkali metal;reacting the hydrohalic acid with a metal carbonate salt, wherein the metal carbonate salt is a carbonate salt of the alkaline earth metal or alkali metal, to form CO2, water, and the metal halide salt, wherein at least some of the metal halide salt formed from the reacting of the hydrohalic acid with the metal carbonate salt is recycled as at least some of the metal halide salt in the hydrolyzing of the metal halide salt to form the hydrohalic acid and the hydroxide salt; andelectrolytically converting the CO2and the water into the syngas composition comprising carbon monoxide and hydrogen. Aspect 2 provides the method of Aspect 1, wherein the metal carbonate salt is BeCO3, MgCO3, CaCO3, SrCO3, BaCO3, RaCO3, Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, Fr2CO3, or a combination thereof. Aspect 3 provides the method of any one of Aspects 1-2, wherein the metal carbonate salt is CaCO3, MgCO3, or a combination thereof. Aspect 4 provides the method of any one of Aspects 1-3, wherein the metal carbonate salt is CaCO3. Aspect 5 provides the method of Aspect 4, wherein the CaCO3is produced from a CO2-capture sorbent, is a CaCO3precipitate formed from water softening, is natural limestone, or a combination thereof. Aspect 6 provides the method of any one of Aspects 1-5, wherein the alkaline earth metal or alkali metal is beryllium, magnesium, calcium, strontium, barium, radium, lithium, sodium, potassium, rubidium, cesium, francium, or a combination thereof. Aspect 7 provides the method of any one of Aspects 1-6, wherein the alkaline earth metal or alkali metal is magnesium, calcium, or a combination thereof. Aspect 8 provides the method of any one of Aspects 1-7, wherein the alkaline earth metal or alkali metal is calcium. Aspect 9 provides the method of any one of Aspects 1-8, wherein the metal halide salt is a beryllium halide salt, a magnesium halide salt, a calcium halide salt, a strontium halide salt, a barium halide salt, a radium halide salt, a lithium halide salt, a sodium halide salt, a potassium halide salt, a rubidium halide salt, a cesium halide salt, a francium halide salt, or a combination thereof. Aspect 10 provides the method of any one of Aspects 1-9, wherein the metal halide salt is beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, radium chloride, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, francium chloride, or a combination thereof. Aspect 11 provides the method of any one of Aspects 1-10, wherein the metal halide salt is CaCl2), MgCl2, or a combination thereof. Aspect 12 provides the method of any one of Aspects 1-11, wherein the metal halide salt is CaCl2). Aspect 13 provides the method of any one of Aspects 1-12, wherein the hydrohalic acid is HCl, HBr, HI, HF, or a combination thereof. Aspect 14 provides the method of any one of Aspects 1-13, wherein the hydrohalic acid is HCl. Aspect 15 provides the method of any one of Aspects 1-14, wherein the hydroxide salt is Be(OH)2, Mg(OH)2, Ca(OH)2, Sr(OH)2, Ba(OH)2, Ra(OH)2, LiOH, NaOH, KOH, RbOH, CsOH, FrOH, or a combination thereof. Aspect 16 provides the method of any one of Aspects 1-15, wherein the hydroxide salt is Ca(OH)2, Mg(OH)2, or a combination thereof. Aspect 17 provides the method of any one of Aspects 1-16, wherein the hydroxide salt is Ca(OH)2. Aspect 18 provides the method of any one of Aspects 1-17, whereinthe metal carbonate salt is CaCO3,the alkaline earth metal or alkali metal is calcium,the metal halide salt is CaCl2),the hydrohalic acid is HCl, andthe hydroxide salt is Ca(OH)2. Aspect 19 provides the method of any one of Aspects 1-18, wherein the hydrolyzing of the metal halide salt is performed at a pressure of 0.1 MPa-100 MPa. Aspect 20 provides the method of any one of Aspects 1-19, wherein the hydrolyzing of the metal halide salt is performed at a pressure of 3 MPa to 9 MPa. Aspect 21 provides the method of any one of Aspects 1-20, wherein the hydrolyzing of the metal halide salt is performed at a pressure of 5-7 MPa. Aspect 22 provides the method of any one of Aspects 1-21, wherein the hydrolyzing of the metal halide salt is performed at a temperature of room temperature to 1000° C. Aspect 23 provides the method of any one of Aspects 1-22, wherein the hydrolyzing of the metal halide salt is performed at a temperature of 300° C. to 500° C. Aspect 24 provides the method of any one of Aspects 1-23, wherein the hydrolyzing of the metal halide salt is performed at a temperature of 350° C. to 450° C. Aspect 25 provides the method of any one of Aspects 1-24, wherein the hydrolyzing of the metal halide salt produces the hydrohalic acid at a molar content of 0.01% to 10%. Aspect 26 provides the method of any one of Aspects 1-25, wherein the hydrolyzing of the metal halide salt produces the hydrohalic acid at a molar content of 0.1% to 1%. Aspect 27 provides the method of any one of Aspects 1-26, wherein the reacting of the hydrohalic acid with the metal carbonate salt is performed at a pressure of 0.1 MPa-100 MPa. Aspect 28 provides the method of any one of Aspects 1-27, wherein the reacting of the hydrohalic acid with the metal carbonate salt is performed at a pressure of 3 MPa to 9 MPa. Aspect 29 provides the method of any one of Aspects 1-28, wherein the reacting of the hydrohalic acid with the metal carbonate salt is performed at a temperature of room temperature to 500° C. Aspect 30 provides the method of any one of Aspects 1-29, wherein the reacting of the hydrohalic acid with the metal carbonate salt is performed at a temperature of 350° C. to 450° C. Aspect 31 provides the method of any one of Aspects 1-30, wherein the metal halide salt formed from the reacting of the hydrohalic acid with the metal carbonate salt is 0.001 wt % to 100 wt % of the metal halide salt used in the hydrolyzing of the metal halide salt to form the hydrohalic acid and the hydroxide salt. Aspect 32 provides the method of any one of Aspects 1-31, wherein the metal halide salt formed from the reacting of the hydrohalic acid with the metal carbonate salt is 80 wt % to 100 wt % of the metal halide salt used in the hydrolyzing of the metal halide salt to form the hydrohalic acid and the hydroxide salt. Aspect 33 provides the method of any one of Aspects 1-32, wherein the hydrolyzing of the metal halide salt and the reacting of the hydrohalic acid with the metal carbonate salt is performed together in a pressurized reactor. Aspect 34 provides the method of any one of Aspects 1-33, further comprising reacting a used CO2-capture sorbent with the hydroxide salt to provide the metal carbonate salt that is a carbonate salt of the metal in the metal halide salt. Aspect 35 provides the method of Aspect 34, wherein the used CO2-capture sorbent is a used hydroxide-based, ammonia-based, and/or amine-based CO2-capture sorbent. Aspect 36 provides the method of any one of Aspects 34-35, wherein the used CO2-capture sorbent is derived from sorption of CO2by a hydroxide-based, ammonia-based, and/or amine-based CO2-capture sorbent. Aspect 37 provides the method of any one of Aspects 34-36, wherein the CO2-capture sorbent is a used hydroxide-based CO2-capture sorbent. Aspect 38 provides the method of any one of Aspects 34-37, wherein the used CO2-capture sorbent is Ca(HCO3)2, Mg(HCO3)2, K2CO3, Na2CO3, or a combination thereof. Aspect 39 provides the method of any one of Aspects 34-38, wherein the reacting of the used CO2-capture sorbent with the hydroxide salt to provide the metal carbonate salt is performed at a pressure of 0.01 MPa to 10 MPa. Aspect 40 provides the method of any one of Aspects 34-39, wherein the reacting of the used CO2-capture sorbent with the hydroxide salt to provide the metal carbonate salt is performed at a pressure of about 0.05 MPa to 0.2 MPa. Aspect 41 provides the method of any one of Aspects 34-40, wherein the reacting of the used CO2-capture sorbent with the hydroxide salt to provide the metal carbonate salt is performed at a temperature of room temperature to 350° C. Aspect 42 provides the method of any one of Aspects 34-41, wherein the reacting of the used CO2-capture sorbent with the hydroxide salt to provide the metal carbonate salt is performed at a temperature of 50° C. to 150° C. Aspect 43 provides the method of any one of Aspects 34-42, further comprising contacting a CO2-capture sorbent with CO2to form the used CO2-capture sorbent. Aspect 44 provides the method of any one of Aspects 34-43, further comprising contacting Ca(OH)2, Mg(OH)2, KOH, and/or NaOH with CO2to form the used CO2-capture sorbent. Aspect 45 provides the method of any one of Aspects 34-44, wherein the reacting of the used CO2-capture sorbent with the hydroxide salt to form the metal carbonate salt also forms an unused CO2-capture sorbent. Aspect 46 provides the method of Aspect 45, wherein the unused CO2-capture sorbent is Ca(OH)2, Mg(OH)2, KOH, and/or NaOH. Aspect 47 provides the method of any one of Aspects 45-46, wherein the unused CO2-capture sorbent is KOH and/or NaOH. Aspect 48 provides the method of any one of Aspects 45-47, further comprising providing the unused CO2-capture sorbent for CO2capture. Aspect 49 provides the method of any one of Aspects 34-48, wherein at least some of the hydroxide salt of the metal formed in the hydrolysis of the metal halide salt to form the hydrohalic acid and the hydroxide salt is recycled as at least some of the hydroxide salt used in the reacting of the used CO2-capture sorbent with the hydroxide salt. Aspect 50 provides the method of Aspect 49, wherein the hydroxide salt of the metal formed in the hydrolysis of the metal halide salt is 0.001 wt % to 100 wt % of the hydroxide salt used in the reacting of the used CO2-capture sorbent with the hydroxide salt. Aspect 51 provides the method of any one of Aspects 49-50, wherein the hydroxide salt of the metal formed in the hydrolysis of the metal halide salt is 80 wt % to 100 wt % of the hydroxide salt used in the reacting of the used CO2-capture sorbent with the hydroxide salt. Aspect 52 provides the method of any one of Aspects 1-51, further comprising reacting NaHCO3, Mg(HCO3)2, Ca(HCO3)2, KHCO3, or a combination thereof, with the hydroxide salt to provide the metal carbonate salt that is a carbonate salt of the metal in the metal halide salt. Aspect 53 provides the method of Aspect 52, wherein the method is a method of softening water. Aspect 54 provides the method of any one of Aspects 1-53, further comprising reacting a bicarbonate salt from a natural water source, wherein the bicarbonate salt is NaHCO3, Mg(HCO3)2, Ca(HCO3)2, KHCO3, or a combination thereof, with the hydroxide salt to provide the metal carbonate salt. Aspect 55 provides the method of Aspect 54, wherein the natural water source comprises salt water, ocean water, brackish water, fresh water, a stream, a pond, a lake, a river, or a combination thereof. Aspect 56 provides the method of any one of Aspects 54-55, wherein the bicarbonate salt is Ca(HCO3)2. Aspect 57 provides the method of any one of Aspects 54-56, wherein at least some of the hydroxide salt of the metal formed in the hydrolysis of the metal halide salt to form the hydrohalic acid and the hydroxide salt is recycled as at least some of the hydroxide salt used in the reacting of the bicarbonate salt with the hydroxide salt. Aspect 58 provides the method of Aspect 57, wherein the hydroxide salt of the metal formed in the hydrolysis of the metal halide salt is 0.001 wt % to 100 wt % of the hydroxide salt used in the reacting of the bicarbonate salt with the hydroxide salt. Aspect 59 provides the method of any one of Aspects 57-58, wherein the hydroxide salt of the metal formed in the hydrolysis of the metal halide salt is 80 wt % to 100 wt % of the hydroxide salt used in the reacting of the bicarbonate salt with the hydroxide salt. Aspect 60 provides the method of any one of Aspects 1-59, wherein the water formed during the reacting of the hydrohalic acid comprises gaseous water. Aspect 61 provides the method of any one of Aspects 1-60, wherein the water formed during the reacting of the hydrohalic acid has a temperature of 100° C. to 500° C. Aspect 62 provides the method of any one of Aspects 1-61, wherein the water formed during the reacting of the hydrohalic acid has a temperature of 100° C. to 150° C. Aspect 63 provides the method of any one of Aspects 1-62, wherein 50-100 wt % of the water formed during the reacting of the hydrohalic acid is gaseous water. Aspect 64 provides the method of any one of Aspects 1-63, wherein 90-100 wt % of the water formed during the reacting of the hydrohalic acid is gaseous water. Aspect 65 provides the method of any one of Aspects 1-64, wherein the electrolytic conversion of the CO2and the water into the syngas composition converts 50% to 100% of the CO2. Aspect 66 provides the method of any one of Aspects 1-65, wherein the electrolytic conversion of the CO2and the water into the syngas composition converts 90% to 100% of the CO2. Aspect 67 provides the method of any one of Aspects 1-66, wherein the electrolytic conversion of the CO2and the water into the syngas composition converts 50% to 100% of the water. Aspect 68 provides the method of any one of Aspects 1-67, wherein the electrolytic conversion of the CO2and the water into the syngas composition converts 90% to 100% of the water. Aspect 69 provides the method of any one of Aspects 1-68, wherein carbon monoxide is 15 mol % to 40 mol % of the syngas composition. Aspect 70 provides the method of any one of Aspects 1-69, wherein carbon monoxide is 30 mol % to 36 mol % of the syngas composition. Aspect 71 provides the method of any one of Aspects 1-70, wherein hydrogen is 30 mol % to 80 mol % of the syngas composition. Aspect 72 provides the method of any one of Aspects 1-71, wherein hydrogen is 60 mol % to 75 mol % of the syngas composition. Aspect 73 provides the method of any one of Aspects 1-72, wherein the syngas composition has a molar ratio of hydrogen to carbon monoxide of 1:1 to 3.5:1. Aspect 74 provides the method of any one of Aspects 1-73, wherein the syngas composition has a molar ratio of hydrogen to carbon monoxide of 1.9:1 to 2.1:1. Aspect 75 provides the method of any one of Aspects 1-74, wherein the syngas composition has a concentration of CO2of 0 mol % to 20 mol %. Aspect 76 provides the method of any one of Aspects 1-75, wherein the syngas composition has a concentration of CO2of 0 mol % to 5 mol %. Aspect 77 provides the method of any one of Aspects 1-76, wherein the syngas composition has a concentration of water of 0 mol % to 33 mol %. Aspect 78 provides the method of any one of Aspects 1-77, wherein the syngas composition has a concentration of water of 0 mol % to 10 mol %. Aspect 79 provides the method of any one of Aspects 1-78, wherein the electrolytically converting the CO2and the water into the syngas composition comprises placing the CO2and/or the water into contact with an electrolytic cell. Aspect 80 provides the method of Aspect 79, wherein the electrolytic cell comprises a reverse fuel cell, a solid oxide electrolysis cell or a molten carbonate electrolysis cell. Aspect 81 provides the method of any one of Aspects 79-80, wherein the electrolytic cell comprises a solid oxide electrolysis cell. Aspect 82 provides the method of Aspect 81, wherein the electrolytic cell comprises an anode, cathode, and an electrolyte, wherein at least one of the anode, cathode, and the electrolyte comprises yttria-stabilized zirconia (YSZ). Aspect 83 provides the method of any one of Aspects 81-82, wherein the electrolytic cell comprises a cathode comprising Ni. Aspect 84 provides the method of any one of Aspects 81-83, wherein the electrolytic cell comprises an anode comprising lithium strontium manganite (LSM). Aspect 85 provides the method of any one of Aspects 81-84, wherein the electrolytic cell comprises an electrolyte comprising yttria-stabilized zirconia (YSZ), a cathode comprising Ni-YSZ, and an anode comprising lithium strontium manganite (LSM)-YSZ cathode. Aspect 86 provides the method of any one of Aspects 79-85, wherein the method comprises using the electrolytic cell at a temperature of 500° C. to 1,000° C. Aspect 87 provides the method of any one of Aspects 79-86 wherein the method comprises using the electrolytic cell at a temperature of 700° C. to 800° C. Aspect 88 provides the method of any one of Aspects 1-87, wherein the electrolytically converting the CO2and the water into the syngas composition comprises placing the CO2into contact with a first electrolytic cell that electrolytically converts the CO2to CO, and placing the water into contact with a second electrolytic cell that electrolytically converts the H2O to H2. Aspect 89 provides the method of any one of Aspects 1-88, wherein the electrolytically converting the CO2and the water into the syngas composition comprises placing the CO2and the water into contact with an electrolytic cell that electrolytically converts the CO2to CO and that electrolytically converts the H2O to H2. Aspect 90 provides the method of any one of Aspects 1-89, wherein the method further comprises using the syngas composition as a starting material to form a product comprising ammonia, methanol, a liquid fuel, a lubricant, gasoline, an oxo alcohol, or a combination thereof. Aspect 91 provides the method of any one of Aspects 1-90, further comprising recycling at least some exothermic heat generated by the formation of the product from the starting material in the method. Aspect 92 provides the method of any one of Aspects 1-91, wherein recycling at least some exothermic heat generated by the formation of the product from the starting material in the method comprises supplying at least part of the generated exothermic heat to the reaction of the hydrohalic acid with the metal carbonate salt to form the metal halide salt. Aspect 93 provides the method of any one of Aspects 1-92, wherein the method further comprises using the syngas composition as a starting material in a Fischer-Tropsch process to form one or more hydrocarbons. Aspect 94 provides the method of any one of Aspects 1-93, wherein the method is a method of making methanol, wherein the method further comprises using the syngas composition as a starting material to form methanol. Aspect 95 provides the method of Aspect 94, wherein forming the methanol comprises reacting the CO and the hydrogen in the presence of a catalyst to form methanol. Aspect 96 provides the method of Aspect 95, wherein the catalyst comprises Cr—Zn, Cu—Zr, and/or Cu—Zn. Aspect 97 provides the method of any one of Aspects 95-96, wherein the catalyst comprises a Cu—Zn catalyst. Aspect 98 provides the method of any one of Aspects 95-97, wherein the forming the methanol comprises reacting the CO and the hydrogen in the presence of the catalyst at a temperature of 20° C. to 500° C. Aspect 99 provides the method of any one of Aspects 95-98, wherein the forming the methanol comprises reacting the CO and the hydrogen in the presence of the catalyst at a temperature of 200° C. to 300° C. Aspect 100 provides the method of any one of Aspects 95-99, wherein forming the methanol comprises reacting the CO and the hydrogen in the presence of the catalyst at a pressure of 0.1 MPa to 40 MPa. Aspect 101 provides the method of any one of Aspects 95-100, wherein forming the methanol comprises reacting the CO and the hydrogen in the presence of the catalyst at a pressure of 3 MPa to 10 MPa. Aspect 102 provides the method of any one of Aspects 94-101, wherein the method further comprises recycling at least some exothermic heat generated by the formation of the methanol from the syngas composition back into the method. Aspect 103 provides a method of forming a syngas composition, the method comprising:hydrolyzing CaCl2to form HCl and Ca(OH)2;reacting the HCl with CaCO3, to form CO2, water, and CaCl2, wherein at least some of the CaCl2formed from the reacting of the HCl with the CaCO3is recycled as at least some of the CaCl2in the hydrolyzing of the CaCl2to form the HCl and the Ca(OH)2; andelectrolytically converting the CO2and the water into the syngas composition comprising carbon monoxide and hydrogen. Aspect 104 provides the method of Aspect 103, further comprising reacting a used CO2-capture sorbent with the Ca(OH)2, to form the CaCO3, wherein at least some of the Ca(OH)2formed in the hydrolysis of the CaCl2to form the HCl and the Ca(OH)2is recycled as at least some of the Ca(OH)2used in the reacting of the used CO2-capture sorbent with the Ca(OH)2. Aspect 105 provides the method of any one of Aspects 103-104, further comprising reacting Ca(HCO3)2from a water source (e.g., ocean water) with the Ca(OH)2, to form the CaCO3, wherein at least some of the Ca(OH)2formed in the hydrolysis of the CaCl2to form the HCl and the Ca(OH)2is recycled as at least some of the Ca(OH)2used in the reacting of the Ca(HCO3)2with the Ca(OH)2. Aspect 106 provides a method of regenerating a used hydroxide-based CO2-capture sorbent, the method comprising:hydrolyzing a metal halide salt to form a hydrohalic acid and a hydroxide salt of the metal in the metal halide salt, the metal comprising an alkaline earth metal or an alkali metal;reacting the used hydroxide-based CO2-capture sorbent with the hydroxide salt, to form a carbonate salt of the metal in the metal halide salt;reacting the hydrohalic acid with the carbonate salt, to form CO2, water, and the metal halide salt, wherein at least some of the metal halide salt formed from the reacting of the hydrohalic acid with the carbonate salt is recycled as at least some of the metal halide salt in the hydrolyzing of the metal halide salt to form the hydrohalic acid and the hydroxide salt; andelectrolytically converting the CO2and the water into a syngas composition comprising carbon monoxide and hydrogen. Aspect 107 provides a method of regenerating a used hydroxide-based CO2-capture sorbent, the method comprising:hydrolyzing CaCl2to form HCl and Ca(OH)2;reacting the used hydroxide-based CO2-capture sorbent with the Ca(OH)2, to form CaCO3;reacting the HCl with the CaCO3, to form CO2, water, and CaCl2, wherein at least some of the CaCl2formed from the reacting of the HCl with the CaCO3is recycled as at least some of the CaCl2in the hydrolyzing of the CaCl2to form the HCl and the Ca(OH)2; andelectrolytically converting the CO2and the water into a syngas composition comprising carbon monoxide and hydrogen. Aspect 108 provides a method of producing a syngas composition, the method comprising:hydrolyzing a metal halide salt to form a hydrohalic acid and a hydroxide salt of the metal in the metal halide salt, the metal comprising an alkaline earth metal or an alkali metal;reacting a bicarbonate salt from a water source comprising ocean water with the hydroxide salt, to form a carbonate salt of the metal in the metal halide salt;reacting the hydrohalic acid with the carbonate salt, to form CO2, water, and the metal halide salt, wherein at least some of the metal halide salt formed from the reacting of the hydrohalic acid with the carbonate salt is recycled as at least some of the metal halide salt in the hydrolyzing of the metal halide salt to form the hydrohalic acid and the hydroxide salt; andelectrolytically converting the CO2and the water into the syngas composition including carbon monoxide and hydrogen. Aspect 109 provides a method of producing methanol, the method comprising:hydrolyzing a metal halide salt to form a hydrohalic acid and a hydroxide salt of the metal in the metal halide salt, the metal comprising an alkaline earth metal or an alkali metal;reacting a bicarbonate salt from a water source comprising ocean water with the hydroxide salt, to form a carbonate salt of the metal in the metal halide salt;reacting the hydrohalic acid with the carbonate salt, to form CO2, water, and the metal halide salt, wherein at least some of the metal halide salt formed from the reacting of the hydrohalic acid with the carbonate salt is recycled as at least some of the metal halide salt in the hydrolyzing of the metal halide salt to form the hydrohalic acid and the hydroxide salt;electrolytically converting the CO2and the water into a syngas composition including carbon monoxide and hydrogen; andreacting the carbon monoxide and the hydrogen in the presence of a catalyst to form the methanol. Aspect 110 provides a method of producing a syngas composition, the method comprising:hydrolyzing CaCl2to form HCl and Ca(OH)2;reacting Ca(HCO3)2from a water source comprising ocean water with the Ca(OH)2, to form CaCO3; andreacting the HCl with the CaCO3, to form CO2, water, and CaCl2, wherein at least some of the CaCl2formed from the reacting of the HCl with the CaCO3is recycled as at least some of the CaCl2in the hydrolyzing of the CaCl2to form the HCl and the Ca(OH)2; andelectrolytically converting the CO2and the water into the syngas composition including carbon monoxide and hydrogen. Aspect 111 provides a method of producing methanol, the method comprising:hydrolyzing CaCl2to form HCl and Ca(OH)2;reacting Ca(HCO3)2from a water source comprising ocean water with the Ca(OH)2, to form CaCO3; andreacting the HCl with the CaCO3, to form CO2, water, and CaCl2, wherein at least some of the CaCl2formed from the reacting of the HCl with the CaCO3is recycled as at least some of the CaCl2in the hydrolyzing of the CaCl2to form the HCl and the Ca(OH)2;electrolytically converting the CO2and the water into a syngas composition including carbon monoxide and hydrogen; andreacting the carbon monoxide and the hydrogen in the presence of a catalyst to form the methanol. Aspect 112 provides the method of any one or any combination of Aspects 1-111 optionally configured such that all elements or options recited are available to use or select from. | 129,291 |
11858820 | BEST MODE Hereinafter, the present disclosure will be described in detail. A Mn4C magnetic material according to one aspect of the present disclosure shows main diffraction peaks of (111), (200), (220), (311) and (222) crystal planes at 2θ values of 40°, 48°, 69°, 82° and 88°, respectively, in an XRD analysis. The strong diffraction peaks of Mn4C mean that the Mn4C magnetic material is a high-purity Mn4C. For example, it may have a purity of 95% or more. Thus, according to one embodiment of the present disclosure, the diffraction peak intensity at 2θ values of 43° and 44°, which correspond to impurities, may be 2.5% or less, for example, 2.0% or less, of the diffraction peak intensity of the (111) crystal plane in XRD analysis. The magnetization of the Mn4C magnetic material according to one embodiment of the present disclosure may start to increase in a temperature range of 30 K to 80 K, for example, 50 K to 70 K, and the increased magnetization may be maintained in a temperature range of 540 K to 640 K, for example, 560 K to 600 K. Thus, the Mn4C magnetic material according to one embodiment of the present disclosure may maintain a stable magnetization state within the working temperature range. A method for producing a Mn4C magnetic material according to another aspect of the present disclosure includes: melting a mixture of manganese and carbon-based compound to obtain a melted mixture; cooling the melted mixture to produce an alloy ingot; and crushing the alloy ingot, and then removing impurities by magnetic separation. The manganese and carbon-based compound that are used in the method may preferably have high purity to obtain a high-purity Mn4C. The carbon-based compound may be one or more selected from graphite, graphene, carbon nanotubes, and carbon fibers. The mixture of manganese and the carbon-based compound may include 93 to 97 wt % of manganese and 3 to 7 wt % of the carbon-based compound. For example, it may include 94 to 96 wt % of manganese and 4 to 6 wt % of the carbon-based compound, or 95 to 96 wt % of manganese and 4 to 5 wt % of the carbon-based compound. When manganese and the carbon-based compound are used in amounts within the above ranges, the amount of unreacted raw materials may be reduced, and a Mn4C having a desired composition ratio may be easily produced. A melting method that is used for the melting is not particularly limited, but the melting may be performed by, for example, a plasma arc melting method. The melting may be performed at a temperature of 1,500 to 2,500 K, for example, 1,700 to 2,300 K, or 1,800 to 2,000 K, under an inert atmosphere. Thereafter, the produced melted mixture may be cooled to a temperature of 200 K to 300 K at a cooling rate of 102K/min to 105K/min, for example, 103K/min to 105K/min, or 104K/min to 105K/min, thereby producing a manganese carbide alloy ingot. A manganese carbide (Mn4C) magnetic material having a desired purity may be obtained by crushing and powdering the alloy ingot, and then magnetically separating the obtained powder to remove impurities. In this case, the crushing method is not particularly limited. The method of magnetic separation is not particularly limited, and for example, impurities may be removed several times using a magnet. MODE FOR INVENTION Hereinafter, the present disclosure will be described in detail with reference to examples. However, the examples according to the present disclosure may be modified into various different forms, and the scope of the present disclosure is not interpreted as being limited to the examples described below. The examples of the present specification are provided to more completely explain the present disclosure to those skilled in the art. Example 1 95 g of manganese (purity: 99.95%; purchased from Taewon Scientific Co., Ltd.) and 5 g of high-purity graphite (purity: 99.5%; purchased from Taewon Scientific Co., Ltd.) were placed in a water-cooled copper crucible of an argon plasma arc melting apparatus (manufactured by Labold AG, Germany, Model: vacuum arc melting furnace Model LK6/45), and melted at 2,000 K under an argon atmosphere. The melt was cooled to room temperature at a cooling rate of 104K/min to obtain an alloy ingot. The alloy ingot was crushed to a particle size of 1 mm or less by hand grinding. Thereafter, the obtained powders were magnetically separated using a Nd-based magnet to remove impurities repeatedly, and the Mn4C magnetic powders were collected. The collected Mn4C magnetic powders were subjected to X-ray diffraction (XRD) analysis (measurement system: D/MAX-2500 V/PO, Rigaku; measurement condition: Cu—Kαray) and energy-dispersive X-ray spectroscopy (EDS) using FE-SEM (Field Emission Scanning Electron Microscope, MIRA3 LM). FIGS.2(a)and2(b) show an X-ray diffraction pattern and an energy-dispersive X-ray spectroscopy graph of the Mn4C magnetic material produced according to Example 1 of the present disclosure, respectively. As can be seen inFIG.2(a), the Mn4C magnetic material showed diffraction peaks of (111), (200), (220), (311) and (222) crystal planes at 2θ values of 40°, 48°, 69°, 82° and 88°, respectively, in the XRD analysis. Thus, it can be seen that the XRD patterns of the Mn4C magnetic material produced according to Example 1 are well consistent with the patterns of the cubic perovskite Mn4C. In addition, the Mn4C magnetic material shows several very weak diffraction peaks that can correspond to Mn23C6and Mn. That is, the diffraction peak intensity at 2θ values of 43° and 44°, which correspond to Mn and Mn23C6impurities, is as very low as about 2.5% of the diffraction intensity of the peak corresponding to the (111) plane. Through this, it can be seen that the powders obtained in Example 1 have high-purity Mn4C phase. The lattice parameter of the Mn4C is estimated to be about 3.8682 Å. FIG.2(b)shows the results of analyzing the atomic ratio of Mn:C in the powder by EDS. The atomic ratio of Mn:C is 80.62:19.38, which is very close to 4:1 within the experimental uncertainties. Thus, it can be seen that the powder is also confirmed to be Mn4C. The M-T curve of the field aligned Mn4C powder obtained in Example 1 was measured under an applied field of 4 T and at a temperature ranging from 50 K to 400 K. Meanwhile, the M-T curve of the randomly oriented Mn4C powder was measured under an applied field of 1 T. The Curie temperature of Mn4C was measured under 10 mT while decreasing temperature from 930 K at a rate of 20 K/min. FIGS.3(a) to3(c)show the M-T curves of the Mn4C magnetic material, produced according to Example 1 of the present disclosure, under magnetic fields of 4 T, 1 T, and 10 mT, respectively. FIG.3shows magnetization-temperature (M-T) curves indicating the results of measuring the temperature-dependent magnetization intensity of the Mn4C magnetic material, produced in Example 1, using the vibrating sample magnetometer (VSM) mode of Physical Property Measurement System (PPMS®) (Quantum Design Inc.). According to the Néel theory, the ferrimagnets that contain nonequivalent substructures of magnetic ions may have a number of unusual forms of M-T curves below the Curie temperature, depending on the distribution of magnetic ions between the substructures and on the relative value of the molecular field coefficients. The anomalous M-T curves of Mn4C, as shown inFIG.3(a), can be explained to some extent by the Néel's P-type ferrimagnetism, which appears when the sublattice with smaller moment is thermally disturbed more easily. For Mn4C with two sublattices of MnIand MnII, as shown inFIG.1, the MnIsublattice might have smaller moment. FIG.3(a)shows the temperature dependence of magnetization of the Mn4C magnetic material produced in Example 1. The magnetization of Mn4C measured at 4.2K is 6.22 Am2/kg (4 T), corresponding to 0.258μBper unit cell. The magnetization of the Mn4C magnetic material varies little at temperatures below 50 K, and is quite different from that of most magnetic materials, which undergo a magnetization deterioration with increasing temperature due to thermal agitation. Furthermore, the magnetization of the Mn4C magnetic material increases linearly with increasing temperature at temperatures above 50 K. The linear fitting of the magnetization of Mn4C at 4 T within the temperature range of 100 K to 400 K can be written as M=0.0072T+5.6788, where M and T are expressed in Am2/kg and K, respectively. Thus, the temperature coefficient of magnetization of Mn4C is estimated to be about ˜2.99*10−4μB/K per unit cell. The mechanisms of the anomalous thermomagnetic behaviors of Mn4C may be related to the magnetization competition of the two ferromagnetic sublattices (MnIand MnII) as shown inFIG.1. FIG.3(b)shows the M-T curves of the Mn4C powders at temperatures within the range of 300 K to 930 K under 1 T. The linear magnetization increment stops at 590 K, above which the magnetization of Mn4C starts to decrease slowly first and then sharply at a temperature of about 860 K. The slow magnetization decrement at temperatures above 590 K is ascribed to the decomposition of Mn4C, which is proved by further heat-treatment of Mn4C as described below. According to one embodiment of the present disclosure, the saturation magnetization of Mn4C increases linearly with increasing temperature within the range of 50 K to 590 K and remains stable at temperatures below 50 K. The increases in anomalous magnetization of Mn4C with increasing temperature can be considered in terms of the Néel's P-type ferrimagnetism. At temperatures above 590 K, the Mn4C decomposes into Mn23C6and Mn, which are partially oxidized into the manganosite when exposed to air. The remanent magnetization of Mn4C varies little with temperature. The Curie temperature of Mn4C is about 870 K. The positive temperature coefficient (about 0.0072 Am2/kgK) of magnetization in Mn4C is potentially important in controlling the thermodynamics of magnetization in magnetic materials. The Curie temperature Teof Mn4C is measured to be about 870 K, as shown inFIG.3(c). Therefore, the sharp magnetization decrement of Mn4C at temperatures above 860 K is ascribed to both the decomposition of Mn4C and the temperature near the Tc of Mn4C. FIG.4is a graph showing the magnetic hysteresis loops of the Mn4C magnetic material, produced according to Example 1 of the present disclosure, at 4.2 K, 200 K and 400 K. The magnetic hysteresis loops were measured by using the PPMS system (Quantum Design) under a magnetic field of 7 T while the temperature was changed from 4 K to 400 K. As shown inFIG.4, the positive temperature coefficient of magnetization was further proved by the magnetic hysteresis loops of Mn4C as shown inFIG.4. The Mn4C shows a much higher magnetization at 400 K than that at 4.2 K. Moreover, the remanent magnetization of Mn4C varies little with temperature and is Δ3.5 Am2/kg within the temperature range of 4.2 K to 400 K. The constant remanent magnetization of Mn4C within a wide temperature range indicates the high stability of magnetization against thermal agitation. The coercivities of Mn4C at 4.2 K, 200 K, and 400 K were 75 mT, 43 mT, and 33 mT, respectively. The magnetic properties of Mn4C measured are different from the previous theoretical results. A corner MnImoment of 3.85μBantiparallel to three face-centered MnIImoments of 1.23μBin Mn4C was expected at 77 K. The net moment per unit cell was estimated to be 0.16μB. In the above experiment, the net moment in pure Mn4C at 77 K is 0.26μB/unit cell, which is much larger than that expected by Takei et al. It was reported that the total magnetic moment of Mn4C was calculated to be about 1μB, which is almost four times larger than the 0.258μBper unit cell measured at 4.2 K, as shown inFIG.4. FIG.5is an enlarged view of the temperature-dependent XRD patterns of the Mn4C magnetic material produced according to Example 1 of the present disclosure. The thermomagnetic behaviors of Mn4C are related to the variation in the lattice parameters of Mn4C with temperature. It is known that the distance of near-neighbor manganese atoms plays an important role in the antiferro- or ferro-magnetic configurations of Mn atoms. Ferromagnetic coupling of Mn atoms is possible only when the Mn—Mn distance is large enough.FIG.5shows the diffraction peaks of the (111) and (200) planes of Mn4C at temperatures from 16 K to 300 K. With increasing temperature, both (111) and (200) peaks of Mn4C shifted to a lower degree at temperatures between 50 K and 300 K, indicating an enlarged distance of Mn—Mn atoms in Mn4C. No peak shift is obviously observed for Mn4C at temperatures below 50 K. The distance of nearest-neighbor manganese atoms plays an important role in the antiferro- or ferro-magnetic configurations of Mn atoms and thus has a large effect on the magnetic properties of the compounds. Thus, it can be seen that the abnormal increase in magnetization of Mn4C with increasing temperature occurs due to the variation in the lattice parameters of Mn4C with temperature. The powder produced in Example 1 was annealed in vacuum for 1 hour at each of 700 K and 923 K, and then subjected to X-ray spectroscopy, and the results thereof are shown inFIG.6. The magnetization reduction of Mn4C at temperatures above 590 K is ascribed to the decomposition of Mn4C, which is proved by the XRD patterns of the powders after annealing Mn4C at elevated temperatures.FIG.6shows the structural evolution of Mn4C at elevated temperatures. When Mn4C is annealed at 700 K, a small fraction of Mn4C decomposes into a small amount of Mn23C6and Mn. The presence of manganosite is ascribed to the spontaneous oxidation of the Mn precipitated from Mn4C when exposed to air after annealing. The fraction of Mn23C6was enhanced significantly for Mn4C annealed at 923 K, as shown inFIG.6. These results prove that the metastable Mn4C decomposes into stable Mn23C6at temperatures above 590 K. The presence of Mn4C in the powder annealed at 923 K indicates a limited decomposition rate of Mn4C, from which the Tc of Mn4C can be measured. Both Mn23C6and Mn are weak paramagnets at ambient temperature and elevated temperatures. Therefore, the magnetic transition of the Mn4C magnetic material at 870 K is ascribed to the Curie point of the ferrimagnetic Mn4C. The Mn4C shows a constant magnetization of 0.258μBper unit cell below 50 K and a linear increment of magnetization with increasing temperature within the range of 50 K to 590 K, above which Mn23C6precipitates from Mn4C. The anomalous M-T curves of Mn4C can be considered in terms of the Néel's P-type ferrimagnetism. | 14,660 |
11858821 | DETAILED DESCRIPTION OF THE INVENTION Various commercially available silicas may be considered for use in the practice of this invention. Some representative examples of silica that can be used in the practice of this invention include, but is not limited to, silicas commercially available from PPG Industries under the Hi-Sil trademark, such as Hi-Sil® 210, Hi-Sil® 233 and Hi-Sil® 243, silicas available from Solvay, with, for example, designations of Zeosil®1085Gr, Zeosil®1115MP, Zeosil®1165MP, Zeosil® Premium and ZHRS®1200MP, and silicas available from Evonik Industries with, for example, designations Ultrasil® 5000GR, Ultrasil® 7000GR, Ultrasil® VN2, Ultrasil® VN3, and BV9000GR, and silicas available from Huber Engineered Materials with, for example, designations of Zeopol® 8745, and Zeopol® 8755LS. It is preferred for the silica to be rice hull ash silica. Such rice hull ash silica can be made in accordance with the teachings of United States Patent Application Publication No. 2002/0081247 A1 or U.S. Pat. No. 7,585,481 B2. The teachings of United States Patent Application Publication No. 2002/0081247 A1 and U.S. Pat. No. 7,585,481 B2 are incorporated herein by reference for the purpose of disclosing methods for making rice hull ash silica that can be utilized in accordance with this invention. The silica coupling agent will typically be a compound of the formula: Z-Alk-Sn-Alk-Z (I) Z-Alk-Sn-Alk (II) Z-Alk-SH (III) Z-Alk (IV) Si(OR1)4(V) in which Z is selected from the group consisting of: wherein R1is an alkyl group containing from 1 to 4 carbon atoms, a cyclohexyl group, or a phenyl group; wherein R2is an alkoxy group containing from 1 to 8 carbon atoms, or a cycloalkoxy group containing from 5 to 8 carbon atoms; wherein Alk is a divalent hydrocarbon of 1 to 18 carbon atoms and wherein n represents an integer from 2 to 8. The mercaptosilanes and blocked mercaptosilanes that can be used in the practice of this invention are described in International Patent Publication Number WO 2006/076670. The teachings of WO 2006/076670 are incorporated herein by reference for the purpose of describing specific mercaptosilanes and blocked mercaptosilanes that can be used in the practice of this invention. The teachings of WO 03091314 are also incorporated herein by reference for the purpose of describing specific silanes that can be utilized in the practice of this invention which emit low levels of volatile organic compounds or no volatile organic compounds. Specific examples of sulfur containing organosilicon compounds which may be used as the silica coupling agent in accordance with the present invention include: 3,3′-bis(trimethoxysilylpropyl) disulfide, 3,3′-bis(triethoxysilylpropyl) tetrasulfide, 3,3′-bis(triethoxysilylpropyl) octasulfide, 3,3′-bis(trimethoxysilylpropyl) tetrasulfide, 2,2′-bis(triethoxysilylethyl) tetrasulfide, 3,3′-bis(trimethoxysilylpropyl) trisulfide, 3,3′-bis(triethoxysilylpropyl) trisulfide, 3,3′-bis(tributoxysilylpropyl) disulfide, 3,3′-bis(trimethoxysilylpropyl) hexasulfide, 3,3′-bis(trimethoxysilylpropyl) octasulfide, 3,3′-bis(trioctoxysilylpropyl) tetrasulfide, 3,3′-bis(trihexoxysilylpropyl) disulfide, 3,3′-bis(tri-2″-ethylhexoxysilylpropyl) trisulfide, 3,3′-bis(triisooctoxysilylpropyl) tetrasulfide, 3,3′-bis(tri-t-butoxysilylpropyl) disulfide, 2,2′-bis(methoxy diethoxy silyl ethyl) tetrasulfide, 2,2′-bis(tripropoxysilylethyl) pentasulfide, 3,3′-bis(tricyclonexoxysilylpropyl) tetrasulfide, 3,3′-bis(tricyclopentoxysilylpropyl) trisulfide, 2,2′-bis(tri-2″-methylcyclohexoxysilylethyl) tetrasulfide, bis(trimethoxysilylmethyl) tetrasulfide, 3-methoxy ethoxy propoxysilyl 3′-diethoxybutoxy-silylpropyltetrasulfide, 2,2′-bis(dimethyl methoxysilylethyl) disulfide, 2,2′-bis(dimethyl sec.butoxysilylethyl) trisulfide, 3,3′-bis(methyl butylethoxysilylpropyl) tetrasulfide, 3,3′-bis(di t-butylmethoxysilylpropyl) tetrasulfide, 2,2′-bis(phenyl methyl methoxysilylethyl) trisulfide, 3,3′-bis(diphenyl isopropoxysilylpropyl) tetrasulfide, 3,3′-bis(diphenyl cyclohexoxysilylpropyl) disulfide, 3,3′-bis(dimethyl ethylmercaptosilylpropyl) tetrasulfide, 2,2′-bis(methyl dimethoxysilylethyl) trisulfide, 2,2′-bis(methyl ethoxypropoxysilylethyl) tetrasulfide, 3,3′-bis(diethyl methoxysilylpropyl) tetrasulfide, 3,3′-bis(ethyl di-sec.butoxysilylpropyl) disulfide, 3,3′-bis(propyl diethoxysilylpropyl) disulfide, 3,3′-bis(butyl dimethoxysilylpropyl) trisulfide, 3,3′-bis(phenyl dimethoxysilylpropyl) tetrasulfide, 3-phenyl ethoxybutoxysilyl 3′-trimethoxysilylpropyl tetrasulfide, 4,4′-bis(trimethoxysilylbutyl) tetrasulfide, 6,6′-bis(triethoxysilylhexyl) tetrasulfide, 12,12′-bis(triisopropoxysilyl dodecyl) disulfide, 18,18′-bis(trimethoxysilyloctadecyl) tetrasulfide, 18,18′-bis(tripropoxysilyloctadecenyl) tetrasulfide, 4,4′-bis(trimethoxysilyl-buten-2-yl) tetrasulfide, 4,4′-bis(trimethoxysilylcyclohexylene) tetrasulfide, 5,5′-bis(dimethoxymethylsilylpentyl) trisulfide, 3,3′-bis(trimethoxysilyl-2-methylpropyl) tetrasulfide, 3,3′-bis(dimethoxyphenylsilyl-2-methylpropyl) disulfide, (3-mercaptopropyl)trimethoxysilane, (3-Mercaptopropyl)triethoxysilane, and 3-(triethoxysilyl)propyl thiooctanoate. The preferred sulfur containing organosilicon compounds are the 3,3′-bis(trimethoxy or triethoxy silylpropyl) sulfides. The most preferred compound is 3,3′-bis(triethoxysilylpropyl) tetrasulfide. Therefore, with respect to formula I, Z is preferably wherein R2is an alkoxy of 2 to 4 carbon atoms, with 2 carbon atoms being particularly preferred; Alk is a divalent hydrocarbon of 2 to 4 carbon atoms with 3 carbon atoms being particularly preferred; and n is an integer of from 3 to 5 with 4 being particularly preferred. The amount of the silica coupling agent that should be incorporated into the elastomeric compositions of this invention will vary depending on the level of the siliceous fillers that are included in the rubbery composition. Generally speaking, the amount of the silica coupling agent used will range from about 0.01 to about 15 parts by weight per hundred parts by weight of silica filler. Preferably, the amount of silica coupling agent utilized will range from about 1 to about 12 parts by weight per hundred parts by weight of the siliceous filler. More preferably, the amount of silica coupling agent utilized will range from about 2 to about 10 parts by weight per hundred parts by weight of the siliceous filler. Most preferably the amount of the silica coupling agent included in the elastomeric compositions of this invention will range from about 6 to about 10 parts by weight per hundred parts by weight of the siliceous filler. The aqueous silica slurry made in accordance with this invention will normally contain from about 5 weight percent to about 25 weight percent silica, based upon the total weight of the aqueous slurry. The aqueous silica slurry will typically contain silica at a level which is within the range of about 7 weight percent to about 20 weight percent and which is preferably within the range of about 8 weight percent to about 12 weight percent. The phase transfer agent will normally be employed in the aqueous slurry at a level which is within the range of about 0.1 phf to 8 phf (parts by weight per 100 parts by weight of silica filler). More typically, the phase transfer agent will normally be employed in the aqueous slurry at a level which is within the range of about 0.5 phf to 5 phf. The phase transfer agent will normally preferably be employed in the aqueous slurry at a level which is within the range of about 0.8 phf to 4 phf, and will more preferably be utilized at a level which is within the range of 1 phf to 3 phf. Phase transfer agents which can be utilized in accordance with this invention are described in U.S. Pat. No. 5,663,396. The teachings of U.S. Pat. No. 5,663,396 are incorporated by reference herein for the purpose of describing such phase transfer agents. Methyl tributyl ammonium chloride (MTBAC) is a highly preferred phase transfer agent for use in the practice of this invention. After the aqueous slurry is made the silica coupling agent is allowed to react with the silica at a temperature and for a time which is sufficient to allow for the silica coupling agent to react with the silica. This temperature will normally be at least about 20° C. In most cases a temperature which is within the range of 20° C. to 100° C. will be utilized. The reaction temperature will normally be within the range of 40° C. to 80° C. with temperatures within the range of 60° C. to 75° C. being most preferred. It is preferred for a catalyst to be present to facilitate the reaction between the silica and the silica coupling agent. It is preferred for the catalyst to be a titanium alkoxide, such as titanium triethanolaminato isopropoxide (TI). The catalyst will normally be present in the aqueous silica slurry at a level which is within the range of 0.1 phf to 4 phf. The catalyst will typically be present in the aqueous silica slurry at a level which is within the range of 0.4 phf to 2 phf and will preferably be present at a level which is within the range of 0.6 phf to 1.4 phf. After the silica coupling agent has been allowed to react with the silica in the aqueous silica slurry the pre-hydrophobated precipitated silica made is recovered from the slurry. This is accomplished by simply removing the water from the silica product. It is normally preferred to recover the pre-hydrophobated precipitated silica by spray drying. This invention is illustrated by the following examples which are merely for the purpose of illustration and are not to be regarded as limiting the scope of the invention or the manner in which it can be practiced. Unless specifically indicated otherwise, parts and percentages are given by weight. COMPARATIVE EXAMPLES 1 & 2 AND EXAMPLES 3 & 4 In this experiment 100 grams of silica was put in a beaker. Then, 900 grams of deionized water was introduced and mixing was initiated. The silica slurry was mixed for 30 minutes at room temperature. Then, 2 grams of methyl tributyl ammonium chloride (MTBAC) was added to the system and mixing was continued for an additional 60 minutes. After that, either Si266 or Si69 was added as a silica coupling agent. Then, 8 grams (8 phf) of the silica coupling agent (either Si266 or Si69) was added. The samples were mixed for an additional 60 minutes. Finally, 1 gram of titanium triethanolaminato isopropoxide (TI) was added and the system was mixed for another 60 minutes. The samples were then placed in pans to start the drying process. After most of the water was removed, the silica samples were broken up with a mortar and pestle and returned for drying. The pre-hydrophobated precipitated silica samples made were then evaluated in rubber formulations made in non-productive and productive mixing stages. These rubber formulations included the constituents listed in Table 1. TABLE 1Evaluation Rubber Formulation2 minutes @ 160° C.or drop @ 160° C.Non-ProductiveFunctionalized Styrene-Butadiene Rubber70phrBudene ® 1207 High Cis-1,4-Polybutadiene30phrRubberN330 Carbon Black3phrMicrocrystalline Wax1.0phrAntioxidant2.0phrStearic Acid3.0phrSilica + Coupling Agent or70 phr + 5.6 phrPretreated Silica72 phrNaphthenic Processing Oil20phrProductiveZinc Oxide1.5phrSulfur1.4phrAccelerator1.4phrDiphenyl Guanidine2.1phrAntioxidant0.7phr A list of the important ingredients/parameters is presented in Table 2. Pretreated silica samples were prepared with Si266 or Si69 at a level of 8 phf (parts by weight per 100 parts by weight of filler). In addition, a control sample was generated with silica passed through the process with no chemicals added. A second control was generated where methyl tributyl ammonium chloride was utilized as a phase transfer agent and a third control with the methyl tributyl ammonium chloride phase transfer agent and titanium triethanolaminato isopropoxide catalyst being utilized. The mixing was performed on a 360 cc Haake mixer. The mixer was set at 100° C. and the initial rotor speed was at 120 rpm. For the pretreated silica 72 phr of silica were used instead of 70+5.6 phr of the neat silica and coupling agent. This reduced value would account for the condensation of silane, the release of ethanol and reduction in water content of the silica. TABLE 2Ingredients/ParametersExampleC1C233SilicaNeatNeatSi266 PretreatedSi266 PretreatedCoupling Agent8 phf Si2668 phf Si698 phf Si2668 phf Si69SilanizationIn SituIn SituPretreatedPretreatedMixing/Heat2 m @160° C.2 m @160° C.Drop @ 160° C.Drop @ 160° C.TreatmentSilica70 phr70 phrSi2665.6 phrSi695.6 phrPretreated Si26672 phrPretreated Si6972 phr The results of rheometer testing is provided in Table 3. It was noted that all samples processed similarly. The introduction of the titanium triethanolaminato isopropoxide catalyst (TI) did increase the on-set of the cure slightly. One thing to note is that the two pretreated samples with coupling agent mixed for only about 2 minutes (after ingredient loading) while the in-situ heat treated samples were mixed for about 2 minutes plus the heat treatment protocol. TABLE 3Rheometer Testing ResultsExampleC1C234G′ @ 0.833 Hz205kPa241kPa202kPa206kPaTan δ @ 0.833 Hz0.7580.6680.7940.727S′(MH)-S′ (ML)10.0dNm10.8dNm11.7dNm11.7dNmTime @ 25% cure S′2.6min2.6min1.9min1.9minTime @ 90% cure S′5.6min5.9min4.3min4.6min The RPA cured properties of the rubber samples are reported in Table 4. As can be seen, the pretreated silica with Si266 and Si69 silica coupling agents performed in an essentially equivalent manner to the in-situ treated samples where a heat treatment protocol of 2 minutes at 160° C. was used. In comparing the pretreated control sample it was noted that it also closely tracked the RPA properties of the in-situ sample treated for 2 minutes at 60° C. TABLE 4RPA DataExampleC1C234First Strain SweepG′ @ 1.000%2740 kPa2710 kPa3154 kPa2904 kPaG′ @ 10.000%1820 kPa1943 kPa2039 kPa2008 kPaTan δ @1.000%0.1280.1040.1240.104 The Rebound values reported in Table 5 and the Metravib results shown in Table 6 tell a similar story. The pretreated samples performed very close to or better than the samples treated for 2 minutes at 160° C. The increased heat treatment at 160° C. for 5 minutes gave the best properties with respect to tire rolling resistance indicators. However, switching to a higher temperature of 170° C. for 5 minutes deteriorated the properties. The silica that was passed through the treatment protocol without the addition of any chemicals performed equal to the neat sample that was heat treated for 2 minutes at 160° C. The silica sample that was treated with MTBAC and TI gave significantly improved properties as compared to the neat silica. Results at sub-ambient temperatures (0° C. and −20° C.) did not show significant differences. TABLE 5Rebound ValuesExampleC1C234Rebound @ 0° C.11.6%11.5%12.4%11.9%Rebound @ 20° C.44%50.4%46.4%51.5%Rebound @ 60° C.62.1%66.8%62.2%66% TABLE 6Metravib ResultsExampleC1C234G′ @−20° C.6.5 × 1066.3 × 1067.3 × 1066.5 × 106Tan δ @ 0° C.0.3050.2810.2970.266Tan δ @ 30° C.0.1920.1480.1820.145Tan δ @ 60° C.0.1520.1140.1460.112 Tensile results are reported in Table 7. It should be noted that for most of the properties the values are close. The one property that does show a significant difference is the elongation at break. Here there is a decrease observed for all samples that went through the treatment process. However, this probably resulted from the drying protocol utilized and would probably not be significant in cases where spray drying procedures are implemented. TABLE 7Tensile PropertiesExampleC1C234Modulus @ 100%2.3 MPa2.8 MPa2.6MPa2.8MPaModulus @ 300%9.4 MPa13.1 MPa10.4MPa13.6MPATensile Stress @ Max14.9 MPa15.1 MPa13.1MPA12.8MPaElongation @ Break410%332%352%290% Abrasion characteristics are reported in Table 8. As can be seen, the samples which were pretreated with a coupling agent performed worse than the in-situ heat treated samples. In fact, the pretreated samples perform close to the in-situ heat treated sample where the temperature was dropped at 160° C. The mixing of these samples was similar. Of course, as for the tensile results the drying protocol could have played a role but especially for the DIN results the indication is that it is mostly the mixing that influences it. It appears that the DIN properties are plateauing after a set of MEQ values have been introduced in the compounds. TABLE 8DIN AbrasionExampleC1C234DIN Rating1001029390 While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject invention. | 16,832 |
11858822 | PREFERRED EMBODIMENT Embodiment 1 (1) First alkali leaching: proceed first alkali leaching for circuit board incineration ash in sodium hydroxide solution, where the mass concentration of sodium hydroxide is 5%, solid-liquid ratio of ash to leach solution is 1:10 Kg/L, leaching temperature is 55° C., leaching time is 0.5 h, first leaching residue and first leaching solution is obtained after filtration; (2) Secondary alkali leaching: water is added to first leaching residue obtained in (1) for secondary alkali leaching, solid-liquid ratio of first leaching residue and water is 1:5 Kg/L, leaching temperature is room temperature and add sodium peroxide in leaching process, solid-liquid ratio of sodium peroxide and water is 20:1 Kg/m3, after adding sodium peroxide, stir 0.5 hours, and filter to get secondary leaching residue and secondary leaching solution, secondary leaching residue is gathered for treatment; (3) Lead and Zinc removal: combine first leaching solution obtained in (1) and secondary leaching solution obtained in (2) to obtain combined leaching solution, the mass ratio of first leaching solution and secondary leaching solution is 1:3, add 98% industrial concentrated sulfuric acid to combined leaching solution until the pH of the combined solution reaches 6.5, lead-zinc removal residue and lead-zinc removal solution are obtained by filtration; (4) Bromide evaporation and crystallization: proceed evaporation and crystallization for lead-zinc removal solution obtained in (3), crude bromide is obtained; (5) Lead separation: add lead-zinc removal residue obtained in (3) into water, solid-liquid ratio of lead-zinc removal residue and water is 1:1 Kg/L, add 98% industrial concentrated sulfuric acid with stirring until the solution pH is 4.5. Filter to get lead sulfate and lead separation solution; (6) Zinc evaporation and crystallization: proceed evaporation and crystallization for lead separation solution obtained in (5), crude zinc sulfate is obtained. Recovery rates of bromide are 98.3%, lead 97.1% and zinc 98.3%. Embodiment 2 (1) First alkali leaching: proceed first alkali leaching for circuit board incineration ash in sodium hydroxide solution, where the mass concentration of sodium hydroxide is 15%, solid-liquid ratio of ash to leach solution is 1:15 Kg/L, leaching temperature is 75° C., leaching time is 1 h, first leaching residue and first leaching solution is obtained after filtration; (2) Secondary alkali leaching: water is added to first leaching residue obtained in (1) for secondary alkali leaching, solid-liquid ratio of first leaching residue and water is 1:10 Kg/L, leaching temperature is room temperature and add sodium peroxide in leaching process, solid-liquid ratio of sodium peroxide and water is 50:1 Kg/m3, after adding sodium peroxide, stir 2 hours, and filter to get secondary leaching residue and secondary leaching solution, secondary leaching residue is gathered for treatment; (3) Lead and Zinc removal: combine first leaching solution obtained in (1) and secondary leaching solution obtained in (2) to obtain combined leaching solution, the mass ratio of first leaching solution and secondary leaching solution is 3:1, add 98% industrial concentrated sulfuric acid to combined leaching solution until the pH of the combined solution reaches 8, lead-zinc removal residue and lead-zinc removal solution are obtained by filtration; (4) Bromide evaporation and crystallization: proceed evaporation and crystallization for lead-zinc removal solution obtained in (3), crude bromide is obtained; (5) Lead separation: add lead-zinc removal residue obtained in (3) into water, solid-liquid ratio of lead-zinc removal residue and water is 1:2 Kg/L, add 98% industrial concentrated sulfuric acid with stirring until the solution pH is 6. Filter to get lead sulfate and lead separation solution; (6) Zinc evaporation and crystallization: proceed evaporation and crystallization for lead separation solution obtained in (5), crude zinc sulfate is obtained. Recovery rates of bromide are 99.3%, lead 99.5% and zinc 99.3%. Embodiment 3 (1) First alkali leaching: proceed first alkali leaching for circuit board incineration ash in sodium hydroxide solution, where the mass concentration of sodium hydroxide is 10%, solid-liquid ratio of ash to leach solution is 1:12 Kg/L, leaching temperature is 65° C., leaching time is 1 h, first leaching residue and first leaching solution is obtained after filtration; (2) Secondary alkali leaching: water is added to first leaching residue obtained in (1) for secondary alkali leaching, solid-liquid ratio of first leaching residue and water is 1:8 Kg/L, leaching temperature is room temperature and add sodium peroxide in leaching process, solid-liquid ratio of sodium peroxide and water is 35:1 Kg/m3, after adding sodium peroxide, stir 1 hours, and filter to get secondary leaching residue and secondary leaching solution, secondary leaching residue is gathered for treatment; (3) Lead and Zinc removal: combine first leaching solution obtained in (1) and secondary leaching solution obtained in (2) to obtain combined leaching solution, the mass ratio of first leaching solution and secondary leaching solution is 1:1, add 98% industrial concentrated sulfuric acid to combined leaching solution until the pH of the combined solution reaches 7, lead-zinc removal residue and lead-zinc removal solution are obtained by filtration; (4) Bromide evaporation and crystallization: proceed evaporation and crystallization for lead-zinc removal solution obtained in (3), crude bromide is obtained; (5) Lead separation: add lead-zinc removal residue obtained in (3) into water, solid-liquid ratio of lead-zinc removal residue and water is 1:1.5 Kg/L, add 98% industrial concentrated sulfuric acid with stirring until the solution pH is 5. Filter to get lead sulfate and lead separation solution; (6) Zinc evaporation and crystallization: proceed evaporation and crystallization for lead separation solution obtained in (5), crude zinc sulfate is obtained. Recovery rates of bromide are 97.8%, lead 98.2% and zinc 99.1%. Embodiment 4 (1) First alkali leaching: proceed first alkali leaching for circuit board incineration ash in sodium hydroxide solution, where the mass concentration of sodium hydroxide is 5%, solid-liquid ratio of ash to leach solution is 1:15 Kg/L, leaching temperature is 55° C., leaching time is 1 h, first leaching residue and first leaching solution is obtained after filtration; (2) Secondary alkali leaching: water is added to first leaching residue obtained in (1) for secondary alkali leaching, solid-liquid ratio of first leaching residue and water is 1:5 Kg/L, leaching temperature is room temperature and add sodium peroxide in leaching process, solid-liquid ratio of sodium peroxide and water is 50:1 Kg/m3, after adding sodium peroxide, stir 0.5 hours, and filter to get secondary leaching residue and secondary leaching solution, secondary leaching residue is gathered for treatment; (3) Lead and Zinc removal: combine first leaching solution obtained in (1) and secondary leaching solution obtained in (2) to obtain combined leaching solution, the mass ratio of first leaching solution and secondary leaching solution is 2:1, add 98% industrial concentrated sulfuric acid to combined leaching solution until the pH of the combined solution reaches 8, lead-zinc removal residue and lead-zinc removal solution are obtained by filtration; (4) Bromide evaporation and crystallization: proceed evaporation and crystallization for lead-zinc removal solution obtained in (3), crude bromide is obtained; (5) Lead separation: add lead-zinc removal residue obtained in (3) into water, solid-liquid ratio of lead-zinc removal residue and water is 1:1 Kg/L, add 98% industrial concentrated sulfuric acid with stirring until the solution pH is 6. Filter to get lead sulfate and lead separation solution; (6) Zinc evaporation and crystallization: proceed evaporation and crystallization for lead separation solution obtained in (5), crude zinc sulfate is obtained. Recovery rates of bromide are 96.9%, lead 96.8% and zinc 97.2%. Embodiment 5 (1) First alkali leaching: proceed first alkali leaching for circuit board incineration ash in sodium hydroxide solution, where the mass concentration of sodium hydroxide is 15%, solid-liquid ratio of ash to leach solution is 1:10 Kg/L, leaching temperature is 75° C., leaching time is 0.5 h, first leaching residue and first leaching solution is obtained after filtration; (2) Secondary alkali leaching: water is added to first leaching residue obtained in (1) for secondary alkali leaching, solid-liquid ratio of first leaching residue and water is 1:10 Kg/L, leaching temperature is room temperature and add sodium peroxide in leaching process, solid-liquid ratio of sodium peroxide and water is 20:1 Kg/m3, after adding sodium peroxide, stir 2 hours, and filter to get secondary leaching residue and secondary leaching solution, secondary leaching residue is gathered for treatment; (3) Lead and Zinc removal: combine first leaching solution obtained in (1) and secondary leaching solution obtained in (2) to obtain combined leaching solution, the mass ratio of first leaching solution and secondary leaching solution is 1:2, add 98% industrial concentrated sulfuric acid to combined leaching solution until the pH of the combined solution reaches 6.5, lead-zinc removal residue and lead-zinc removal solution are obtained by filtration; (4) Bromide evaporation and crystallization: proceed evaporation and crystallization for lead-zinc removal solution obtained in (3), crude bromide is obtained; (5) Lead separation: add lead-zinc removal residue obtained in (3) into water, solid-liquid ratio of lead-zinc removal residue and water is 1:2 Kg/L, add 98% industrial concentrated sulfuric acid with stirring until the solution pH is 4.5. Filter to get lead sulfate and lead separation solution; (6) Zinc evaporation and crystallization: proceed evaporation and crystallization for lead separation solution obtained in (5), crude zinc sulfate is obtained. Recovery rates of bromide are 97.2%, lead 99.1% and zinc 96.1%. Embodiment 6 (1) First alkali leaching: proceed first alkali leaching for circuit board incineration ash in sodium hydroxide solution, where the mass concentration of sodium hydroxide is 12%, solid-liquid ratio of ash to leach solution is 1:14 Kg/L, leaching temperature is 70° C., leaching time is 1 h, first leaching residue and first leaching solution is obtained after filtration; (2) Secondary alkali leaching: water is added to first leaching residue obtained in (1) for secondary alkali leaching, solid-liquid ratio of first leaching residue and water is 1:6 Kg/L, leaching temperature is room temperature and add sodium peroxide in leaching process, solid-liquid ratio of sodium peroxide and water is 30:1 Kg/m3, after adding sodium peroxide, stir 1.5 hours, and filter to get secondary leaching residue and secondary leaching solution, secondary leaching residue is gathered for treatment; (3) Lead and Zinc removal: combine first leaching solution obtained in (1) and secondary leaching solution obtained in (2) to obtain combined leaching solution, the mass ratio of first leaching solution and secondary leaching solution is 2.5:1, add 98% industrial concentrated sulfuric acid to combined leaching solution until the pH of the combined solution reaches 7.5, lead-zinc removal residue and lead-zinc removal solution are obtained by filtration; (4) Bromide evaporation and crystallization: proceed evaporation and crystallization for lead-zinc removal solution obtained in (3), crude bromide is obtained; (5) Lead separation: add lead-zinc removal residue obtained in (3) into water, solid-liquid ratio of lead-zinc removal residue and water is 1:1.6 Kg/L, add 98% industrial concentrated sulfuric acid with stirring until the solution pH is 5.8. Filter to get lead sulfate and lead separation solution; (6) Zinc evaporation and crystallization: proceed evaporation and crystallization for lead separation solution obtained in (5), crude zinc sulfate is obtained. Recovery rates of bromide are 99.1%, lead 98.0% and zinc 96.9%. | 12,270 |
11858823 | DETAILED DESCRIPTION OF THE INVENTION The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with the general description of the invention given above and the detailed description of an embodiment given below, serve to explain the principles of the present invention. Similar components of the devices are similarly numbered for simplicity. FIG.1is a process flow schematic drawing of one embodiment of the invention for the treatment of cattle manure (e.g., from a CAFO) comprising solids separation, anaerobic digestion, stripping, condensation, concentration, and crystallization. In the process according toFIG.1, there is no chemical addition to adjust pH prior to, or in, the stripping process. The present invention excludes the use of pH adjustment chemicals. In the process according toFIG.1, there is also no external supply of carbon dioxide. The carbon dioxide dissolved in solution within the anaerobic digester's digestate, which derives directly from the cattle manure waste, is the sole source for carbon dioxide in the process. As depicted inFIG.1, raw manure10with or without associated dairy waste generated at the CAFO is transported to a solids separation unit/process20(it being understood that a mixing or holding tank/vessel could be used prior to solids separation and/or can be used for solids separation). The solids separation unit/process may be a single stage or chamber unit or it could be a series of stages or chambers for coarse solids separation and intermediate solids separation. The slurry/effluent24from the solids separation unit20is input into an anaerobic digester30which digests much, preferably most, of the dissolved organics and small organic particulates to produce biogas32and an effluent digestate34. The effluent digestate34from the anaerobic digester30contains residual solids, dissolved salts and organics, and concentrations of dissolved ammonia and carbon dioxide. The present invention collects the ammonia and carbon dioxide and captures them in a subsequent multistage process to re-form solid ammonium bicarbonate. Each stage of the subsequent multistage process operates at different temperatures to take advantage of the solubility properties of ammonium bicarbonate for its concentration in dissolved form and then its formation as a nitrogen rich solid. The temperature of digestate34out of a typical anaerobic digester treating cattle manure is about 35 degrees Celsius. For the process of the invention, the digestate needs to be heated to greater than about 80 degrees Celsius for treatment in the stripper40. The stripper operating at a temperature of greater than about 80 degrees Celsius, without any chemical addition to increase pH, removes dissolved ammonia and dissolved carbon dioxide from the digestate34creating exhaust vapor42containing water vapor, gaseous carbon dioxide, and gaseous ammonia. Vapor42will also contain traces of organic volatiles and semi-volatiles. InFIG.1, footnote 1 denotes the vapor is constant composition for continuous operation and varies during a batch process—H20, CO2, and NH3 evolve with traces of organic volatiles and semi volatiles. The treated water and solids44out of the stripper can be further treated for application to land or water using current treatment technologies. The temperature of the stripper40can be maintained using a heat exchanger46. The vapor42created by stripping the digestate34in that first stage, the separation stage, is then treated in a second condensation and concentration stage to create a concentrated dissolved ammonium bicarbonate solution. Condenser50and reverse osmosis filter60are then used to treat vapor42at a temperature of between about 35 degrees Celsius and 50 degrees Celsius. A pressure control valve48can be used between the stripper40and the condenser50to maintain a differential between the two. InFIG.1, footnote 2 denotes pressure control valve is set to maintain differential between distillation unit and condenser—Condenser temperature, T, must be less than 50 degrees Celsius to keep NH4 and HCO3 in solution, while distillation temperature must be greater than 80 degrees Celsius to convert to NH3 and CO2. Operating the condenser50between about 35 and 50 degrees Celsius allows the water vapor, ammonia, and carbon dioxide to form dissolved ammonium bicarbonate. Maintaining between about 35 and 50 degrees Celsius in the condenser50, and a pH less than 9, prevents precipitation of dissolved ammonium bicarbonate or ammonium carbonate and keeps it in dissolved form. The temperature of the condenser50can be maintained using a heat exchanger56. The non-condensed water and gases52exiting the condenser50can be discharged to the atmosphere. InFIG.1, footnote 3 denotes AB solution in condenser is distillate of feed to stripping device. Following the condenser50, and operating at about the same temperature as the condenser50, the effluent ammonium bicarbonate solution54is treated in a reverse osmosis filter60. Reverse osmosis filter60removes water thereby concentrating the ammonium bicarbonate in the solution. The resulting concentrated effluent64out of the reverse osmosis filter60contains about 50-100 times the concentration of dissolved ammonium bicarbonate in the digestate34. InFIG.1, footnote 5 denotes AB concentrate is supersaturated relative to temperature of crystallizer. Control of the reverse osmosis temperature avoids precipitation of the ammonium bicarbonate on the membrane while achieving a concentration sufficient for saturation at the temperature in the crystallizer. The permeate62is a clean water than can be reused or discharged. The concentrated effluent64out of the reverse osmosis filter60is then treated at a temperature of less than about 35 degrees Celsius in stage three using a crystallizer70. It is understood that lower temperatures, e.g., 20 degrees Celsius, could be used in the crystallizer depending upon the concentrations of dissolved ammonium carbonate and ammonium bicarbonate in the reverse osmosis concentrate. Solid crystals of ammonium bicarbonate are grown in the crystallizer70under controlled conditions, separated from the liquid fraction to produce an ammonium-salt74which may be dried, pelletized or granulated to form a final product. In some embodiments, a portion of the saturated ammonium bicarbonate supernatant is recycled72to the reverse osmosis filter60, after it is heated to the required temperature in a heat exchanger56. InFIG.1, footnote 4 denotes heat exchange on recirculation liquid to minimize size of heat exchanger56to match temperature of reactor liquid. Due to the unique sequence of the preceding unit operations, the resulting ammonium salt may be dried and packaged for commercial distribution as a specialized nitrogen fertilizer, that is high-purity, phosphorus free, and certified USDA organic. The resulting product is high-purity and phosphorous free due to the two purification operations, namely, 1) the distillation process which removes ammonia and separates it from salts that are left behind in the distillation unit's liquid effluent, and 2) the crystallization process which removes solid ammonium bicarbonate from other contaminants including traces of phosphorous containing salts. If synthetic chemicals are not used in obtaining the solids or liquid digestate, the ammonium bicarbonate product will have the potential for designation as organic (USDA 2012) fertilizer. The USDA designation is of economic importance as the price of organic fertilizer expressed as dollars per pound ammonia nitrogen, is materially higher than that of chemical (non-organic) fertilizers that are equally uniform, high purity, and concentrated sources of NH3-N. As with synthetic fertilizer, the material is nearly odorless, and has low transport and application costs relative to manure and digestate. If the ammonia is captured with an industrial acid or is derived from application of caustic or other industrial alkali—it will not qualify as organic fertilizer. The ammonium salt according to the invention resolves this conflict by (1) producing ammonia gas thermally with no chemical addition, and (2) using the carbon dioxide found in the digestate to recover the ammonia from the digestate to form an organic fertilizer, ammonium bicarbonate. The ammonium salt74can be stored80for use on or off site. Another embodiment of the invention for a wastewater that utilizes solids reduction prior to membrane separation of ammonia is shown inFIG.2. In such instances, stage 1 of the foregoing described process can be modified to remove solids (effluent suspended solids of 0.1% or less) so that a membrane separation device could be employed to separate the gases water vapor, carbon dioxide, and ammonia from the digestate liquid. As depicted inFIG.2, raw manure110with or without associated dairy waste generated at the CAFO is transported to a solids separation unit/process120(it being understood that a mixing or holding tank/vessel could be used prior to solids separation or for the separation). The solids separation unit/process120may be a single stage or chamber unit or it could be a series of stages or chambers. InFIG.2, the footnotes 1-4 denote the following:[1]—mesophilic digester, 35 Cdigested dairy manure, typical ammonia nitrogen is 1000 ppmAB is ammonium bicarbonate. Calculated from NH3-N and MW ratioAB concentration is 1% of saturation at 35 Cdigested manure is high in TSSNo pH adjustment by either chemical addition or CO2 removal[2]—gas from Separation Device has 20× concentration of ammonia as inputNH3-N is 60% NH3 at 80 C, 34% NH3 at 60 C, and 4% NH3 at 20Temperature must be about 80 C or higher to convert NH4+ to NH3AB concentration is about 5% of saturation at 80 CNearly all the TSS is removed by the uF[3]—Condensate <50 C to convert dissolved NH3 and CO2 to dissolved AB, and >35 C to avoid precipitation in lines or ROAB concentrate from RO is about 81% of saturation at 50 CpH must be less than 9 to avoid carbonate formation and precipitationRecycle of liquor from crystallizer to RO has about the same concentration as the RO concentrate, and must be heated to the RO temperature[4] Solids from crystallizer are high-purity, certifiable organic N-fertilizer The output/effluent from the solids separation unit124is input into an anaerobic digester130which digests much, preferably most, of the dissolved organics and small organic particulates to produce biogas132and an effluent digestate134. The temperature of digestate134, about 35 degrees Celsius, is heated to greater than about 80 degrees Celsius for treatment in stage 1, as described in detail below. Here again, as for the previous embodiment, the invention excludes the addition of chemicals to increase pH and also excludes the addition of carbon dioxide from a non-organic source (preferably, the carbon dioxide used in the process comes directly from the waste being treated). For the embodiment shown inFIG.2, an input vapor similar to that created in the foregoing embodiment shown inFIG.1containing water vapor, gaseous carbon dioxide, and gaseous ammonia, is created using a different unit process than shown inFIG.1. InFIG.2, the separation of the gaseous ammonia and gaseous carbon dioxide from the digestate134is accomplished using a membrane device143instead of a stripper. The membrane passes gases, such as water vapor, ammonia, and carbon dioxide, but not liquid water. It therefore performs the same gas-separation function as the separation device shown in stage 1 ofFIG.1. As shown inFIG.2, the digestate134is treated for solids removal prior to stage 1, the ultrafilter136, and prior to gas separation in the membrane device143. An ultra filter136is shown inFIG.2for the solids removal it being understood that other solids removal methods producing the equivalent result of fine solids removal, for example passing only solids of less than 0.5 micron, are included within the scope of the invention. The concentrated solids138from the ultra filter136can be mixed with the solids from the initial solids separation step, or processed as a high phosphorus solid product. The ultra filter136removes a substantial portion of the total suspended solids in the digestate. The low suspended-solids (0.1% or less) digestate137is then treated in the gas-separation process of the invention which in this embodiment includes use of membrane device143. The temperature of the low-solids digestate137is raised to at least about 80 degrees Celsius using a heat exchanger146. Membrane device143includes a hydrophobic membrane that allows gas molecules to pass, such as water vapor, ammonia, and carbon dioxide, but not the liquid and its contaminants. The preceding uF is required to remove solids and organic material that might otherwise foul the hydrophobic membrane. Vapor142will also contain traces of organic volatiles and semi-volatiles. The treated water and solids149out of the membrane device143can be further treated for application to land or water using current treatment technologies. The vapor142created from the digestate using the membrane device143in that first stage, the separation stage, is then treated in stage 2 and stage 3 using condensation and concentration, respectively, followed by crystallization, similar to the embodiment shown inFIG.1. Condenser150and reverse osmosis filter160are used to condense vapor142and concentrate its condensate154at a temperature of between about 35 and 50 degrees Celsius, to hold stable ammonium bicarbonate in solution. The effluent ammonium bicarbonate solution154out of the condenser150contains the dissolved ammonium bicarbonate from the ammonia and carbon dioxide of the digestate134. The non-condensed water and gases152exiting the condenser150can be discharged to the atmosphere. Following the condenser150, and operating at about the same temperature as the condenser150, the effluent ammonium bicarbonate solution154is treated in a reverse osmosis filter160. Reverse osmosis filter160removes water thereby concentrating the ammonium bicarbonate in the solution. The resulting concentrated effluent164out of the reverse osmosis filter160contains about 10 times the concentration of dissolved ammonium bicarbonate in the condenser effluent154. The permeate162is a clean water than can be reused or discharged. The concentrated effluent164out of the reverse osmosis filter160is then treated at a temperature of less than about 35 degrees Celsius, preferably less than 20 degrees Celsius, in stage 3 using a crystallizer170. Solid crystals of ammonium bicarbonate are grown in the crystallizer170under controlled conditions, separated from the liquid fraction to produce an ammonium-salt174which may be dried, pelletized or granulated to form a final product. In some embodiments, a portion of the saturated ammonium bicarbonate supernatant is recycled172to the reverse osmosis filter160. A resulting ammonium salt174solid, having physical and chemical properties as stated above for the first embodiment will result. The ammonium salt can be stored180for use on or off site. Yet another embodiment of the invention using an external source for carbon dioxide is shown inFIG.3. Such an embodiment could be used for wastes that do not contain the carbon dioxide needed to convert the ammonia to ammonium bicarbonate. Examples of such wastes include waste not processed using anaerobic digestion, such as high-solids manure or other organic waste. In the embodiment shown inFIG.3, as compared to the embodiment shown inFIG.1, stage 1 and stage 2 are modified. InFIG.3, stage 1 comprises a dryer247in place of a stripper and stage 2 includes the addition of membrane modules253with a source of carbon dioxide255along with a condenser250and a reverse osmosis filter260. InFIG.3, the footnotes 1-4 denote the following:[1]—dryer exhaust to 2-stage condenserammonia water at 2× exhaust ammonia concentration, temperature between 20 and 35 C[2]—ammonia stabilized with CO2 as acidP adjusted to provide CO2 to stabilize ammonia water in effluentCO2 flow rate equals CO2 as HCO3 in effluent liquid.[3]—Ammonium bicarbonate at 20 C in cystallizerMother liquor recycled to RO, and must be heated to the RO temperature[4]—inject compressed vent gas (CO2, H20, NH3) into ammonia water feed line. Here again, as for the previous embodiments, the invention excludes the addition of chemicals to increase pH. For the embodiment shown inFIG.3, a solution of ammonium bicarbonate is created and crystallized as in the foregoing embodiments shown inFIGS.1and2. InFIG.3, the separation of the gaseous ammonia from the waste234is performed using a dryer247, an ammonia water is created using condensers250, and gaseous carbon dioxide is contacted with the ammonia water solution using membrane device253to create a solution of ammonium bicarbonate. As depicted inFIG.3, the waste (such as layer manure)234is treated in stage 1 of the process of the invention which in this embodiment includes use of dryer247. The temperature of the dryer is at least about 80 degrees Celsius. Dryer247operates at a sufficiently high temperature that the ammonia in the waste is converted to gas and removed with the water vapor. The dryer functions as a separation device in a manner analogous to the distillation process40inFIG.1. The exhaust vapor242from the dryer247contains water vapor and gaseous ammonia and lower than desired concentrations of carbon dioxide. In this embodiment, it is assumed that there is an insufficient amount of carbon dioxide in the waste to react with and convert substantially all of the gaseous ammonia into dissolved ammonium bicarbonate and thus, additional carbon dioxide is required. The dried waste244out of the dryer247can be processed further into solid products such as fertilizer, animal feed supplement, or fuel. The vapor242created using the dryer247in stage 1, the separation stage, is then treated in stage 2 using condensation, carbon dioxide addition, and concentration. FIG.3shows an example of a two-step condenser250to create an ammonia water258from the dryer exhaust gas242. The first step removes about one half of the water and nearly no ammonia (NH3) and the second step is complete condensation producing ammonia water at about 50 degrees Celsius or less. The concentration of the dissolved ammonia in the condensate will be about twice that in the dryer vapor, for example about 0.5% by weight. The non-condensed water and gases252exiting the condenser250can be discharged to the atmosphere. The ammonia water258is then treated in a membrane device253where an external source of gaseous carbon dioxide255is added. The gaseous carbon dioxide passes through the membrane, dissolves into the ammonia water, and reacts to create a solution of ammonium bicarbonate254. For example, the solution of ammonium bicarbonate may be 2.3% by weight ammonium bicarbonate at about pH 6.5-8.5, depending on the amount of CO2 added and the temperature. The ammonium bicarbonate254is then treated in a reverse osmosis filter260. Reverse osmosis filter260removes water thereby concentrating the ammonium bicarbonate in the solution. The resulting concentrated effluent264out of the reverse osmosis filter260contains about 20 times the concentration of ammonia in the dryer gas. The permeate262is a clean water than can be reused or discharged. Stage 2 which includes the condenser250, the membrane device253and the reverse osmosis filter260operate at a temperature of between about 35 degrees Celsius and 50 degrees Celsius. The dissolved ammonium bicarbonate solution264is then treated in stage 3 using crystallization, similar to the embodiments shown inFIGS.1and2. The concentrated effluent264out of the reverse osmosis filter260is cooled to a temperature of less than about 35 degrees Celsius in stage 3 using a crystallizer270. Solid crystals of ammonium bicarbonate are grown in the crystallizer270under controlled conditions, separated from the liquid fraction to produce an ammonium-salt274which may be dried (such as using dryer285), pelletized or granulated to form a final product. A resulting ammonium salt solid having physical and chemical properties as stated above for the first and second embodiments will result. However, the certification as an organic product is contingent upon use of carbon dioxide produced organically. If synthetic carbon dioxide is used, the ammonium bicarbonate product cannot be designated as an organic fertilizer. Carbon dioxide produced by fermentation of either animal waste or agricultural material (for example to produce ethanol) is certifiably organic; and is readily available from agricultural sources to assure that the carbon dioxide is neither synthetic nor contaminated with synthetic carbon dioxide. FIG.4is a process flow schematic drawing of a variation on the embodiment of the invention shown inFIG.1for the treatment of cattle manure (e.g., from a CAFO) comprising solids separation, anaerobic digestion, stripping, absorption, concentration, and crystallization. In the process according toFIG.4, there is no chemical addition to adjust pH prior to, or in, the stripping process. The present invention excludes the use of pH adjustment chemicals. In the process according toFIG.4, there is also no external supply of carbon dioxide. The carbon dioxide dissolved in solution within the anaerobic digester's digestate, which derives directly from the cattle manure waste, is supplemented by carbon dioxide from the biogas to assure maintenance of CO2 in the water to stabilize the ammonia in the absorber column.FIG.4shows the biogas32processed in a CO2 removal device35to provide CO2 to provide carbonated water for capture of ammonia as ammonium bicarbonate. For example, the device could be a pressure swing adsorption device which is commonly used to separate gases, such as CH4 and CO2, with materially different properties. InFIG.4, footnotes 1-5 denote the following:[1]—vapor is constant composition for continuous operation and varies during a batch process. H20, CO2, and NH3 evolve with traces of organic volatiles and semi-volatiles.[2]—pressure control valve is set to maintain differential between stripper unit and absorber. Absorber temperature, T, must be less than 50 C to keep NH4 and HCO3 in solution, while stripper temperature must be greater than 80 C to convert to NH3 and CO2.[3]—AB solution in absorber is formed from Digester biogas[4]—HX on recycled stripper gas to match temperature of stripper liquid.[5]—AB concentrate is supersaturated relative to temperature of crystallizer. As depicted inFIG.4, raw manure10with or without associated dairy waste generated at the CAFO is transported to a solids separation unit/process20(it being understood that a mixing or holding tank/vessel could be used prior to solids separation and/or can be used for solids separation). The solids separation unit/process may be a single stage or chamber unit or it could be a series of stages or chambers for coarse solids separation and intermediate solids separation. The slurry/effluent24from the solids separation unit20is input into an anaerobic digester30which digests much, preferably most, of the dissolved organics and small organic particulates to produce biogas32and an effluent digestate34. The effluent digestate34from the anaerobic digester30contains residual solids, dissolved salts and organics, and concentrations of dissolved ammonia and carbon dioxide. The present invention collects the ammonia and carbon dioxide and captures them in a subsequent multistage process to form solid ammonium bicarbonate. Each stage of the subsequent multistage process operates at different temperatures to take advantage of the solubility properties of ammonium bicarbonate for its concentration in dissolved form and then its formation as a nitrogen rich solid. The temperature of digestate34out of a typical anaerobic digester treating cattle manure is about 35 degrees Celsius. For the process of the invention, the digestate needs to be heated to greater than about 80 degrees Celsius for treatment in the stripper40. The stripper operating at a temperature of greater than about 80 degrees Celsius, without any chemical addition to increase pH, uses gas (biogas, CH4, CO2, air, etc) to remove dissolved ammonia and dissolved carbon dioxide from the digestate34creating exhaust vapor42containing water vapor, gaseous carbon dioxide, and gaseous ammonia. Vapor42will also contain traces of organic volatiles and semi-volatiles. The treated water and solids44out of the stripper can be further treated for application to land or water using current treatment technologies. The temperature of the stripper40can be maintained using a heat exchanger46to heat the recycled stripper gas45from the absorber. The vapor42created by stripping the digestate34in that first stage, the separation stage, is then treated with a cold water stream53saturated with CO2, in an absorption stage50to create a dissolved ammonium bicarbonate solution. Ammonia is removed from the vapor distillate, producing recycled stripper gas45which is heated in heat exchanger46prior to entry at the bottom of stripper40. Absorber50and reverse osmosis filter60are used to treat vapor42at a temperature of between about 35 degrees Celsius and 50 degrees Celsius. A pressure control valve48can be used between the stripper40and the absorber50to maintain a differential between the two. Operating the absorber50between about 35 and 50 degrees Celsius allows the water vapor, ammonia, and carbon dioxide to form dissolved ammonium bicarbonate. Maintaining between about 35 and 50 degrees Celsius in the absorber50, and a pH less than 9, prevents precipitation of dissolved ammonium bicarbonate or ammonium carbonate and keeps it in dissolved form. Temperature of the absorber50can be maintained by control of the flow and temperature of the cold water53. Following the absorber50, and operating at about the same temperature as the absorber50, the effluent ammonium bicarbonate solution54is treated in a reverse osmosis filter60. Reverse osmosis filter60removes water thereby concentrating the ammonium bicarbonate in the solution. The resulting concentrated effluent64out of the reverse osmosis filter60contains about 50-100 times the concentration of dissolved ammonium bicarbonate in the digestate34. Control of the reverse osmosis temperature is critical to avoid precipitation of the ammonium bicarbonate on the membrane while achieving a concentration sufficient for saturation at the temperature in the crystallizer. The permeate62is a clean water than can be reused or discharged. The concentrated effluent64out of the reverse osmosis filter60is then treated at a temperature of less than about 20 degrees Celsius in stage three using a crystallizer70. Solid crystals of ammonium bicarbonate are grown in the crystallizer70under controlled conditions, separated from the liquid fraction to produce an ammonium-salt74which may be dried, pelletized or granulated to form a final product. In some embodiments, a portion of the saturated ammonium bicarbonate supernatant is recycled72to the reverse osmosis filter60, after it is heated to the required temperature in heat exchanger56. Due to the unique sequence of the preceding unit operations, the resulting ammonium salt may be dried and packaged for commercial distribution as a specialized nitrogen fertilizer, that is high-purity, phosphorus free, and certified USDA organic. The ammonia recovery step is the equivalent of distillation. This allows nearly no salt (including phosphorus salts) carry over to the input to reverse osmosis. Crystallization is another purification step, so that “high-purity, phosphorus free” product is achieved. If synthetic chemicals are not used in obtaining the solid AB or liquid digestate, the ammonium bicarbonate product will have the potential for designation as organic (USDA 2012) fertilizer. The USDA designation is of economic importance as the price of organic fertilizer expressed as dollars per pound ammonia nitrogen, is materially higher than that of chemical (non-organic) fertilizers that are equally uniform, high purity, and concentrated sources of NH3-N. As with synthetic fertilizer, the material is nearly odorless, and has low transport and application costs relative to manure and digestate. If the ammonia is captured with an industrial acid or is derived from application of caustic or other industrial alkali—it will not qualify as organic fertilizer. The ammonium salt according to the invention resolves this conflict by (1) producing ammonia gas thermally with no chemical addition, and (2) using the carbon dioxide found in the digestate to recover the ammonia from the digestate to form an organic fertilizer, ammonium bicarbonate. The ammonium salt74can be stored80for use on or off site. FIG.5is a process flow schematic drawing of a variation on the embodiment of the invention shown inFIG.1for the treatment of livestock manure (e.g., from a Controlled Animal Feeding Operation, CAFO) comprising solids separation, physical influent conditioning, anaerobic digestion, stripping, condensation (concentration), absorption, and crystallization. In theFIG.5process, there is no chemical addition to adjust pH prior to, or in, the stripping process. The present invention excludes the use of pH adjustment chemicals. In the process according toFIG.5, there is also no external supply of carbon dioxide. The carbon dioxide, which derives directly from the livestock manure waste, is supplemented by carbon dioxide from the biogas to assure maintenance of CO2 in the water to stabilize the ammonia in the absorber column.FIG.5shows the biogas32processed in a CO2 removal device35to provide CO2 to for capture of ammonia as ammonium bicarbonate. For example, the device could be a pressure swing adsorption device which is commonly used to separate gases, such as CH4 and CO2, with materially different properties. InFIG.5, footnotes 1-4 denote the following:[1]—vapor is constant composition for continuous operation and varies during a batch process. H20, CO2, and NH3 evolve with traces of organic volatiles and semi-volatiles.[2]—pressure control valve(s) is set to maintain differentials between a) the stripper unit and the condenser, and b) the condenser and the absorber. Absorber temperature, T, must be less than 50 C to keep NH4 and HCO3 in solution, while stripper temperature must be greater than 80 C to convert to NH3 and CO2.[3]—AB solution in absorber is formed from Digester biogas[4]—AB concentrate is supersaturated relative to temperature of crystallizer. As depicted inFIG.5, raw livestock manure10is transported to a solids separation and physical conditioning unit/process20(it being understood that a mixing or holding tank/vessel could be used prior to solids separation and/or can be used for solids separation). The solids separation unit/process may be a single stage or chamber unit or it could be a series of stages or chambers for coarse solids separation, intermediate solids separation, and physical mixing and conditioning. Physical conditioning may include dilution, grinding, mixing, heating etc., depending on the specific livestock manure processed; dilution may be necessary for some manure to provide the appropriate consistency and concentration for the AD, grinding and mixing may be needed to help solubilize and make more available the organic content for digestion, heating may be needed for the anaerobic digester influent but may also be used to sterilize and prevent biological competition during digestion. The slurry/effluent24from the solids separation unit20is input into an anaerobic digester30which digests much, preferably most, of the dissolved organics and small organic particulates to produce biogas32and an effluent digestate34. The effluent digestate34from the anaerobic digester30contains residual solids, dissolved salts and organics, and concentrations of dissolved ammonia and carbon dioxide. The present invention collects the ammonia and carbon dioxide and captures them in a subsequent multistage process to form solid ammonium bicarbonate. Each stage of the subsequent multistage process operates at different temperatures to take advantage of the solubility properties of ammonium bicarbonate for its concentration in dissolved form and then its formation as a nitrogen rich solid. The temperature of digestate34out of a typical anaerobic digester treating livestock manure is about 35 degrees Celsius. For the process of the invention, the digestate needs to be heated to greater than about 80 degrees Celsius for treatment in the stripper40. The stripper operating at a temperature of greater than about 80 degrees Celsius, without any chemical addition to increase pH, creates exhaust vapor42containing water vapor, gaseous carbon dioxide, and gaseous ammonia. Vapor42will also contain traces of organic volatiles and semi-volatiles. The treated water and solids44out of the stripper can be further treated for application to land or water using current treatment technologies. The water vapor42created by stripping the digestate34in that first stage, the separation stage, is then condensed in the condenser. The condenser is operated as a single or multistage unit to condense the water vapor at a high temperature, to separate water from the gaseous ammonia and CO2 effectively concentrating them in the gas. The amount of ammonium carbonate and ammonium bicarbonate concentration in the concentrated gas is at least 2 times greater than in the gas before treatment with condensation and could be as high as 100 times to 1000 times higher. The high temperature condensed water55is removed from the condenser and may be channeled back to the stripper to reclaim any re-dissolved ammonia and carbon dioxide, may be discharged from the process, may be used as seed liquid in the absorber, or may be recycled to combine with the fresh livestock manure entering the digester. Absorber50is used to treat vapor142at a temperature of between about 20 degrees Celsius and 50 degrees Celsius. Pressure control valves48can be used between the stripper40, the condenser, and the absorber50to maintain proper differential pressure between the unit processes. Operating the absorber50between about 20 and 50 degrees Celsius allows the water vapor, ammonia, and carbon dioxide to form dissolved ammonium bicarbonate. Maintaining between about 20 and 50 degrees Celsius in the absorber50, and a pH less than 9, prevents precipitation of dissolved ammonium bicarbonate or ammonium carbonate and keeps it in dissolved form. Temperature of the absorber50can be controlled with a heat exchanger56and by regulating the temperature of the carbon dioxide. Since a majority of the water is condensed and removed from the vapor phase prior to the absorber, the amount of water used to generate the concentrated AB solution is minimized and controlled. The ammonia and carbon dioxide gasses continue to absorb and form an AB solution in the controlled volume of water until they reach close to saturation at the selected temperature between 20 and 50 degrees Celsius. The concentrated effluent64out of the absorber is then treated at a temperature of less than about 20 degrees Celsius in stage four using a crystallizer70. Solid crystals of ammonium bicarbonate are grown in the crystallizer70under controlled conditions, separated from the liquid fraction to produce an ammonium-salt74which may be dried, pelletized or granulated to form a final product. The more dilute AB solution, following this crystallization process, is returned to the absorber as seed liquid to dissolve more ammonia and carbon dioxide as AB under the higher temperature conditions, between 20 and 50 degrees Celsius. The embodiment of the invention shown inFIG.5may increase the overall efficiency by potentially eliminating the need for any other concentrating unit process, specifically the RO, instead performing the concentration through removal of water vapor. Substantial reductions in capital cost, energy costs, operating costs, and maintenance costs could all be realized with that embodiment of the invention. The potential for product losses may also be reduced by eliminating or reducing the reverse osmosis, especially since reverse osmosis operates at relatively high pressures. A safer process may also created by eliminating or reducing the high pressure reverse osmosis, it being understood that the present invention also includes variations with the addition of a reverse osmosis step. The embodiment of the invention shown inFIG.5may eliminate the need for any other concentrating unit process, specifically the RO, instead performing the concentration through removal of water vapor in the partial condenser and capturing the dissolved AB in the absorber. Substantial reductions in capital cost, energy costs, operating costs, and maintenance costs may be realized with that embodiment of the invention. While the present invention has been illustrated by description of various embodiments and while those embodiments have been described in considerable detail, it is not the intention of applicant to restrict or in any way limit the scope of the appended claims to such details. Additional advantages and modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the spirit or scope of applicants' invention. | 37,814 |
11858824 | DETAILED DESCRIPTION OF THE FLOW DIAGRAM Before providing a more detailed description of a preferred embodiment of the present invention with reference to experimental data, it will be useful to provide some explanation of the flow diagram ofFIGS.1and2. FIG.1shows the precipitation of rare earth sulphates (section A), together with the pre-processing of rare earth rich calcium phosphates (section B) and an associated phosphoric acid regeneration stage (section C). InFIG.2, there is shown a series of subsequent rare earth processing stages (section D). It will be appreciated that the focus of the present invention is on the precipitation of rare earth sulphates in section A. Referring firstly toFIG.1, and in process flow order starting with section B, various steps can be seen relating to the production of a suitable crude rare earth sulphate solution10from a rare earth rich calcium phosphate concentrate12, being a product of the beneficiation of a rare earth containing calcium phosphate rich ore by whole-of-ore flotation (not shown). These pre-processing steps include the pre-leach of the concentrate with phosphoric acid in a multi stage counter current configuration14,16to remove calcium phosphate and to form a pre-leach residue18enriched in rare earths and a pre-leach solution19containing monocalcium phosphate, impurities and minor amounts of rare earths. In this embodiment, the leach14,16is operated at a low temperature (typically 30 to 45° C.), with residence times kept to between 30 to 90 minutes for each stage, and with the overall feed acid to feed concentrate mass ratio kept between 2 and 12 grams of P in the acid per gram of Ca in the concentrate. The pre-leach residue18is then combined and cracked using concentrated sulphuric acid in a sulphation stage, being mixed20with sulphuric acid22either at or below an acid bake temperature for a time of up to about 30 minutes to ensure that the resulting mixture is fully homogenised prior to the next steps. Subsequent heating24of the mixture converts the rare earths in the pre-leach residue18to water-soluble rare earth sulphates26. The water-soluble rare earth sulphates26are then cooled to a temperature less than about 50° C. over a time period of up to about 300 minutes to remove as much heat out of the sulphated material26discharging the acid bake24as is practical prior to its use in a subsequent water leach28. The cooled water-soluble rare earth sulphates27are then subjected to a water leach28to place in solution the rare earth sulphate, phosphoric acid and any remaining sulphuric acid, and thus to form the crude rare earth sulphate solution10mentioned above and a water leach residue30containing insoluble gangue material for disposal. Turning now to section A, being the inventive precipitation of rare sulphates,FIG.1shows the sulphate precipitation stage32where the crude rare earth sulphate solution10is subjected to precipitation in the presence of a water soluble, volatile, organic compound (such as methanol)34to produce a rare earth sulphate precipitate36and an acidic supernatant38. The sulphate precipitation32ideally occurs at a temperature in the range of 60 to 65° C. with a residence time in the range of 20 to 40 minutes. While the rare earth sulphate precipitate36subsequently undergoes further process steps that will be described below in relation toFIG.2, the acidic supernatant38produced in the sulphate precipitation step32also undergoes further process steps (section C) aimed at the recovery of the organic compound and the regeneration of phosphoric acid. Section C ofFIG.1thus shows recovering the organic compound from the acidic supernatant38by distillation40, resulting in the formation of recovered organic compound34and a dilute mixed acid solution42, with the recovered organic compound34being recycled for use in the sulphate precipitation step32as the methanol34, and the dilute mixed acid solution42being subjected to additional concentration44by evaporation to form a concentrated mixed acid solution45for use in a phosphoric acid regeneration stage46. Following the phosphoric acid pre-leach14,16mentioned above, heat is applied48to the phosphoric acid pre-leach solution19to precipitate out of solution any minor amounts of rare earths as rare earth phosphates50, leaving a recovery solution52. As can be seen, the rare earth phosphates50are then returned to the acid mix20and acid bake24steps described above. The heating48of the phosphoric acid pre-leach solution19occurs in several stages of increasing temperatures, the temperatures all being in the range of 60° C. to 110° C., with stage residence times of between 60 and 180 minutes. The recovery solution52is then dosed with sulphuric acid54in the acid regeneration stage46and, in this embodiment, also with the concentrated mixed acid solution45, to convert mono calcium phosphate to recoverable phosphoric acid56and form a calcium sulphate precipitate57which may be disposed. This acid addition46is conducted in stages at a temperature of about 40° C. and a residence time of between 30 and 60 minutes per stage. Part of the phosphoric acid formed from the recovery solution58is also used by the pre-leach14,16, while surplus phosphoric acid59is bled out of the system. Turning now toFIG.2, and the final section (section D) of the flow diagram, which shows the subsequent rare earth processing stages, this subsequent processing includes washing and drying the rare earth sulphate precipitate (actually shown inFIG.1as stage60), and subsequently leaching62in water the washed and dried rare earth sulphate precipitate36to dissolve soluble rare earth sulphate and form a leach solution64rich in rare earth sulphate and a leach residue66containing impurities in the form of insoluble phosphates. Then, impurities are precipitated68, with the addition of magnesia63, from the rare earth sulphate leach solution64to form a purified rare earth sulphate solution70and a purification residue72, followed by the precipitation74of the rare earths in the purified rare earth sulphate solution70as rare earth hydroxide precipitate76. Sodium hydroxide77is added to the purified rare earth sulphate solution70to precipitate the rare earths as rare earth hydroxide76, with the addition of hydrogen peroxide78to oxidise cerium contained in the precipitate. The production of rare earth hydroxide76occurs in a two-stage counter current process, with purified rare earth sulphate solution70feeding into the precipitation stage (stage one)74to precipitate a crude rare earth hydroxide75containing some sulphate using spent solution71from the refining stage (stage two)73, with the conversion of rare earth sulphate compounds to rare earth hydroxide compounds occurring with the addition of fresh sodium hydroxide77in rare earth hydroxide refining (stage two)73. The rare earth hydroxide precipitate76then undergoes selective leaching79,80,82with hydrochloric acid to form the rare earth chloride solution86and the residue88with the rare earth solution86containing negligible cerium, and the residue88consisting primarily of cerium (IV) hydroxide. The selective leaching79,80,82of the rare earth hydroxide precipitate76is conducted in a multi stage configuration, with hydrochloric acid diluted to 10% w/w using polished stage one80leach solution prior to its addition to stage one80and stage two82leach tanks, over multiple tanks in each stage, and stage two82solution is used to re-pulp and leach rare earth hydroxide cake prior to stage one80leach. The cerium (IV) hydroxide residue88is then packaged as a crude cerium product, while the rare earth chloride solution86is dosed with barium chloride90to remove radium via co-precipitation with barium sulphate and form a purified rare earth chloride solution92. The purified rare earth chloride solution92is then concentrated by evaporation94. Description of Experimental Data Attention will now be directed to a description of experimental data developed to illustrate a preferred embodiment of the present invention. Rare Earth Sulphate Precipitation Rare earth sulphate precipitation tests were conducted by contacting a measured quantity of pre-heated water leach solution with a measured quantity of ambient temperature methanol in a suitable well agitated baffled vessel fitted with reflux condenser to minimise evaporative loss. The resulting mixture was maintained at a setpoint temperature for a specified duration, then vacuum filtered. The filter cake was then washed thoroughly with methanol to remove entrained solution prior to drying. The Influence of Temperature (Tests 1 and 2) Two rare earth sulphate precipitation tests were conducted to evaluate the influence of reaction temperature on performance. One test was conducted at 60 to 65° C. (Test 1) while the other was conducted at 40 to 45° C. Both tests were conducted on the same water leach solution (Table 1) and were contacted with 1 gram of methanol per gram of water leach solution for 30 minutes. The results are summarised in Tables 2 to 4. The results indicate that operating at lower temperatures results in reduced Al, P, Fe, Th, and U co-precipitation with rare earth sulphate. TABLE 1Feed solution compositionLREMREHREYTREAlPSCaFeThUTestg/Lmg/Lmg/Lmg/Lg/Lg/Lg/Lg/Lmg/Lg/Lg/Lmg/L1 & 215.07109013015.92.6933.276.53393.321.59156 TABLE 2Final solution compositionLREMREHREYTREAlPSCaFeThUTestmg/Lmg/Lmg/Lmg/Lmg/Lg/Lg/Lg/Lmg/Lg/Lg/Lmg/L14279228646101.4619.239.6731.806607724749528636591.3918.639.6561.7771077 TABLE 3Rare earth sulphate precipitate composition (% w/w or g/t)LREMREHREYTREAlPSCaFeThUTest%%g/tg/t%g/t%%%g/t%g/t140.31.2161175741.64760.2314.10.416290.761.6240.71.1751463742.04240.1814.10.465590.471.2 TABLE 4Precipitation extent (%)TestLREMREHREYTREAlPSCaFeThU194.871.729.918.792.90.60.26.452.30.718.10.0294.069.125.115.692.10.60.26.159.70.610.70.0 The Influence of Contact Ratio and Residence Time (Tests 3 to 9) Two sets of rare earth sulphate precipitation tests were conducted to evaluate the influence of organic to aqueous contact ratio and residence time on performance. Four contact ratios (0.25, 0.5, 0.75, and 1) were tested in the first set of tests (Tests 3 to 6 respectively). Subsamples were collected at 30, 60, and 120 minutes (subsamples A, B, and C) in each of the tests 3 to 6. The second set of tests (Tests 7 to 9) evaluated shorter residence times (10, 20, and 30 minutes respectively) with a contact ratio of 1 using a different feed solution to the first set (see Table 5). All tests (Tests 3 to 9) used methanol as the organic phase, and were conducted with a 60 to 65° C. temperature target while experienced temperatures ranging between 55 to 70° C. The results are summarised in Tables 6 to 8. The results indicate that operating at lower organic to aqueous contact ratios reduces the rare earth element precipitation extent. The results indicate that rare earth sulphate precipitation is effectively complete within the shortest residence time tested (10 minutes in Test 7), while the precipitation of impurities such as thorium are effectively complete by 20 minutes, with negligible additional precipitation observed with extended contact durations. TABLE 5Feed solution compositionLREMREHREYTREAlPSCaFeThUTestg/Lmg/Lmg/Lmg/Lg/Lg/Lg/Lg/Lmg/Lg/Lg/Lmg/L3-629.2104816224130.73.314.453.49503.02.332357-924.689011520525.84.014.140.412202.41.90168 TABLE 6Final solution compositionLREMREHREYTREAlPSCaFeThUTestmg/Lmg/Lmg/Lmg/Lmg/Lg/Lg/Lg/Lmg/Lg/Lg/Lmg/L3A2748939864881.56.0119.31301.30.911063B2919040875081.56.0419.11401.40.931073C2649040914851.66.1818.71401.50.971134A67410643969191.77.0823.31701.61.011214B782107459810321.77.2324.21801.61.051264C5889742948211.76.7922.01701.60.961215A17212116513321302.18.2325.82501.91.291475B18392226714122692.28.7829.82601.91.381545C25442487315130162.39.4332.23002.11.501626A572145710017664532.610.437.05202.41.801846B528744810018660212.710.435.25302.41.861866C726549810619380622.811.036.45702.61.9819173895624585271.76.0514.2801.10.397584435823575801.76.2016.3<501.00.287593945222545231.86.2916.8<501.00.2778 TABLE 7Rare earth sulphate precipitate composition (% w/w or g/t)LREMREHREYTREAlPSCaFeThUTest%%g/tg/t%g/t%%%g/t%g/t3A40.71.19695103042.11060.3714.80.747691.065.13B40.51.18682100041.81060.3714.90.777691.014.73C40.61.17698102041.91060.3814.90.807691.065.54A40.41.21801126041.92120.4114.90.778391.167.54B39.21.16755114040.52120.3914.70.768391.086.04C39.51.18758114040.91590.4114.80.808391.165.45A40.31.0657682641.51060.4014.90.767690.946.05B39.51.0956780140.7530.3914.80.737690.934.55C39.81.0857080041.0530.4014.80.776990.945.36A41.00.9036947342.0<530.3514.70.494900.622.06B40.30.8835545341.2<530.3414.70.475600.602.16C40.80.8735546141.7<530.3814.70.555250.582.5738.91.21881135040.316411.2114.11.5222382.1230837.91.20939144039.324871.8913.61.6535672.6553938.11.26997159039.625401.8913.71.6733572.7452 TABLE 8Precipitation extent (%)TestLREMREHREYTREAlPSCaFeThU3A97.880.335.326.896.30.21.918.963.61.826.20.13B97.880.435.126.496.30.21.919.663.31.725.30.13C98.181.436.627.296.70.22.021.065.71.726.90.24A95.580.039.431.594.10.42.018.361.41.828.70.24B94.779.637.829.593.40.41.918.060.21.927.00.24C96.382.341.131.795.00.42.320.464.32.031.70.25A90.366.726.119.888.60.21.918.754.61.622.40.25B89.766.425.318.687.90.11.816.753.11.621.40.15C87.065.025.018.585.30.11.816.552.21.421.10.16A72.942.412.29.271.0—1.213.026.30.811.50.06B76.746.013.49.574.8—1.415.327.81.012.20.06C69.341.311.98.767.5—1.414.027.80.810.50.1796.786.152.040.395.72.75.522.484.65.661.31.2896.286.154.843.295.34.28.319.9—9.673.92.1996.788.157.747.495.94.18.420.0—9.375.52.0 The Influence of Feed Composition (Tests 10 to 24) Fifteen rare earth sulphate precipitation tests were conducted to evaluate the influence of variation in feed composition on precipitation performance. Each test used a different crude rare earth sulphate feed solution (Table 9), was contacted with methanol with a 1 to 1 w/w contact ratio for 30 minutes, with a 60 to 65° C. temperature target while experienced temperatures ranging between 55 to 70° C. The results are summarised in Tables 10 to 12, from which it can be seen that most tests resulted in a relatively clean rare earth sulphate precipitate with some variation in iron aluminium and phosphate co-precipitation. To understand this impurity co-precipitation, the results have been condensed down and sequenced according to the free sulphuric acid content of crude rare earth sulphate feed solution for each test (Table 13). This free acid value is a calculated value for convenience and may not reflect the actual speciation which takes place in the feed solution. The free acid content was determined by summing up all the cations and anions measured and inferred from solution assay result with the concentration of protons calculated to balance cations and anions. It was then assumed that all phosphate is present as phosphoric acid with remaining protons assigned as sulphuric acid. For Test 13 this resulted in a negative content of sulphuric acid which suggests that either the phosphate is not fully protonated or that assay uncertainty has biased cations over anions. Either way, Test 13 is low on free acid, and a significant fraction of the precipitating rare earth elements have precipitated as phosphates. Overall the results suggest that in order to minimise the precipitation of rare earth elements as phosphates, the from phosphate containing crude rare earth sulphate solution should contain 5% w/w or more free H2SO4as it has been defined here. TABLE 9Feed solution compositionLREMREHREYTREAlPSCaFeThUTestg/Lmg/Lmg/Lmg/Lg/Lg/Lg/Lg/Lmg/Lg/Lg/Lmg/L1013.45087312214.10.96.2524.811800.800.781101111.84496410812.41.711.251.310431.280.69971220.76257915521.67.631.350.48104.902.241931320.86848516321.712.140.125.433203.301.171671427.798513123329.18.029.547.98503.802.472221527.6107315323229.05.3937.91124204.712.352281634.1142416728835.93.8326.699.78183.413.483071732.8132315826734.53.2323.891.65732.373.292851834.2153417033236.32.6524.81065753.963.733381922.580211620423.61.5831.495.07200.592.241972024.690713023325.91.7133.21065250.912.512252115.557410922416.42.2139.41293061.402.86265229.623458518610.22.8444.41571472.303.35319238.69245651499.143.5251.2184943.293.763672415.44936412316.16.8948.089.54645.251.81169 TABLE 10Final solution compositionLREMREHREYTREAlPSCaFeThUTestmg/Lmg/Lmg/Lmg/Lmg/Lg/Lg/Lg/Lmg/Lg/Lmg/Lmg/L101892111282500.32.018.51800.36849.8112694917353710.74.5220.12300.535343.5125905217457043.512.416.51001.961783.413104156191443.713.38.871100.62053.3144133716425092.410.815.0<501.541480.6152808736674682.517.545.31252.1781799.0163927130695631.5810.736.01901.38923125172903522554011.299.9734.51000.97816130183938239835971.0311.144.11201.631165159193545924564940.6313.839.71080.2562981.6203206827624780.7215.045.6870.3969286.6213666828655260.8817.45.24640.56896102223455222544720.9318.45.06280.75937102234774920505961.3724.67.16101.261275134244416017405573.0923.83.52552.2173271.9 TABLE 11Rare earth sulphate precipitate composition (% w/w or g/t)LREMREHREYTREAlPSCaFeThUTest%%g/tg/t%%%%%%%g/t1035.81.221172189037.30.111.6214.22.120.212.24451138.11.0867093239.40.0050.2915.31.440.050.792.61238.81.01706119039.90.151.6613.61.330.161.90291324.30.77799141025.33.3811.47.213.582.203.354101436.51.24964151038.00.121.7312.40.970.172.42191540.01.18712105041.4<0.0050.2214.70.320.060.611.41640.11.23910147041.60.0050.2314.60.490.061.243.61740.11.281225220041.70.0050.2414.60.440.061.704.51839.71.381056167041.4<0.0050.2114.50.400.071.535.41940.11.22865136041.6<0.0050.2814.90.730.041.172.92041.71.29926143043.2<0.0050.2514.80.410.041.152.22141.81.17979155043.3<0.0050.2314.70.290.041.442.42241.20.97898152042.4<0.0050.2314.70.180.051.882.42340.90.68596104041.7<0.0050.2515.00.300.051.667.02439.70.8849878740.70.020.7314.70.930.060.515.5 TABLE 12Precipitation extent (%)TestLREMREHREYTREAlPSCaFeThU1096.388.860.348.295.44.910.018.878.68.882.01.21194.673.332.424.793.00.10.88.743.71.221.70.11293.380.546.836.192.40.92.815.073.91.839.70.71398.894.681.372.198.423.822.721.891.855.798.320.91495.889.560.448.095.11.34.017.7—2.960.20.61597.578.434.829.595.9—0.38.040.70.716.50.01696.582.344.936.495.20.10.69.841.11.126.50.11797.691.662.254.096.80.10.711.156.61.738.00.11896.582.343.135.795.0—0.58.448.01.226.70.11996.181.743.734.794.8—0.47.659.53.528.80.12096.881.243.834.595.4—0.46.951.82.427.60.12194.070.232.124.691.8—0.23.737.90.818.00.02289.156.121.716.286.0—0.11.930.30.412.00.02385.649.217.012.782.9—0.11.467.60.38.30.02492.968.330.022.591.40.10.45.771.10.49.20.1 TABLE 13Rare earth sulphate composition and precipitationextents as a function of free acidFeed FreePrecipitate CompositionPrecipitation ExtentAcid(% w/w)(%)Test% w/w H2SO4TREEPAlFeTREEPAlFe13−2.525.311.43.382.2098.422.723.855.7104.337.31.620.110.2195.410.04.98.8144.538.01.730.120.1795.14.01.32.9125.739.91.660.150.1692.42.80.91.8119.939.40.290.0050.0593.00.80.11.22413.740.70.730.020.0691.40.40.10.41714.841.70.240.0050.0696.80.70.11.71615.941.60.230.0050.0695.20.60.11.11916.141.60.28<0.0050.0494.80.4—3.51816.941.40.21<0.0050.0795.00.5—1.21517.741.40.22<0.0050.0695.90.3—0.72017.743.20.25<0.0050.0495.40.4—2.42121.343.30.23<0.0050.0491.80.2—0.82225.242.40.23<0.0050.0586.00.1—0.42328.141.70.25<0.0050.0582.90.1—0.3 Phosphoric Acid Pre-Leach Pre-leach tests were conducted by contacting a measured quantity of temperature controlled phosphoric acid solution with a measured quantity of concentrate in a suitable well agitated baffled vessel. The resulting mixture was maintained at a setpoint temperature for a specified duration, then vacuum filtered. The filter cake was then washed thoroughly with DI water to remove entrained solution prior to drying. The Influence of Concentrate Feed Variability Five pre-leach tests were conducted to evaluate the influence of variability in the feed concentrate composition (Table 14) on the performance of pre-leach. Each test was conducted using the same feed acid (Table 15), with an acid to concentrate contact ratio of 8.4 grams of P in acid per gram of Ca in the concentrate, at 30° C. for two hours. The results are summarised in Table 16. TABLE 14Feed concentrate composition (% w/w or g/t)LREMREHRETREMgAlPSCaFeThUTest%%g/t%%%%%%%%g/t245.300.213655.620.251.4712.80.2429.31.240.48355255.190.203565.500.071.3713.00.1929.32.110.49395263.710.142273.920.371.0111.20.1331.70.670.44217275.500.213875.830.044.1811.70.0722.40.440.57415285.870.223486.190.010.0816.00.2434.60.250.90373 TABLE 15Feed acid composition (g/L or mg/L)LREMREHRETREMgAlPSCaFeThUTestmg/Lmg/Lmg/tmg/Lg/Lg/Lg/Lmg/Lg/Lg/Lmg/Lmg/L24 to 280.3——0.46.76.6207<104.36.20.4<0.001 TABLE 16Dissolution extent (%)TestLREMREHRETREMgAlPSCaFeThU2436.642.947.237.176.59.083.222.887.111.638.031.02534.845.452.135.544.32.883.785.884.01.632.738.42672.474.475.172.517.09.787.587.386.811.774.176.02718.427.134.819.146.816.663.159.372.03.846.326.12838.543.149.938.841.417.083.189.187.50.727.734.5 The Influence of Feed Acid Composition Five pre-leach tests were conducted to evaluate the influence of variability in the feed acid composition (Table 17) on the performance of pre-leach. Each test was conducted using the same feed concentrate (Table 18), with an acid to concentrate contact ratio of 13 grams of acid per gram of feed concentrate, at 30° C. for two hours. The results are summarised in Table 19. TABLE 17Feed acid composition (% w/w or g/t)LREMREHRETREMgAlPSCaFeThUTestmg/Lmg/Lmg/Lmg/Lg/Lg/Lg/Lmg/Lg/Lg/Lmg/Lmg/L2950.3——50.43.73.6176<104.73.4<0.1<0.13047.1——47.37.47.2181<104.96.91.2<0.13140.3——40.613.37.0174<104.96.3<0.1<0.13230.0——30.27.210.91825105.06.8<0.1<0.13336.0——36.27.27.3177<104.93.3<0.1<0.1 TABLE 18Feed concentrate composition (% w/w or g/t)LREMREHRETREMgAlPSCaFeThUTest%%g/t%%%%%%%%g/t29 to 335.570.223925.900.231.3213.10.2330.11.160.51377 TABLE 19Dissolution extent (%)TestLREMREHRETREMgAlPSCaFeThU2931.236.746.331.780.4085.290.590.16.931.225.73030.135.341.930.581.03.374.582.979.48.431.626.23125.227.632.925.579.50.363.072.768.16.226.919.93229.431.937.929.780.82.069.177.274.07.832.223.53331.632.138.431.880.91.676.384.381.27.933.525.0 Continuous Two Stage Counter Current Leach A continuous two-stage pre-leach circuit test was conducted (Test 34). For this test, a thickener was used for first stage solid liquid separation, while thickening with filtration of thickener underflow was used for solid liquid separation in the second stage. The first stage featured a single tank with 30 minute residence time operated at 40 to 45° C., while the second stage contained two 30 minute residence time tanks operated at 30° C. Stage one thickener underflow fed into the first stage two leach tank along with phosphoric acid (Table 20). Stage two thickener overflow was combined with primary filtrate and spent wash solution, then fed into the stage one leach tank along with damp (9% moisture) concentrate (Table 21). Stage one thickener overflow was continuously withdrawn from the system as was washed leach residue cake from stage two. For every kilogram of concentrate (dry basis) feeding into the stage one leach tank, 10.6 kg of phosphoric acid was fed into the first stage two leach tank. The circuit performance is summarised in Table 22. TABLE 20Feed acid composition (g/L or mg/L)LREMREHREYTREAlPSCaFeThuTestg/Lmg/Lmg/Lmg/Lg/Lg/Lg/Lg/Lg/Lg/Lg/Lg/L34—————5.721226.37.2—— TABLE 21Feed concentrate composition (% w/w or g/t)LREMREHREYTREAlPSCaFeThUTest%%g/tg/t%%%%%%%g/t345.60.244138355.91.512.40.229.61.30.46422 TABLE 22Pre-leach residue composition (% w/w or g/t)LREMREHREYTREAlPSCaFeThUTest%%g/tg/t%g/t%%%g/t%g/t3411.20.42663128011.73.86.51.912.53.00.97852 Rare Earth Recovery Rare earth recovery tests were conducted by heating a measured quantity of pre-leach solution (rare earth recovery feed solution) to boiling in a suitable well agitated baffled vessel fitted with a reflux condenser. The resulting mixture was maintained under a continuous state of boiling for 120 minutes, then vacuum filtered. The filter cake was then washed thoroughly with DI water to remove entrained solution prior to drying. Five rare earth recovery tests were conducted to evaluate the influence of variability in the feed solution composition (Table 23) on the performance of rare earth recovery. The results are summarised in Tables 24 and 25. TABLE 23Feed solution composition (% w/w or g/t)LREMREHREYTREMgAlPCaFeThUTestg/Lmg/Lmg/Lmg/Lg/Lg/Lg/Lg/Lg/Lg/Lmg/Lmg/L352.1111223422.283.833.5819236.53.4413914361.9510321382.117.457.1619633.26.7313814371.748818331.8814.17.2018229.56.7011412381.849520361.997.4010.918631.56.9012912391.9110522382.077.097.0018232.83.3014114 TABLE 24Precipitate composition (% w/w or g/t)LREMREHREYTREMgAlPCaFeThUTest%%g/tg/t%g/t%%%%%g/t3531.21.0570364532.4<600.1311.74.560.342.97243625.60.7449946926.4<600.179.163.420.482.448.03725.30.7756253226.2<600.169.213.370.702.338.93824.10.6645541124.8<600.198.823.220.562.29113925.70.7553050026.5<600.199.083.470.272.528.8 TABLE 25Precipitation extent (%)TestLREMREHREYTREMgAlPCaFeThU3580.152.122.67.676.9—0.180.300.610.4991.80.823671.242.216.96.468.1—0.120.240.520.3780.00.303781.147.117.88.077.5—0.110.250.560.5185.40.383868.635.211.55.665.2—0.080.230.500.3976.00.433973.642.617.16.870.1—0.140.260.540.4183.10.33 Phosphoric Acid Regeneration A continuous phosphoric acid regeneration circuit test was conducted (Test 40). The circuit featured a single 55 minute residence time precipitation tank (Tank 1) operated at 44° C., followed by a 78 minute stabilisation tank (Tank 2) and batch vacuum filtration, which was supported by duty standby filter feed tanks and was operated with counter current washing. Recovery solution was fed into the precipitation tank along with mixed acid (Table 26). The regeneration performance is summarised in Tables 27 and 29. TABLE 26Feed solution composition (g/L or mg/L)LREMREHREYTREAlPSCaFeThUSolutionmg/Lmg/Lmg/Lmg/Lmg/Lg/Lg/Lg/Lg/Lg/Lmg/Lmg/LRecovery57094401167044.871840.8227.05.422653Mixed—————3.284379—3.2—— TABLE 27Precipitate composition (% w/w or g/t)LREMREHREYTREAlPSCaFeThUTankg/tg/tg/tg/tg/tg/t%%%g/tg/tg/t11134852452124418521.7919.225.4420312.221082862454119217991.6819.225.3420311.9 TABLE 28Regenerated solution composition (g/L or mg/L)LREMREHREYTREAlPSCaFeThUTankmg/Lmg/Lmg/Lmg/Lmg/Lg/Lg/Lg/Lg/Lg/Lmg/Lmg/L143683381055584.7519.42.223.915.8826.553.1246186391145864.6319.31.663.825.9127.253.8 TABLE 29Overall precipitation extent (%)TankLREMREHREYTREAlPSCaFeThU121.09.56.04.818.53.80.989.886.90.710.80.4218.08.55.54.216.03.50.891.586.10.79.50.3 Acid Bake and Water Leach Acid bake water leach tests were conducted by contacting a measured quantity of sulphuric acid with a measured quantity of pre-leach residue with thorough mixing in a suitable dish. The resulting mixture was placed in a furnace and raised to 250° C. over a period of up to 50 minutes, then held at 250° C. for a period of 30 minutes, withdrawn from furnace and allowed to cool. The cool sulphated material was then added to a measured quantity of 5° C. DI water, agitated for 10 minutes, then vacuum filtered. The filter cake was then washed thoroughly with DI water to remove entrained solution prior to drying. Six acid bake water leach tests (Tests 41 to 46) were conducted to evaluate the influence of variability in the feed pre-leach residue composition (Table 30) on the performance of acid bake water leach. Each test was conducted using an acid to residue contact ratio of 1600 kg of H2SO4per tonne of leach residue, and 2.5 g of DI per gram of pre-leach residue. The results are summarised in Tables 31 to 33. TABLE 30Feed pre-leach residue composition (% w/w or g/t)LREMREHREYTREAlPSCaFeThUTest%%g/t%%%%%%%%g/t4111.20.406420.1311.74.457.160.6412.53.640.988144210.10.335100.1010.63.996.330.0814.06.200.99729434.150.152290.054.363.695.670.0717.02.400.46211448.440.294750.098.866.568.070.0511.80.800.585774518.50.658910.1919.40.3613.90.1322.21.283.3312504612.50.447060.1413.19.666.460.022.291.851.42839 TABLE 31Water leach solution composition (g/L or mg/L)LREMREHREYTREAlPSCaFeThUTestg/Lg/Lmg/Lmg/Lg/Lg/Lg/Lg/Lg/Lg/Lg/Lmg/L4134.91.2417030836.71.7922.71040.583.082.792804228.00.8610819329.21.5618.71080.867.352.502194310.00.32346510.40.5316.798.61.300.201.06664425.30.819718326.40.8723.392.91.460.161.561984552.11.7120737252.10.9538.786.00.613.484.683744642.51.4922038242.50.5817.996.41.370.274.35315 TABLE 32Water leach residue composition (% w/w or g/t)LREMREHREYTREAlPSCaFeThUTest%g/tg/tg/t%%%%%%g/tg/t410.262641182000.323.930.5413.810.62.4425116.5420.29193831530.344.070.368.8912.23.6314121.6430.18152621160.213.550.239.4512.42.1048012.4440.10139621090.135.560.9214.35.340.662678.6450.688972614330.840.350.3421.325.90.26466024.9460.1273561100.147.471.1514.74.151.3560914.6 TABLE 33Dissolution extent (%)TestLREMREHREYTREAlPS[1]CaFeThU4198.094.584.185.097.71.493.925.51.531.797.698.44297.995.586.385.897.715.596.214.52.249.398.898.04395.589.068.168.394.95.496.519.92.83.589.495.34498.594.080.982.098.24.187.436.03.86.294.198.44597.490.379.480.796.956.998.233.51.086.783.098.64698.897.889.788.598.61.777.440.816.84.294.097.9[1]deportment from sulphuric acid to water leach residue for S Rare Earth Sulphate Dissolution Rare earth sulphate dissolution tests are typically conducted by contacting a measured quantity of dry rare earth sulphate precipitate with a measured quantity of DI water with thorough mixing in a suitable well agitated baffled vessel, at 40° C. for a period of 120 minutes, then vacuum filtered. The filter cake was then washed thoroughly with DI water to remove entrained solution prior to drying. Five rare earth sulphate dissolution tests (Tests 47 to 51) were conducted to evaluate the influence of variability in the feed composition (Table 34) on the performance of dissolution. Each test was conducted using a water to feed solids contact ratio of 13 grams of DI water per gram of feed solid. Test 47 was operated with a 60 minute dissolution at 22° C., while tests 48 to 51 were operated with a 120 minute dissolution at 40° C. The results are summarised in Tables 35 to 37. TABLE 34Feed rare earth sulphate composition (% w/w or g/t)LREMREHREYTREAlPSCaFeThUTest%%g/tg/t%g/t%%%g/t%g/t4735.21.05833136336.591853.8812.21.9769022.511234840.01.18712105041.4<530.2214.70.325600.611.44943.41.28999168044.92120.2414.90.517691.473.75041.20.97898152042.4<530.2314.70.174901.882.45140.31.2161175741.64760.2314.10.416290.761.6 TABLE 35Dissolution solution composition (g/L or mg/L)LREMREHREYTREAlPSCaFeThUTestg/Lmg/Lmg/Lmg/Lg/Lmg/Lmg/Lg/Lmg/Lmg/Lmg/Lmg/L4711.4401436811.950029506.286904004.83.34834.51120927835.8190514.3223101030.154929.610849411930.920<312.1293202860.385034.68439112235.6<10412.8239<103450.175127.2875707228.2<10<310.1166101100.19 TABLE 36Dissolution residue composition (% w/w or g/t)LREMREHREYTREAlPSCaFeThUTest%%g/tg/t%g/t%%g/tg/t%g/t4735.20.9147153636.257168.037.5319900146184.971454836.90.8618011737.8179910.20.35<72573523.33.84922.50.5316814223.12657.778.011001510639.13.7505.010.1251415.13<538.252.82<71545651.04.15130.80.641054631.43188.654.13786566421.83.7 TABLE 37Dissolution extent (%)TestLREMREHREYTREAlPSCaFeThU4753.559.573.781.753.871.03.571.353.01.37.645.04897.898.299.499.797.8—2.799.982.221.26.293.24998.799.099.699.898.796.9—98.799.532.334.197.55099.999.999.910099.9—2.099.8——73.198.35198.298.899.699.998.298.4—99.399.620.932.694.5 Rare Earth Purification Rare earth purification tests (Tests 52 and 53) were conducted by dosing magnesia, to a pH 5 endpoint target, to a measured quantity of impure rare earth sulphate solution at 40° C. in a suitable well agitated baffled vessel with online pH measurement. The resulting mixture was mixed for a period of 30 minutes following magnesia addition to allow it to stabilise, then vacuum filtered. The filter cake was then washed thoroughly with DI water to remove entrained solution prior to drying. Two rare earth purification tests were conducted to evaluate the influence of variability in the source magnesia (Table 38) on the performance of rare earth purification from a common feed solution (Table 39). The results are summarised in Tables 40 to 42. In both tests (52 and 53), 0.16 kg of MgO was dosed per tonne of feed solution. There was 97.3% utilisation of magnesia in Test 52, and a 91.1% utilisation of magnesia in Test 53. TABLE 38Magnesia composition (% w/w or g/t)LREMREHRETREMgAlPSCaFeThUTestg/tg/tg/tg/t%%g/tg/t%%g/tg/t52289.83.74939.90.0922802.420.18<10.1553268.63.84638.30.05<4400.510.0650.09 TABLE 39Feed solution composition (g/L or mg/L)LREMREHRETREMgAlPSCaFeThUTestg/Lmg/Lmg/Lg/Lmg/Lmg/Lmg/Lg/Lmg/Lmg/Lmg/Lmg/L52 & 5320.27254821.1<2<10147.6488<11130.76 TABLE 40Precipitate composition (% w/w or g/t)LREMREHRETREMgAlPSCaFeThUTest%%g/t%%%g/t%%%%g/t5230.12.38153332.70.611.368827.330.212.0618.517.25324.51.74103026.42.851.8311576.050.102.6722.717.2 TABLE 41Purified rare earth sulphate solution composition (g/L or mg/L)LREMREHRETREMgAlPSCaFeThUTestg/Lmg/Lmg/Lg/Lmg/Lmg/Lmg/Lg/Lmg/Lmg/Lmg/Lmg/L5220.17044520.979<10118.4892<10.560.455319.87224520.765<10<38.2989<11.740.13 TABLE 42Precipitation extent (%)TestLREMREHRETREMgAlPSCaFeThU520.440.970.950.46——1.90.280.67—99.541.2530.230.460.420.24——1.60.150.22—98.582.9 RE Hydroxide Precipitation The Influence of Reagent Rare earth hydroxide precipitation tests (Tests 54 to 56) were conducted by contacting a measured quantity of magnesia or sodium hydroxide to a measured quantity of purified rare earth sulphate solution at 55° C. in a suitable well agitated baffled vessel. The resulting mixture was mixed for a period of 30 minutes following each dose of reagent addition to allow it to stabilise, then subsample collected, and vacuum filtered. Subsample filter cake was then washed thoroughly with DI water to remove entrained solution prior to drying. For each test, a range of subsamples were collected to cover a range of reagent doses. Following the final precipitation subsample, a measured quantity of hydrogen peroxide was added to the remaining slurry. The resulting mixture was mixed for a period of 30 minutes to allow it to stabilise, then vacuum filtered. Two of the rare earth hydroxide precipitation tests (Test 54 and 55) were conducted to evaluate the influence of variability in the source of magnesia (Table 43) on the performance of rare earth hydroxide precipitation, while the third test (Test 56) evaluated the use of sodium hydroxide. All three tests were based on a common feed solution (Table 44). Reagent dosing is summarised in Table 45. The results are summarised in Tables 46 and 47. From the results it can be seen that the use of magnesia results in significantly increased impurities in the resultant precipitate relative to precipitation using sodium hydroxide. In addition, increased dose rates result in reduced overall deportment of sulphate to rare earth hydroxide precipitate. TABLE 43Magnesia composition (% w/w or g/t)LREMREHRETREMgAlPSCaFeThUTestg/tg/tg/tg/t%%g/tg/t%%g/tg/t54289.83.74939.90.0922802.420.18<10.1555268.63.84638.30.05<4400.510.0650.09 TABLE 44Feed solution composition (g/L or mg/L)LREMREHRETREMgAlPSCaFeThUTestg/Lmg/Lmg/Lg/Lmg/Lmg/Lmg/Lg/Lmg/Lmg/Lmg/Lmg/L54 to 5620.57604821.472<10<37.4990<10.730.21 TABLE 45Reagent Addition[1]SampleABCDE548.69.19.610.2125558.69.09.610.11265616.917.919.020.1126[1]Subsamples A through D correspond to periods of magnesia (Tests 54 and 55) or sodium hydroxide (Test 56) addition, where dosing is in the units kg Magnesia or NaOH per t of feed. Subsample E corresponds to a period of hydrogen peroxide dosing with reagent addition expressed as a percentage of stoichiometry. TABLE 46Precipitate composition (% w/w or g/t)LREMREHRETREMgAlPSCaFeThUTest%%g/t%%g/tg/t%%g/tg/tg/t54A51.91.5271353.62.803181096.570.177691091.2554B53.91.6074455.72.98318925.730.16839781.4854C57.01.6778358.92.46265924.250.21909821.3354D56.61.6577758.42.76265833.450.14909841.3454E58.61.7582660.52.48529923.040.171049871.4455A51.41.5473353.12.35212926.770.06489741.1655B50.71.5171552.42.36159875.810.15489751.1755C50.61.5071752.32.40159875.170.20489741.2155D50.11.5071051.72.81159834.850.21559731.1955E52.71.5776254.42.53212924.410.20629791.2156A58.81.7384460.80.23<53833.100.34489861.3356B63.81.8993465.90.23<53962.600.41489971.4856C63.11.8888665.20.22<53921.600.46489931.4856D63.91.9090766.00.22<53741.170.44420961.5556E67.82.0496870.10.23<53870.460.51489972.20 TABLE 47Precipitation extent (%)TestLREMREHRETREMgAlPSCaFeThU54A99.499.399.299.4———38.422.5—90.39754B99.999.999.899.9———33.020.7—90.3>9754C10099.9100100———23.322.3—92.2>9754D99.999.999.999.9———17.915.2—93.8>9754E99.999.910099.9———14.617.4—94.1>9755A99.510010099.5———36.515.4—93.5>9755B99.999.999.999.9———30.136.8—94.9>9755C10099.899.599.9———31.848.1—90.5>9755D99.999.999.999.9———24.947.6—87.9>9755E99.999.999.999.9———22.448.0—92.8>9756A99.899.899.799.8———13.586.5—93.3>9656B99.999.999.999.9———11.393.7—94.4>9656C99.999.899.999.9———6.6>97—95.1>9556D99.899.899.899.8———4.6>97—95.3>9556E99.999.999.999.9———1.7>97—95.8>95 Two Stage Rare Earth Hydroxide Production A rare earth hydroxide precipitation test (Test 57) was conducted by contacting a measured quantity sodium hydroxide (97% of stoichiometry) to a measured quantity of purified rare earth sulphate solution (Table 48) at 55° C. in a suitable well agitated baffled vessel. The resulting mixture was mixed for a period of 30 minutes to allow it to stabilise, then a measured quantity of hydrogen peroxide (117% of stoichiometry) was added. The resulting mixture was mixed for a period of 30 minutes to allow it to stabilise, then vacuum filtered. For the second stage, the unwashed cake from the first stage was repulped in DI water along with a measured quantity of sodium hydroxide (same mass as first stage). The mixture was agitated for 60 minutes at 55° C. then vacuum filtered. The resultant cake was washed. The results are summarised in Tables 49 to 50. TABLE 48Feed solution composition (g/L or mg/L)LREMREHRETREMgAlPSCaFeThUTestg/Lmg/Lmg/Lg/Lmg/Lmg/Lmg/Lg/Lmg/Lmg/Lmg/Lmg/L5720.56323921.280<10<38.12283<101.20.05 TABLE 49Precipitate composition (% w/w or g/t)LREMREHRETREMgAlPSCaFeThUStage%%g/t%%g/tg/t%%g/tg/tg/t164.61.5774866.40.29<531752.380.33350692.09266.91.6980268.80.34<53870.300.46280732.36 TABLE 50Precipitation (Stage 1) or dissolution (Stage 2) extent (%)StageLREMREHRETREMgAlPSCaFeThU199.999.899.999.997.0——10.075.6—97.9>80200000009300521 Selective Dissolution The Influence of Rare Earth Concentration A series of four two stage rare earth hydroxide dissolution tests (Tests 58 to 61) were conducted at 70° C. in a suitable well agitated baffled vessel with online pH measurement. Each test starts by simulating the second stage by dosing with a measured portion of 10% w/w hydrochloric acid to a measured portion of rare earth hydroxide cake (Table 51) that has been repulped in DI water (Test 58) or rare earth chloride solution (Tests 59 to 61), followed by a 30 minute period of stabilisation. Typically, this results in a slurry pH of around 1.2 to 2.2. Each test then concludes with the second stage by adding a measured quantity of rare earth hydroxide cake (typically 1.5 times that used to initiate the test), observing a 30 minute period of stabilisation, then dosing with a measured portion of 10% w/w hydrochloric acid, followed by a 30 minute period of stabilisation. Typically, this results in a slurry pH of around 3 to 4. The test is then concluded with vacuum filtration, followed by cake washing. Tests 59 to 61 were initiated using rare earth chloride solution from test 58, with 2.8, 5.3, and 8.4 g of rare earth chloride solution added to tests 59 to 61 respectively per gram of rare earth hydroxide consumed by each test. The results are summarised in Tables 52 to 53. TABLE 51Feed Solid composition (% w/w or g/t)LREMREHRETREMgAlPSCaFeThuTest%%g/t%%g/tg/t%%g/tg/tg/t58 to 6166.91.6980268.80.34<53870.300.46280732.36 TABLE 52Final dissolution solution composition (g/L or mg/L)LREMREHRECeMgAlPSCaFeThUTestg/Lg/Lmg/Lmg/Lmg/Lmg/Lmg/Lmg/Lmg/Lmg/Lmg/Lmg/L5851.22.16110<148230<3<11330<100.14<0.01591375.14261<1122060<3<13620<100.05<0.016025910.0501<12180110<3<16820<100.04<0.016136614.0704<12970150<3409400<100.03<0.01 TABLE 53Overall dissolution extent (%)TestLaCePrNdMREHREYMgAlCaTh5894.8<0.002182.078.369.160.667.694.2—98.70.95992.5<0.001573.167.149.039.939.090.6—97.306094.8<0.001379.274.658.646.645.389.9—98.506195.2<0.001280.475.157.443.443.787.6—98.50 Two Stage Selective Dissolution A two stage rare earth hydroxide dissolution test (Test 62) was conducted at 70° C. in a suitable well agitated baffled vessel with online pH measurement. The test was initiated by repulping 60% of the rare earth hydroxide cake (Table 54) in de-ionised water followed by the controlled dosing of 10% w/w hydrochloric acid to online pH targets of pH 2 (sample 1), then pH 1 (sample 2). At pH 1, all of the rare earth hydroxide precipitate had been dissolved. The remaining 40% of the rare earth hydroxide cake was then added and the mixture allowed to stabilise under agitation for 30 minutes (sample 3). Controlled acid addition was then resumed to pH 3 (sample 4), pH 2 (sample 5), and pH 1 (sample 6). This time the rare earth hydroxide cake did not completely dissolve. The final slurry was allowed to agitate for a further 50 minutes prior to collection of the final sample (sample 7). Following each period of acid dosing and achievement of an on-line pH target, the resultant mixture was allowed to mix for at least 15 minutes prior to sample collection. Subsamples were vacuum filtered, followed by cake washing. The results are summarised in Tables 55 to 57. From the results, despite completely dissolving all the cerium in rare earth hydroxide by sample 2, the addition of additional rare earth hydroxide drove a reprecipitation such that by sample 4 (targeting pH 3, achieving pH 3.2 after stabilisation) the concentration of cerium in solution was below detection limit. This suggests that the cerium dissolved as cerium IV in this test. TABLE 54Feed Solid composition (% w/w or g/t)LREMREHREYMgAlPSCaFeThUTest%%g/tg/t%g/tg/t%%g/tg/tg/t6268.31.81216352900.181591480.320.494203.51.9 TABLE 55Subsample dissolution solution composition (g/L or mg/L)LaCePrNdMREHREYMgAlSCaSampleg/Lmg/Lg/Lg/Lg/Lmg/Lmg/Lmg/Lmg/Lg/Lmg/L113.81422.588.841.2114936456<202978217.4324003.5112.11.80228500206<202421206318.2201.835.510.28153278<20<21494422.6<24.1614.31.8620155290<20101592520.8204.2014.51.9622453880<2041426626.229005.5119.12.6030376012220241784731.249406.4422.23.1737290013020202140 TABLE 56Subsample solid composition (% w/w or g/t)LaCePrNdMREHREYMgAlSCaFeSample%%%%%g/tg/t%g/t%g/tg/t11.1263.10.893.290.5589415300.182650.612866992————————————33.1447.73.0511.52.23302170900.152650.4657256040.9263.21.033.610.69119415600.114230.6021469950.6465.00.682.430.4673510200.102120.6121462960.5466.00.541.850.355527520.1010060.63214118970.6168.20.562.010.365678420.102650.64214909 TABLE 57Overall dissolution extent (%)SampleLaCePrNdMREHREYMgAlCaTh197.20.688.988.286.082.386.959.0—99.016.72100100100100100100100100100100100388.00.05343.137.613.85.85.439.5—97.114.3497.6<0.00587.086.781.673.685.456.5—99.211.3598.40.05792.091.788.985.090.759.2—99.211.9699.413.997.497.496.595.397.481.442.399.741.5799.419.697.597.496.795.797.381.071.799.739.7 A person skilled in the art will understand that there may be variations and modifications other than those specifically described. It is to be understood that the invention includes all such variations and modifications. The invention also includes all steps, features, compositions and compounds referred to, or indicated in this specification, individually or collectively, and any and all combinations of any two or more of the steps or features. | 43,868 |
11858825 | DETAILED DESCRIPTION Various embodiments disclosed herein are directed to a method of making an acid-deficient solution of uranyl nitrate having the formula UO2(OH)y(NO3)2-y, where 0.1<y<0.5, 0.2<y<0.5, or 0.3<y<0.5. The mole ratio of nitrate ions to uranium ions in the uranium compound should be from 1.5 to 1.9, from 1.5 to 1.8, or from 1.5 to 1.7. The present disclosure describes techniques for preparing acid deficient uranyl nitrate solutions in less than six hours, from 0.5 to 5 hours, from 0.5 to 3 hours, from 0.5 to 2 hours, or from 1 to 3 hours. The method includes a first step of preparing a solution of uranium(VI) in aqueous nitric acid. The uranium may be provided as an oxide. If the uranium is provided as a uranium oxide, the oxide may be the formula UxOz, where x is 1-3 and z is 2 to 8. In various embodiments, the oxide may be UO2, UO3, U3O8, or a mixture thereof. In various embodiments, the appropriate mass of a uranium compound, which may be an oxide of uranium(IV) or uranium(VI), is measured and placed in a digestion vessel. The uranium compound may be provided as a powder. An aqueous solution of nitric acid is added to the digestion vessel, in an amount such that the molar ratio of nitrate ions to uranium ions in the solution ranges from 1.5 to 2.0, from 1.5 to 1.9, from 1.6 to 1.8, from 1.5 to 1.7, or from 1.55 to 1.7. In some cases, the molar ratio of nitrate ions to uranium ions in the solution may exceed the molar ratio of nitrate ions to uranium ions in the desired product. For example, where the uranium an oxide of uranium(IV) or uranium(V), a portion of the nitric acid may be consumed by oxidation of uranium to uranium(VI). For example, the majority of the uranium, e.g., >50%, >60%, or ≥70% of the uranium, in U3O8is uranium(V) and uranium (IV). When preparing acid deficient uranyl nitrate from U3O8, a portion of the nitric acid may be consumed by oxidation of uranium(V) to uranium(VI). Thus, to make a solution of acid deficient uranyl nitrate where the mole ratio of nitrate to uranium is 1.7, a starting solution of U3O8in aqueous nitric acid may require a ratio of nitric acid to uranium atoms of about 1.85 to 1.9. Since uranium trioxide contains mostly uranium(VI), acid deficient uranyl nitrate with a mole ratio of nitrate to uranium of 1.7 may be prepared using a starting solution with a ratio of nitric acid to uranium atoms of about 1.7. An amount of deionized water is then added to the digestion vessel. The water should be added in an amount such that the concentration of uranium ions upon dissolution ranges from 0.25 M to 3.5 M, from 1 M to 3 M, from 1.5 to 3 M, or from 2.5 to 3 M. Table 1 shows the amount of the reagents required to make an acid deficient uranyl nitrate solution, at various NO3:U ratios ranging from 1.5 to 1.9 and a uranium ion concentration of 1 M. In such embodiments, a uranium compound is place in a digestion vessel in an amount such that one mole of uranium atoms per liter of the final solution is present in the digestion vessel. The amount of uranium compound to be used may be determined by dividing the molar mass of the compound by the number of uranium atoms in the empirical formula of the compound. Thus, if UO2is used as a uranium compound, one mole of the oxide per liter may be used. However, if U3O8is used as a uranium compound, one third mole of the oxide per liter should be used. To produce a 1 M uranium nitrate solution with a NO3:U ratio of 1.5, a nitric acid solution should be added in an amount such that 1.5 moles nitric acid are present per liter of the final solution. If a concentrated aqueous solution containing 70% by weight nitric acid is used, 95 ml 70% HNO3should be added to the digestion vessel for each liter of the final solution. If a different uranium concentration in the final solution is desired without changing the NO3:U ratio, the amount of uranium compound and the amount of nitric acid should each be scaled appropriately. If a different NO3:U ratio in the final solution is desired without changing the uranium concentration, the amount of the amount of nitric acid should be scaled appropriately without altering the amount of uranium compound. The uranium concentration and the NO3:U ratio may each be independently adjusted. Where an oxide of uranium is used as the uranium source, the initial mixture of uranium oxide and aqueous nitric acid is a slurry of uranium oxide and acid. As the uranium oxide reacts with nitric acid to produce uranyl nitrate, the concentration and pH changes until the reaction is complete and an acid deficient uranyl nitrate solution is obtained. The digestion vessel is then placed in a pressure vessel in a microwave digestion system or electrical resistance heating apparatus. The pressure vessel is sealed and pressurized with an inert gas. The inert gas may be nitrogen or argon. The pressure vessel is pressurized to a desired pressure which is greater than atmospheric pressure, and may be from 2 to 100 atmospheres, from 4 to 50 atmospheres, from 5 to 40 atmospheres, or from 8 to 20 atmospheres. Microwaves or electrical power are applied to the pressure vessel to heat the reaction mixture in the digestion vessel. In various embodiments, a slightly acidic base load, e.g., an aqueous solution containing 3% by weight nitric acid, may be present in the pressure vessel, with the digestion vessel being surrounded by the base load. In such embodiments, microwaves are applied to the pressure vessel to heat the base load, where the base load in turn heats the reaction mixture. Microwaves are applied until a desired temperature is achieved. The solution is heated at a rate of from 3° C./min to 20° C./min, 4° C./min to 15° C./min, or 5° C./min to 10° C./min. Once the reaction mixture and/or the base load reaches the desired temperature, the power of the microwaves applied to the reaction mixture is regulated to maintain the temperature of the reaction mixture at the desired temperature for a desired hold time. TABLE 1Preparation of acid-deficient uranyl nitrate solutions.Uranium Compound70% Nitric AcidRequired for SolutionRequired for Solution(g/l)(ml 70% HNO3/l)Solution pHNO3:UUranium1M3M1M3M1M3MRatioCompoundU(VI)U(VI)U(VI)U(VI)U(VI)U(VI)1.5UO227081095285~2.7~1.61.7UO2270810108324~2.4~1.31.9UO2270810120360~1.8~1.21.5UO328685895285~2.7~1.61.7UO3286858108324~2.4~1.31.9UO3286858120360~1.8~1.21.5U3O828184395285~2.7~1.61.7U3O8281843108324~2.4~1.31.9U3O8281843120360~1.8~1.21.5UO2(NO3)23941,18295285~2.7~1.61.7UO2(NO3)23941,182108324~2.4~1.31.9UO2(NO3)23941,182120360~1.8~1.2 In various embodiments, the desired temperature is between 120° C. and 300° C., between 140° C. and 275° C., between 150° C. and 250° C., between 160° C. and 225° C., or between 170° C. and 200° C. The uranium solution may be maintained at the desired temperature under a pressure of from 10 and 70 atmospheres, from 15 to 60 atmospheres, from 20 to 50 atmospheres, or from 30 to 50 atmospheres for a desired hold time, where the desired hold time is from 15 minutes to 6 hours. The uranium solution may be maintained at the desired temperature for a hold time ranging from 0.5 to 3 hours, from 0.5 to 2 hours, or from 0.75 to 1.5 hours. At the end of the hold time, the applied microwaves are turned off. Then the system will be allowed to degas by releasing the pressure inside the pressure vessel while maintaining the desired temperature. The pressure will be allowed to reduce to a pressure which is greater than the vapor pressure of the solution at the desired temperature, thereby preventing the solution from boiling. The reaction chamber will then be allowed to cool to a temperature below 100° C., a temperature of 30° C. to 90° C., a temperature of 60° C. to 90° C., or a temperature of about 80° C. The pressure in the pressure vessel is released at a controlled rate. Once the system reaches atmospheric pressure, the digestion vessel is removed from the pressure vessel. The acid deficient uranyl nitrate solution is removed from the reaction chamber. To determine if the formation of the acid deficient uranyl nitrate solution is complete, the density and pH of the solution are measured. The density of an acid deficient uranyl nitrate solution ([ADUN]) is dependent on the density of water ([H2O]), the uranium concentration U (mol/l), and the nitrate concentration N (mol/l), by equation (1): [ADUN]=[H2O]+0.27U+0.028N (1) Since the uranium and nitrate concentrations are known, the correct density for an acid deficient uranyl nitrate solution can be calculated from Equation (1). For example, a 1 M uranyl nitrate solution with a NO3:U ratio of 1.5 should have a density of 1.31 M. In various embodiments where the acid deficient uranyl nitrate solution has a NO3:U ratio of 1.5 to 1.7, the density of an acid deficient uranyl nitrate solution (Q[ADUN]) is approximately represented by equation (2): [ADUN]=[H2O]+0.31U (2) Theoretically, if the concentration of uranium in the acid deficient uranyl nitrate solution is between 2.7 M and 3 M, the solution density should range from 1.837 to 1.93 g/cm3, based on equation (2). A solution with a concentration of uranium between 2.7 M and 3 M and a density of between 1.75 and 1.95 g/cc is acceptable for use in preparation of uranium oxide microspheres. The pH of an acid deficient uranyl nitrate solution pH with a uranium concentration between 2.7 M and 3 M should be between 1.2 to 1.4. Acid deficient uranyl nitrate solution with similar uranium concentrations and pH values may be achieved by traditional means, under ambient pressure, e.g. by processing at 20° C. to 70° C. at atmospheric pressure. However, the time required to prepare such solutions is typically measured in days. The technique disclosed herein alloys preparation of the acid deficient uranyl nitrate solutions in less than six hours, from 0.25 to 5 hours, from 0.5 to 4 hours, from 0.5 to 3 hours, from 0.5 to 2 hours, or from 1 to 3 hours. The process disclosed herein allows making acid deficient uranyl nitrate solutions at elevated pressures and temperatures. Temperature of the solution can be increased using a variety of heating elements, including radiant or conductive heating elements. Temperature can be increased using microwaves to heat the solution. The pressure can be delivered by an external pressure and/or as a result of increasing the vapor pressure of the working fluid (i.e. the ADUN solution) during heating. The uranium oxide/nitric acid slurry may be placed under elevated pressure by placing the mixture under an inert pressurized atmosphere at low temperature, and further increasing pressure by heating the solution to increase its vapor pressure. In various embodiments, the acid deficient uranyl nitrate solution has a NO3:U ratio of 1.5, with a uranium concentration of from 0.5 M to 3.5 M and a pH of 1.4 to 2.9, a uranium concentration of from 1 M to 3 M and a pH of 1.6 to 2.7, a uranium concentration of from 2 M to 3 M and a pH of 1.7 to 2.2, or a uranium concentration of from 2.7 M to 3 M and a pH of 1.7 to 1.9. In various embodiments, the acid deficient uranyl nitrate solution has a NO3:U ratio of 1.6, with a uranium concentration of from 0.5 M to 3.5 M and a pH of 1.24 to 2.75, a uranium concentration of from 1 M to 3 M and a pH of 1.3 to 2.5, a uranium concentration of from 2 M to 3 M and a pH of 1.4 to 2, or a uranium concentration of from 2.7 M to 3 M and a pH of 1.4 to 1.6. In various embodiments, the acid deficient uranyl nitrate solution has a NO3:U ratio of 1.7, with a uranium concentration of from 0.5 M to 3.4 M and a pH of 0.8 to 2.6, a uranium concentration of from 1 M to 3 M and a pH of 1.6 to 2.4, a uranium concentration of from 2 M to 3 M and a pH of 1.2 to 1.8, or a uranium concentration of from 2.7 M to 3 M and a pH of 1.2 to 1.4. In various embodiments, the acid deficient uranyl nitrate solution has a NO3:U ratio of 1.5 to 1.9; a uranium concentration of from 0.5 M to 3.5 M; and a pH of 0.5 to 2.8. In various embodiments, the acid deficient uranyl nitrate solution has a NO3:U ratio of 1.5 to 1.7; a uranium concentration of from 0.5 M to 3.5 M; and a pH of 0.8 to 2.8. EXAMPLES Comparative Example 1 32.3 mL of 70% nitric acid is added to a vessel containing 23 mL of distilled water. The vessel is heated to 60° C. and 76 g of U3O8are added in increments of 25%, 25%, 25%, 10%, 10%, and 5% over the course of 6 days. The vessel is continuously kept at 60° C. and stirred over the course of this 6-day period. Distilled water is added over the course of the 6-day period to keep the volume of the reaction mixture constant in the reactor vessel and prevent precipitation. The vessel is cooled to 20° C., and allowed to equilibrate for another 24 hours. After 24 hrs, the density and pH are tested, and distilled water is added if necessary. The uranyl nitrate solution is removed and filtered to remove unreacted uranium oxides. Example 1 6 g of U3O8(7.13 mmol U3O8; 21.4 mmol U) are added to 1.8 to 3 ml of distilled water to form a uranium oxide slurry. The uranium oxide slurry is mixed, and 1.3 to 2.5 mL of 70% Nitric Acid are added. The uranium oxide slurry is again mixed, and placed in an acid digester. The water to U3O8mass ratio ranges from 0.3 to 0.5. The nitric acid to U3O8mass ratio ranges from 0.3 to 0.6. The digestion vessel is pressurized to 5 to 40 bar with argon and heated to between 200° C. to 250° C. This temperature is maintained for 30 to 120 min. At the end of this time, the system is degassed to partially vent pressure, while remaining at a temperature between 200° C. to 250° C. and a pressure above the vapor pressure of the heated digested solution to prevent boiling. After partially venting pressure, the temperature is reduced to 30° C. The pressure is reduced to atmospheric pressure, and the product uranyl nitrate solution is unloaded. Example 2 6 g of U3O8(7.13 mmol ILOs; 21.4 mmol U) are added to 3 ml distilled water. The U3O8and water are mixed, and 2.5 mL 70% nitric acid (15.8 M aqueous HNO3; 39.52 mmol HNO3; 2.49 g HNO3) is added and the resulting solution is mixed and placed in an acid digester. The nitric acid to U3O8mass ratio is 0.5. The nitric acid to U3O8mole ratio is 1.85. The vessel is sealed and pressurized to between 5 bar and 40 bar with argon, and heated with microwaves to between 200° C. to 250° C., with the temperature being increased at a ramp rate of 3° C./min to 20° C./min. The temperature is then maintained at between 200° C. to 250° C. for between 30 and 120 min. At the end of this time, the system is degassed to vent pressure, while remaining at a pressure above the vapor pressure of the digested solution to prevent boiling. This may be done by maintaining the temperature to 200° C. to 250° C., while partially reducing the pressure to a pressure which exceeds the vapor pressure of the digested solution at between 200° C. to 250° C. After partially reducing the pressure, the solution temperature is reduced to 30° C. The pressure is reduced to 1 atmosphere, and the product uranyl nitrate solution is unloaded. Example 3 400 g of U3O8(0.48 mol U3O8; 1.44 mol U) are added to 194 ml distilled water. The U3O8and water are mixed and 170 mL 70% nitric acid (15.8 M aqueous HNO3; 2.69 mol HNO3) is added to the uranium solution, and the resulting solution is mixed and placed in an acid digester. The nitric acid to U3O8mass ratio is 0.42. The nitric acid to U3O8mol ratio is ˜1.87. The vessel is sealed and pressurized to 30 bar with argon and heated with microwaves to 230° C., with the temperature being increased at a ramp rate of 3° C./min to 20° C./min. The temperature is then maintained at between 230° C. for 60 minutes. At the end of this time, the system is degassed to vent pressure to 35 bar. The temperature is reduced to 30° C., the remaining pressure is vented, and the product uranyl nitrate solution is removed from the vessel and may be filtered to remove unreacted uranium oxides. Example 4 6 g of UO2are added to 1.8 to 3 ml of distilled water to form a uranium oxide slurry. The uranium oxide slurry is mixed, and 1.3 to 2.5 mL of 70% nitric acid are added. The uranium oxide slurry is again mixed, and placed in an acid digester. The water to UO2mass ratio ranges from 0.3 to 0.5. The nitric acid to UO2mass ratio ranges from 0.3 to 0.6. The digestion vessel is pressurized to 5 to 40 bar with argon and heated to between 200° C. to 250° C. This temperature is maintained for 30 to 120 min. At the end of this time, the system is degassed to partially vent pressure, while remaining at a temperature between 200° C. to 250° C. and a pressure above the vapor pressure of the heated digested solution to prevent boiling. After partially venting pressure, the temperature is reduced to 30° C. The pressure is reduced to atmospheric pressure, and the product uranyl nitrate solution is unloaded. If the density and pH levels are not as desired, repeat procedure. Although the various embodiments have been described in detail with particular reference to certain exemplary aspects thereof, it should be understood that the invention is capable of other embodiments and its details are capable of modifications in various respects. As is readily apparent to those skilled in the art, variations and modifications can be affected while remaining within the spirit and scope of the invention. Accordingly, the foregoing disclosure and description are for illustrative purposes only and do not in any way limit the invention, which is defined only by the claims. | 17,593 |
11858826 | Reference is made to the accompanying drawings throughout the following detailed description. In the drawings, similar symbols typically identify similar components, unless context dictates otherwise. The illustrative implementations described in the detailed description, drawings, and claims are not meant to be limiting. Other implementations may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented here. It will be readily understood that the aspects of the present disclosure, as generally described herein, and illustrated in the figures, can be arranged, substituted, combined, and designed in a wide variety of different configurations, all of which are explicitly contemplated and made part of this disclosure. DETAILED DESCRIPTION OF VARIOUS EMBODIMENTS Electrode materials which undergo anion insertion are a void in the materials innovation landscape and a missing link to energy efficient electrochemical desalination. Layered hydroxides (LHs) have been widely used in electrochemical applications. Prior work described in U.S. Provisional Application No. 62/418,534 posited that LHs could be used as an electrode material for anion insertion electrochemistry. Further described herein are extensions to the basic concept of LHs as electrode materials, include both new materials for use with LHs, such as layered mono-hydroxides (LMH) and higher order layered poly-hydroxides (LPHs), including layered double hydroxides (LDH) as well as methods for synthesizing improved LH material such as with conductive supports or through the use of cross-linking. Poly-layer hydroxides generally consists of the formula (M1)x(M2)y(M3)z. . . (OH)6A, where M is the cation and A is the anion, with M1, M2, M3. . . each being different cations. LMH have only M1while DLH have M1and M2. Finally, also described herein are embodiments enabling the use of LHs as flow electrodes as well as the use of thin (2d) LH materials (TLH) for surface redox reactions. Layered Double Hydroxides The LH material provides a structure capable of allowing an ion to move in and out of the physical structure. In some of the illustrated embodiments, a bias is applied to move the ion relative to the structure. LHs allow for facile synthesis and a modularity of possible compositions, enabling tunable (electro)chemical properties. LHs consist of alternating layers of (a) positively charged planes of metal centers (cations) which are octahedrally coordinated to hydroxyl groups and (b) interplanar anions and water. The cation material in the LH may be any suitable cation material, including alkaline, alkaline earth, transition metals and nonmetals. While it is believed that a blend of cations which have 2+and 3+valence provide improved functionality, LH can be stable with alkaline (1+), alkaline earth, transition metals, nonmetals, and lanthanides. In one embodiment, the anion insertion material comprises a cation material capable of forming a 1+,2+, or 3+state. In a particular embodiment the 1+/2+material includes Ca, Cd, Co, Cu, Li, Mg, Mn, Ni, Zn. In a particular embodiment, the 3+material includes Al, Cr, Fe, V, and Co. The ratio of 2+/3+can vary from 1:0 up to 1:2 or larger. The layered structure is expected to be more stable when the ratio is 1:1 or greater. When considering redox active 2+or 3+metal centers, the redox active component should ideally be high enough to provide a large capacity, but low enough to provide structural stability. Redox active metals include Mn, Ni, Co, Fe, V, Mo, and other transition metals. Structural metals include Mg, Al, Si, Ge, Ca, Li, and other alikali metals, alkaline earth metals, post-transition metals, and metalloids. Here a redox active metal is meant as a transition metal which has an equilibrium potential where the oxidation state of the transition metal nominally changes state (but remains as a cation) within the potential limits of water splitting, e.g. Fe3+/Fe2+ at 0.77 V vs NHE, along with a subset of examples in the electrochemical series. Redox active metal centers should be 20-80% of the structural cations for multiplayer LH particles, and 50-100 atomic weight % of cations for single layer or 2d LHs to balance these requirements. Note that the redox active metal center can be either 2+or 3+. The metal hydroxide planes in LHs can be comprised of a single metal center (e.g., cobalt hydroxide with root formula Co(OH)2), two metal centers, termed LDHs (e.g., naturally occurring hydrotalcyte with root formula Mg3Al(OH)8), or more than two metal centers (LPH). Metal centers in the metal hydroxide planes may be homogeneous. In another embodiment, the metal centers are heterogenous, for example a blend of divalent (e.g., Mg, Co) and trivalent (e.g., Al, Cr, V, Co) cations. Interplanar anions in the LH structure balance charge with tri-valent metal cations in the metal hydroxide planes and cohere the planes together into nanoplatelet stacks. In order to investigate LHs, experiments were performed with advanced in situ characterization during electrochemical operation and ab initio material modeling to probe the anion insertion electrochemistry of LH nanoplatelets. The unified electrochemical band-diagram (UEB) framework enables modeling of the thermodynamics of anion insertion (and other structural changes) under applied bias despite the lack of a convenient computational anion reference. As descried below, coupling computational results within the UEB framework with in situ experimental measurements including quartz crystal microbalance (QCM), high energy X-ray diffraction (HE-XRD), and X-ray absorption spectroscopy (XAS) provides compelling evidence of anion insertion electrochemistry in LHs. Example I—LDH Nanoparticle Synthesis and Characterization Layered hydroxide nanoparticles were synthesized using co-precipitation. Salt solutions for nanoparticle synthesis were prepared using chloride salts for Co: cobalt(II) chloride (anhydrous, 99.7%, Alfa Aesar), Cr: chromium(III) chloride hexahydrate (98%, Alfa Aesar), V: vanadium(III) chloride (anhydrous, 99%, Alfa Aesar), Al: aluminum chloride hexahydrate (99%, Alfa Aesar), and Mg: magnesium chloride hexahydrate (ACS Grade, Ampresco). For LDHs, 1.5 mmol of M3+salt was combined with 0.5 mmol of M2+salt in 5 mL of deionized (DI) water (18.2 MΩ, Millipore Direct-Q) to make a salt solution. For Co LH, 2 mmol of salt was dissolved in 5 mL of DI water to make a salt solution. 20 mL of 0.15M NaOH (ACS Grade, EMD Millipore) was purged for >15 minutes under argon (Ar, UHP, General Air Service and Supply) atmosphere in a 3-neck flask at room temperature (˜20° C.). 5 mL of salt solution (see above) was rapidly injected into the NaOH solution, and held under Ar atmosphere for >15 minutes to seed nanoparticle formation. The nanoparticles were rinsed three times by: (1) centrifuging the ˜25 mL nanoparticle suspension for 3 minutes at 7000 rpms, (2) pouring off the supernatant, and (3) resuspending the nanoparticles in DI water to return the total volume of the suspension to ˜25 mL. The resulting aqueous suspensions contained ˜3 μg/μL of nanoparticles. Following this synthesis procedure, the nanoparticles were either aged using hydrothermal treatment at 100° C. for 4 hours, or at room temperature for at least one week. Cobalt-containing LHs for anion insertion. The seminal work identifying the LDH structure and synthesis and demonstrating particle size control were based on Mg—Al compositions. While Mg—Al LDH synthesis is robust and well-studied, it is not expected that Mg—Al LDHs to be useful as anion insertion electrodes because Mg and Al do not undergo redox electrochemistry within the potential limits of water stability. Incorporating metal centers into the LH structure which are redox-active within the potential limits for water stability provides a strategy for enabling aqueous anion-insertion electrochemistry. Here, Co-containing LHs are focused on because successful Co-LDH syntheses are known, and Co-containing compounds (e.g., LiCoO2) have been shown to undergo redox reactions within the potential stability limits of aqueous electrolytes. Using coprecipitation of metal chloride salts in strong basic solution, aqueous suspensions of LH nanoparticles are synthesized. LHs spontaneously form a nanoplatelet morphology as depicted inFIGS.1A-C. Upon dropcasting, these nanoparticles coalesce into nearly uniform coatings on electrode surfaces. A nanoplatelet morphology was observed for all of the LDH compositions examined in this work. In most cases, nanoplatelets were ˜100 nm in diameter and 2-5 nm thick, as demonstrated in STEM images for Co—Al and Mg—Al compositions inFIGS.1B and1C, respectively. Various examination techniques were used for qualitative and quantitative analysis of the resultant materials. For Inductively Coupled Plasma—Optical Emission Spectroscopy (ICP-OES), LH aqueous suspensions were gravimetrically diluted to 1% concentrations in DI water. Then 5 g of 1% dilutions are gravimetrically combined with 5 g of 10% nitric acid. These solutions and DI-water and nitric acid control solutions were submitted to the Laboratory for Environmental and Geological Studies (LEGS) at the University of Colorado Boulder for ICP-OES measurement and analysis. Ultra-violet Visible Spectroscopy (UV-Vis) (Cary 8454, Agilent Technologies) was performed between 230 nm and 900 nm in polystyrene disposable cuvettes (1 cm path length, PLASTIBRAND). 100 μL of nanoparticle suspension was diluted in 2 mL of DI water, and a DI water blank was measured before each sample. Tauc plot analysis was performed for direct allowed transitions (r=½). High resolution ADF Scanning Transmission Electron Microscopy (STEM-EDS) imaging was performed on a JEOL ARM200F with a Schottky field emission source operating at 200 kV. Samples were prepared by diluting LH suspensions to 1% in DI water and drop casting 5 μL of sample onto ultrathin carbon coated lacey carbon grids (Ted Pella, USA) and plasma cleaning in a 97% hydrogen, 3% oxygen plasma (Fischione model1070plasma cleaner) for 1 minute directly prior to imaging. ADF STEM images were acquired under relatively low dose conditions to avoid damage of the LHD particles. The beam current was ˜20 pA and the pixel dwell time was 25 μs. The ADF detector inner collection angle was ˜70 mrad. STEM-EDS elemental mapping was performed on an FEI Talos F200X TEM operating at 200 kV with a Schottky field emission source and Bruker ChemiSTEM EDS system. Pixel intensities in the EDS maps for Mg, Al, and O were computed by integrating the Lα1peaks for each element. STEM imaging on Co LH were performed in a similar manner using a Talos™ operating at 200 kV. HE-XRD was performed both in situ and ex situ at the 6-ID-D beamline at the Advanced Photon Source (APS) at Argonne National Lab using 100 keV irradiaton. Supplemental ex situ HE-XRD measurements of Mg2Al and Co LHs were performed at 11-ID-B and 11-ID-D beamlines using 58.65 and 105 keV irradiaton, respectively. All measurements were performed in a transmission configuration with the sample-to-detector distance set to maximize the sampled q-range. For HE-XRD characterization, LH nanoparticle suspensions were frozen overnight at −80° C., then lyophilized (VirTis, Benchtop K) to produce bulk nanoparticle powders. For ex situ measurements, these powders were crushed and ground into fine particles, then loaded into Kapton capillaries (1 mm dia., Cole-Palmer) and measured in an automated fashion with a multi-sample stage. In situ measurements during electrochemical operation were performed using a capillary working electrode cell geometry as described elsewhere. Conductive granular activated carbon (Norit GAC 400 M-1746) is used as an electrode support inside of the carbon fiber capillary working electrode, and lyophilized LH powder is added on top of the GAC. The X-ray beam position was adjusted to the GAC/active material interface to probe active LH material in electrical contact with the conductive carbon support. Background correction, conversion to total structure functions, and Fourier transformation to produce atomic pair distribution functions (PDFs) was performed using PDFgetX3. Diffracted X-ray intensity, i(Q), reduced total scattering factor, F(Q), and pair distribution function, G(r), for the Mg—Al LDH are plotted inFIG.7A. Using starting structures from ab initio modeling (see below), a first-pass structural fit was performed on a unit cell structure using PDFgui with optimization of lattice vectors only. The output structures from PDFgui were expanded into supercells with 40 Å minimum dimensions, and used as starting structures for reverse monte carlo (RMC) modeling. RMC modeling was performed for ex situ samples using the fullrmc python package. The fitted RMC structure for the Mg—Al LDH is shown inFIG.7B. Additional plots of i(Q), F(Q), and G(r) for the Co, Co-V, Co—Al, and Co—Cr LHs are presented inFIGS.8A-D, respectively. XAS and subsequent extended X-ray absorption fine structure analysis (EXAFS) was performed using in situ XAS measurements during electrochemical characterization at the 10-BM beamline at the APS at Argonne National Lab. 400 μL of LH suspension were dropcast onto nonwoven carbon fiber paper (Fuel Cell Earth, Toray Carbon Paper, ˜300 μm thickness) in 50 μL aliquots, resulting in a mass loading of ˜1 μg. This carbon paper was loaded into a custom polyether ether ketone (PEEK) electrochemical cell with Kapton windows and titanium wire current collector as depicted in other work. A BioLogic SP-300 potentiostat was used for electrochemical control. EXAFS measurements were performed on the Co K-edge (7.71 keV) in a fluorescence geometry using a 4-element Vortex Silicon Drift Diode. For each measurement a constant voltage was applied to the cell and EXAFS scan were taken from −200 eV to +800 eV relative to the Co K-edge. SeeFIG.9for Co K-edge X-ray absorption near-edge spectra (XANES) of the Co-V LDH under various applied biases. Subsequent data processing and EXAFS modeling as performed using the Athena and Artemis programs of the Demeter XAS software package. 2EXAFS modeling was first performed on reference Co foil to obtain an S02value of 0.755 for all subsequent modeling efforts. EXAFS modeling on Co-V LDH at various potentials was performed using theoretical scattering paths from DFT generated structures (seeFIGS.10and11for the amplitude and real space fitting results, respectively). Given the difficulty in distinguishing Co from V theoretical scattering paths, models were performed by treating all metal scatters as a singular elemental species. EXAFS modeling produced similar Co—O coordination number (˜6) and Co—O Debye-Waller factors (˜0.008) for each voltage condition, which were then considered as defined constants for subsequent modeling efforts to obtain Co-metal structure and Co—O nearest neighbor distances. All fittings resulted in R-factors of less than 0.02, indicating a high quality fit. Ab initio modeling was performed. LH electrochemical thermodynamics were modeled using the UEB framework, as described in prior work. Various point defects were modeled in LH structures including substitutions, vacancies, and interstitials, with primary focus on the electrochemically active Co3(OH)6Cl and Co2V(OH)6Cl structures and Cl insertion/removal. Total energy calculations are performed for perfect and (charged) defect structures using density functional theory (DFT) and the projector augmented-wave (PAW) method as implemented in the Vienna Ab initio Simulation Package (VASP). Chemically relevant cobalt 3d and 4s; vanadium 3p, 3d, and 4s; chlorine 3s and 3p; oxygen 2s and 2p; and hydrogen 1s electrons are calculated explicitly using PAWs, while pseudopotentials describe core electrons. A fully automatic Γ-centered Monkhorst-Pack K-point mesh was generated for all structures using VASP with I=14. A modified Heyd-Scuseria-Ernzerhof (HSEsol) range-separated functional was applied for charged defect calculations to correct for self-interaction error in defect calculations. Multi-step ionic and cell-shape relaxations were carried out as implemented in the pylada python module. The pH and applied bias were accounted for in formation energies calculations by using the hydroxide-forming limit and setting the chemical potential of H based on the pH as described previously. Bulk crystal hydroxide structures are used instead of individual hydroxide molecules for reference calculations (note a sign correction in the applied bias as compared with this prior work). All calculations are performed using a surface description by accounting for band bending at the electrode surface. For this, it is assumed that the Nernstian relationship V=VPZC+0.059(pHPZC−pH), as described previously, and use a pHPZC value of 11.4 based on the PZC reported for Co(OH)2. The idealized 2:1 M2+-M3+molar ratio LDH structure depicted inFIG.1Ewith a honeycomb metal configuration based on the 2:1 Mg—Al LDH structure as depicted inFIG.12A. The band edges of the material are aligned within an electrochemical reference frame using work function calculations for the dominant {100} surface which is perpendicular to the LH planes as depicted inFIG.12B. This employed ≥17 Å thick slabs, and ≥15 Å vacuum space, with ionic relaxation on all atoms >5 Å from the center plane of the slabs. The potential difference between vacuum and the bulk material is calculated using the Purdew-Burke-Ernzerhof (PBEsol) functional and correct the band edge positions at the HSEsol level in a similar fashion to work correcting band edge energies using quasiparticle calculations. Electrochemical characterization for ex situ and in situ HE-XRD and XAS studies was performed with a potentiostat (Biologic, SP-300) using a Ag/AgCl reference electrode (BASi) and graphite counter electrode (7 mm dia. Graphite electrode, BioLogic). Electrolyte solutions for all electrochemical studies were purged with Ar for >15 minutes prior to and throughout electrochemical operation. For ex situ electrochemical characterization, 7 μL aliquots of LH nanoparticle suspensions were dropcast onto glassy carbon electrodes (GCEs, ALS Co. 3 mm dia.) and dried under vacuum for >15 minutes prior to electrochemical measurement. Galvanostatic (constant current) measurements were performed in 0.1 M NaCl (Alfa Aesar, ACS Grade 99.0% min) aqueous electrolyte tuned to a pH of 10 using NaOH. During in situ HE-XRD, a 0.1 M NaBr (ACS Grade, Alfa Aesar) electrolyte was used to enhance the diffraction signal arising from interplanar anions (Br vs. Cl). A continuous electrolyte flow of 0.4 mL/min was maintained during in situ HE-XRD electrochemical operation using a peristaltic pump (Ismatec IPC). Fresh electrolyte was used for each experiment, and electrolyte was recirculated during electrochemical characterization. NaBr was also used for XAS studies to be consistent with HE-XRD studies. For Electrochemical Quartz Crystal Microbalance (EQCM) studies, LH nanoparticle suspensions were diluted into equal parts DI water and 20 μL volume aliquots were dropcast onto titanium coated QCM crystals (FilTech, 4.95 MHz, 14 mm), and dried for >20 minutes under vacuum. LH-coated QCM crystals were loaded into a Q-sense electrochemistry module (Biolin Scientific) using a platinum plate counter electrode and Ag/AgCl reference electrode (Dri-Ref 2SH, World Precision Instruments). 0.1M NaCl was tuned to a pH of 10 using NaOH and used as the electrolyte solution. The electrolyte was purged for >15 minutes using Ar prior to use, and kept under continual purge during experimentation. The pH of the source electrolyte was monitored during operation and remained between 10 and 10.5. Electrolyte was used to purge the cell and tubing for >5 minutes at a flow rate of 0.4 mL/min using a peristaltic pump (Ismatec IPC). Electrolyte flow was stopped during electrochemical characterization to eliminate flow eddies and vibrations present during flow and improve QCM resolution. Presented inFIG.13is a ADF STEM image of the Co-V LH. The nanoplatelet morphology and size observed is consistent with the LH structure and agrees closely with the STEM results for Mg—Al and Co—Al LHs presented inFIG.12. An exemplary energy dispersive x-ray spectroscopy (EDS) measurement of a Co-V nanoplatelet is presented inFIG.14. This EDS spectrum clearly shows the presence of both Co and V in these nanoplatelets. The signal for Cu arises from the TEM grid. EDS quantitative analysis identified an average Co:V ratio of 3.3±0.4 by sampling seven particles. One measurement indicated a Co:V ratio of 5.8, but was a statistical outlier and was excluded from the calculation of this average value. Interestingly, the Co:V ratio of ˜3 determined by STEM-EDS is much smaller than the value of 48 determined by ICP-OES following digestion. It is believed that this discrepancy is due to a bias in the STEM-EDS analysis toward larger, structurally defined nanoplatelets. During STEM of the Co-V agglomerates of smaller nanoplatelets which were not stable under the electron beam and could not be characterized by EDS were not observed. Further, it is believed that these smaller nanoplatelets were Co(OH)2, leading to a lower average concentration of V when the entire sample is digested. Presented inFIG.15is an ADF STEM micrograph of Co LH nanoplatelets synthesized without a trivalent metal center. These nanoplatelets are similar in shape to the LDH structures, but are only ˜10 nm in diameter rather than ˜100 nm as observed for the LDH compositions. These smaller Co(OH)2 nanoplatelets are consistent with the explanation above describing the presence of Co(OH)2in the Co-V nanoplatelet sample. Presented inFIG.16is a Tauc plot of UV-Vis data collected on aqueous LH suspensions. Tauc analysis is performed for direct allowed transitions. The band gap of each layered hydroxide is determined by extrapolating the linear portion of the trace to the intersection of (αhv)2=0. Band gaps are calculated to be 4.4 eV (Co—Al), 4.4 eV (Co—Cr), 2.7 eV (Co-V), and 3.7 eV (Co). No absorption was observed for Mg2Al for the range of photon energies examined by UV-Vis, suggesting a band gap >5.3 eV. The linear region >4 eV is used for determination of the Co LH band gap, and attribute the lower-energy absorption to defect states. For the Co-V trace two linear regions were observed: one between 2.5 and 3.7 eV, and one between 4 eV and 5.3 eV. The lower-energy linear region of the Co-V trace is used for band gap determination. Using the higher energy region, a bandgap of −3.5 eV was calculate. Similarly, a minority absorption is also observed at lower energies for Co—Al and Co—Cr corresponding to a band gap of −3.5 eV. A 3.5 eV band gap agrees closely with the band gap determined for the Co LH (Co(OH)2). It is believed that the secondary absorption observed for each of the binary LDHs arises from local regions of Co(OH)2present in these compositions. Synthesis of Mg—Al LHs in this work yielded a bulk M2+:M3+(Mg:Al) molar ratio of 1.7 as measured by inductively coupled plasma optical emission spectroscopy (ICP-OES). This is in agreement with prior work on Mg—Al LDHs indicating stable Mg—Al LDHs with Mg:Al stoichiometric ratios between 1 and 5. STEM-EDS indicates uniform distribution of Mg and Al in LDH particles as depicted inFIG.3C. Co—Al and Co—Cr LHs synthesized in this work exhibited M2+:M3+molar ratios of 1.8 and 2.0, respectively, by ICP-OES. These stoichiometric ratios are in agreement with prior work which reports molar ratios of ˜2 for these compositions. In addition, we Co-V LDHs were synthesized, which to our knowledge have not been reported previously. ICP-OES measurements indicated a bulk Co:V molar ratio of 48:1, corresponding to Co LH (Cox(OH)2xCl) with ˜2% V-doping. However, STEM-EDS analysis of Co-V LHs identified particles containing a 3:1 ratio of Co:V, suggesting a mixture of Co3V(OH)8Cl and Co LH. A low bulk V concentration is expected considering the favorability of V vacancies in the Co-V structure. Despite the low V concentrations in the Co-V LDH, the atomic structure of the Co-V LDH (FIG.1B) is in close agreement with the other LDH structures. We also emphasize that the measured UV-vis band gap of the V-doped cobalt hydroxide structure (2.7 eV) is in close agreement with calculated band gap for a 3:1 Co:V stoichiometric ratio (2.75 eV for Co3V LDH), and do not agree with calculated band gaps for the Co(OH)2cobalt hydroxide structure (3.6 eV) indicating that 2% V-doping is sufficient to impact the bulk electronic properties. Although the electronegativity of V (1.63) falls between that of Al and Cr (1.61 and 1.66, respectively), the band gap of the Co-V LDH is dramatically lower than the other structures. We attribute this to differences in the t2g-egfilling for V vs. Cr. Presented inFIG.17are UEB defect plots calculated for the Co3V LDH structure. These calculations predict that under applied negative bias, Cl— is stable in the Co3V LDH structure over a wide potential range, and is not predicted to be removed until a negative bias exceeding −1.6 V vs. Ag/AgCl. The formation of O2−vacancies is predicted to occur before the formation of Cl−vacancies at a lower negative bias of −1.4 V vs. Ag/AgCl In Co3V. Additionally, Cl−insertion (Cli) is not predicted to occur until a positive potential exceeding +0.4V vs. Ag/AgCl. Based on these results, Cl−will not reversibly incorporate in Co3V under applied bias. However, the formation of vanadium vacancies, labeled vv, is predicted to be highly favorable (ΔEf<−2 eV) over the full range of applied potential, while a reduction of these vacancies is predicted to occur at negative potentials exceeding −1.4V. Similarly, cobalt vacancies (vCo) are predicted to be moderately favorable (ΔEf<−0.2 eV) in Co3V LDH, with oxidation of these vacancies predicted at positive potentials exceeding −0.1 V vs. Ag/AgCl. FIG.1Bdepicts a ˜5 nm thick particle, where the metal hydroxide layer separation is measured to be ˜8 Å. We observe an equivalent atomic structure among the Mg—Al, Co—Al, Co—Cr, Co-V, and Co-only LHs studied in this work. Atomic PDF analysis derived from HE-XRD patterns as depicted inFIG.1Dis useful here due to the nanoscale of the LH platelets and the fine structural detail of interest during in situ measurement of anion insertion (seeFIG.4). Atomic PDFs provide sub-Angstrom structural details in terms of real-space atomics distances, and more intuitively showcase the structural features present in the LDH compositions (Mg—Al, Co—Al, Co—Cr, and Co-V). Main atomic pair features at ˜2, ˜3, and ˜8 Å correspond to first-coordination sphere metal-oxygen, metal-metal, and interlayer metal-metal pair distances, respectively, for all materials examined. Reverse Monte Carlo (RMC) fits (thin black lines inFIG.1D) were performed using starting LH structures determined from ab initio calculations, an example of which is depicted inFIG.1E. RMC fits are in close agreement with measured PDFs indicating formation of the LDH structure in all cases. The interlayer metal-metal peak at ˜8A for the Co—Al LDH inFIG.1Dis also consistent with the interplanar spacing observed by STEM inFIG.1B. Synthesis of a LH using only Co(II) without M3+cations resulted in a qualitatively different PDF (top ofFIG.1D), which was fit using a Co(OH)2LH structure without interplanar anions. Initially, we hypothesized that the conduction band edge energy would determine the potential at which anion insertion occurs in an LH. As a negative bias is applied and increases the fermi energy of the electrode, we expected that electrons would transfer into the material when the conduction band edge energy is reached, driving reduction of the LH and leading to reversible anion insertion according to M(III)(OH)6Cl+e−M(II)(OH)6+Cl−. Based on this picture, we computationally evaluated the band edge positions for the LHs synthesized inFIG.1D(rigid band model) using the idealized 2:1 M2+-M3+molar ratio LDH structure depicted inFIG.1E. By calculating the fermi level energy of the bulk material with respect to an electron in vacuum in this way, we determine the absolute band edge positions as presented inFIG.1F. Our computational results show that composition strongly impacts the electronic properties of the LH structures, which are predicted to have band gaps ranging from 2.8 eV (Co-V) to 6.4 eV (Mg—Al). We also note that the computed band gaps for the LH structures inFIG.1Fare in agreement (within 0.4 eV) of experimental band gaps reported beneathFIG.1Fdetermined using ultraviolet-visible (UV-Vis) spectroscopy. Of the compositions presented inFIG.1D, we selected the Co-V and Co LHs for further analysis because our ab initio modeling predicted their conduction band edge positions lie at the lowest energies. Projected density of states (PDOS) for Co-V and Co LHs are presented inFIGS.1G and1H, respectively. The conduction band edge of the Co-V LDH is predicted to be V-character, whereas the conduction band edge of the Co LH is predicted to be Co-character. We expected these species to take on electron density under applied negative bias. However, electrochemical evaluation of the Co-V and Co LHs yielded a surprising result. While we do observe reversible anion insertion electrochemistry in both the Co-V and Co LHs, sit occurs under oxidizing (positive) potentials rather than reducing (negative) potentials as we hypothesized. Presented inFIG.2Ais electrochemical quartz crystal microbalance (EQCM) trace for the Co-only LH. In these EQCM measurements the working electrode is the titanium surface of a quartz resonator, which can be used to measure in situ mass changes during electrochemical operation. Here we observe compelling evidence of anion insertion when cycling under positive bias between +0.2 V and −0.4 V vs. Ag/AgCl. We observe a monotonic mass gain under positive potential (oxidation) and mass loss under negative potential (reduction). This is qualitatively consistent with anion insertion-under applied positive bias, Cl−is drawn into the Co LH structure as depicted inFIG.2B, and under applied negative bias Cl−is expelled from the Co LH structure as depicted inFIG.2C. The region marked with dashed lines and arrows inFIG.2yields a calculated m/z of 32.9 g/mol e−, in close agreement with the value of 34.5 g/mol e−expected for stoichiometric Cl−insertion. The six cycles shown inFIG.2yield an average m/z of 30.2±2.8 g/mol e−on the oxidizing sweep, and 23.0±2.6 g/mol e−on the reducing sweep. The lower value on the reducing sweep indicates some irreversibility, which we attribute to ion-decoupled electron transfer as described elsewhere. This evidence for anion insertion provides strong support for Cl−insertion in Co LH under oxidizing potentials. In order to reconcile the unexpected potential region for anion insertion, we more closely examine the electrochemical behavior of various LHs under negative potential conditions. Under applied negative current, the Fermi level in each LH (FIGS.1D and1E) increases, corresponding to more negative potentials for the experimental measurements inFIG.3A. By the rigid band description inFIG.1D, electrons are expected to transfer into unoccupied V orbitals (FIG.1E) in the Co-V structure at a potential of −1.5V vs Ag/AgCl (FIG.1D). While we do observe a plateau in potential for Co-V LH inFIG.3A, it is at a significantly lower potential of ˜−1.0V vs. Ag/AgCl, at odds with the rigid band description. Additionally, we observe a plateau at a similar potential to the Co-V LDH for the Co—Al LDH and a plateau at a dramatically lower potential for the Co-only LH, neither of which are predicted by the rigid band description. We attribute the irreversible charge transfer at −1.2V vs. Ag/AgCl for the bare glassy carbon electrode (GCE), as well as Mg—Al LDH, and Co—Cr LDH measurements to the onset of the hydrogen evolution reaction (HER), which precludes the study of these LHs at more reducing potentials. Upon switching to a positive current at a time t=2 min inFIG.3A, the Fermi level decreases, and electrons transfer back out of the Co-V, Co—Al, and Co LH structures, leading to plateaus in potential under positive current as depicted inFIG.3A. The width of the plateau corresponds to the amount of charge transferred. We observe the widest plateau for the Co LH, corresponding to 36% coulombic efficiency, while ˜20% coulombic efficiencies are observed for the Co-V, and Co—Al LHs. We again employ EQCM here to understand the electrochemical behavior of these LHs under negative bias. The results from an EQCM measurement on the Co-V LH platelets is depicted inFIG.3B. We attribute the overall decrease in mass for the Co-V LDH inFIG.3Bto the delamination of the LH particles and dissolution of V (vide infra) during operation. For anion insertion charge storage, one would expect a mass loss under applied negative bias and a mass gain under applied positive bias. The predominant signal we measure inFIG.3Bis the inverse of this, with a mass gain under applied negative bias (−1.0V vs. Ag/AgCl), and a mass loss under applied positive bias (−0.5V vs. Ag/AgCl). This is at odds with anion insertion, and suggests a cation-based mechanism, such as the reversible formation of Co or V vacancies or the insertion of electrolyte cations (e.g., Na+) into the structure. We also observe a slower process following the initial mass spikes, highlighted with the dashed lines inFIG.3B, which is consistent with an anion-based mechanism. However, the mass-to-charge ratio (m/z) we derive from the slopes highlighted inFIG.3Bis m/z=17 g/mol e−, which agrees precisely with the mass-to-charge ratio expected for OH— and strongly suggests that OH—, not Cl−, is the species involved in this process. To better understand this electrochemical behavior, we expand upon the rigid band description and employ the UEB construct to model the thermodynamics of charged defects in LH structures under applied bias. We emphasize that conventional ΔEr×ncalculations versus a metallic reference commonly employed for studying cation insertion cannot be employed here because (a) no convenient electrochemical reference (e.g., bulk metal) is available for Cl−anions, and (b) the reactions occurring may involve multiple species. Within the UEB construct, an applied bias shifts the Fermi level within the band gap of these LH structures, and drives structural perturbations and the formation of charged defects and electronic states inside the band gap. In defect plots (i.e.,FIGS.4and17), the formation energy, ΔEf, is calculated for various defect charge states while accounting for the applied bias and electrolyte pH. A structural change is predicted to exist at a given potential when a given defect has a ΔEf<0, and that defect is expected to give rise to charge transfer when it changes charge state—corresponding to the kinks marked with symbols. Using the UEB computational framework we predict electrochemical behavior which agrees with our experimental observations as discussed below. STEM and ICP-OES analysis of the Co-V sample indicate a blend of V-rich Co3V(OH)8Cl (Co3V LDH) and V-deficient Co3(OH)6Cl. In order to understand the electrochemical behavior of the Co-V LDH inFIG.3B, we study both V-rich Co3V LDH and V-deficient Co3(OH)6Cl LH within the UEB construct. We examine vacancy, substitution, and interstitial point defects at various charged states within these structures. V-rich Co3V LDH domains in the Co-V LH sample do not contribute to the reversible charge storage we observe inFIGS.3A and3B—no defects in the Co3V LDH are predicted to be thermodynamically favorable and change charge state in the potential range of {0,−1.0} V vs. Ag/AgCl. Based on these calculations, electrochemical insertion of Cl— into the Co3V LDH requires a potential >0.4V vs. Ag/AgCl, and anion extraction requires a potential <−1.6V vs. Ag/AgCl. Additionally, V vacancies (vv) are predicted to be highly favorable (ΔEf<−2 eV), driving the conversion of Co3V LDH to Co LH. Considering this, we examine the UEB construct of Co3(OH)6Cl, as presented inFIG.4. We use the chlorinated Co LH for this study to enable the study of chloride vacancies. We note that this structure we use for modeling nominally contains a mixture of both Co(II) and Co(III). The predicted electrochemistry of the Co LH is in line with our experimental observations. First, UEB calculations on Co3(OH)6Cl provide an explanation for the cation-mediated mechanism we observe for the Co-V sample inFIG.3C. Under reducing current, at −1V vs. Ag/AgCl protons on Co vacancies (HCo) are predicted to exchange for V on Co vacancies (VCo), giving rise to charge transfer and cation uptake. In other words, V ions which have dissolved from the Co-V sample will reinsert into Co vacancies under applied negative bias. When the current is reversed to oxidizing conditions, the V is predicted to go back into solution and be replaced by a proton. Considering how rapidly these processes proceed inFIG.3B, the Co vacancies responsible for this mechanism likely reside at the edges of LH platelets, allowing for rapid V uptake. Secondly, UEB calculations on Co3(OH)6Cl predict the formation of Cl−vacancies at a potential more negative than −0.7V vs. Ag/AgCl. This may contribute to the anionic charge storage observed inFIG.3B, but only to a limited extent (see discussion below). Also, considering the measured m/z of 17 g/mol e−, OH— is likely responsible for the anion mechanism inFIG.3B. We note that that at a pH of 10, the Pourbaix diagram for cobalt predicts that potentials more negative than ˜0.6V vs. Ag/AgCl will drive the reduction of Co(OH)2to form metallic Co, depicted by the vertical dashed line inFIG.4. This process is likely responsible for the anion mechanism measured inFIG.3B, and is consistent with the plateau observed for the Co LH measured inFIG.3A. Extensive structural reorganization necessary to convert Co(OH)2to metallic Co will limit the rate of this process, in line with the slow rate of the anion-mediated process inFIG.3B. We note that the UEB calculations we perform do not capture the conversion of Co(OH)2to Co because we limited our modeling to incremental structural changes, and did not evaluate complete structural reorganizations. Although our calculations indicate that reversible anion incorporation does not occur in the Co-V LDH under applied negative bias, the UEB model predicts that Cl−insertion is expected to take place in Co3(OH)6Cl under positive bias as we observe inFIG.2. Examining the vcltrace inFIG.4, the formation energy of vclis greater than zero at potentials more positive than −0.8V vs. Ag/AgCl. This suggests Cl−will insert into interplanar ve, sites in this potential region. However, the corresponding electron transfer (kink in trace marked by a symbol) is not predicted to occur until potentials >0.1V vs. Ag/AgCl. Based on these calculations, we expect charge accumulation will limit the extent of Cl−insertion into vclsites until a potential >0.1 vs. Ag/AgCl is reached, at which point electron transfer will take place, driving additional incorporation of Cl−into interplanar vclsites. We also note that Pourbaix diagrams for Co suggest a transition from Co(OH)2to Co(OH)3at potentials >0.1V at a pH of 10 as indicated by the vertical dashed line inFIG.4. The nominal change in oxidation state from Co(II) to Co(III) suggested by the Pourbaix diagram is expected to coincide with Cl−insertion according to M(II)(OH)6+Cl−M(III)(OH)6Cl+e−. This Pourbaix description is consistent with the prediction of Cl−insertion inFIG.4. Based on this UEB modeling inFIG.4and Pourbaix diagram description, we expect that anion insertion will occur in the Co-V LDH sample under applied positive bias, arising from domains of Co LH. To evaluate this, we examine in situ EQCM, HE-XRD, and XAS data for Co-V LH platelets cycled in potential loops of {−0.9V, −0.2V, +0.2V, −0.2V}. We first examine the EQCM data inFIG.5A. We attribute the overall decrease in mass of the Co-V LDH to the favorable dissolution of V as predicted from UEB modeling. The potential-dependent mass changes for both the Co-V and Co LH samples inFIG.5Aare consistent with anion insertion. We observe a mass gain under positive bias (+0.2V) highlighted with blue arrows as anions are drawn into the interplanar space of the LHs, and a mass loss under reverse bias as anions leave the LHs. The similarity in results for the Co-V and Co LH samples inFIG.5Asupports the prediction that anion insertion takes place in Co LH domains of the Co-V LH sample. These results are also consistent with the EQCM results for the Co LH presented inFIG.2A. We also performed in situ HE-XRD measurements using a custom electrochemical cell to elucidate the structural changes during electrochemical cycling. Depicted inFIG.5Bare PDFs calculated from in situ HE-XRD data during electrochemical operation. In these traces, we observe a peak at a pair distance of r=4.2 Å which corresponds to the distance between interplanar anions and metal ions in the hydroxide sheets. Twice this distance corresponds to the interplanar spacing, here 8.4 Å. This is larger than the interplanar distance of ˜8 Å observed inFIG.1D. We attribute the increase in interplanar distance here to the use of the Br— anion for in situ measurements—the diameter of Br— is 3.92 Å, while the diameter of Cl—is 3.62 Å. We interpret an increase in G(r) intensity at r≈4.2 Å inFIGS.5B and5Cas an increase in the number of interplanar anions. InFIG.5C, G(r) intensity increases at r≈4.2 Å when switching from −0.2V (trace1) to +0.2V (trace2) vs. Ag/AgCl, indicating the incorporation of anions at +0.2V. G(r) intensity then decreases at r≈4.2 Å when switching from +0.2V (trace2) to −0.2V (trace3) vs. Ag/AgCl, indicating the release of interplanar anions. Furthermore, we note little change in the G(r) intensity at r≈4.2 Å when switching from −0.2V (trace3) to −0.9V (trace4) vs. Ag/AgCl, further corroborating our conclusion that interplanar anions do not leave the structure under negative bias. These HE-XRD results are consistent with the EQCM results presented above. While EQCM and PDF analysis provide strong support of electrochemical anion insertion in Co LH domains of the Co-V LDH sample, EXAFS measurements on the Co-V LDH over longer timescales suggests a competing Co dissolution mechanism. See supporting information for details on EXAFS experimentation. The results of steady-state EXAFS measurements are depicted inFIG.6, which indicate that the Co—Co/V nearest neighbor distance increases from 3.12 Å to 3.15 Å, and the Co—O nearest neighbor distances increase from 2.08 Å to 2.11 Å when switching from −0.2V to +0.2V vs. Ag/AgCl. While ab initio modeling predicts minimal changes in the Co—Co and Co—O distances due to Cl−insertion, these structural changes are in line with the formation of vCoat this potential. Ab initio calculations for the formation of Co vacancies near V dopants (modeled in the Co3V(OH)8Cl structure) predict these defects to occur at potentials >+0.2V vs. Ag/AgCl inFIG.3D, leading to an increase the average Co—Co distance from 3.01 Å in the perfect structure to 3.14 Å in a charged vCostructure, and an increase in the average Co—O distance from 2.06 Å in the perfect structure to 2.09 Å in a charged vCostructure. However we do not observe indicators for this mechanism in EQCM or PDF measurements. The formation of vComay proceed at too slow of a rate to be observed during relatively fast EQCM and PDF measurements (minutes timescale), but allowing for observation at the timescale of our EXAFS measurement (hours timescale). We also note that we do not observe changes in Co oxidation state in the X-ray absorption near-edge spectrum (XANES) at various applied biases (FIG.9). While a change in the charge state of Co ions is not requisite during charging of the Co LH for anion insertion, a charge state change is expected for the formation of metallic Co under applied negative bias (−0.2V), as described above. The absence of zero-valent Co in the XANES data under negative bias may suggest that the thermodynamic description laid out in the Co Pourbaix diagram does not fully capture the processes occurring under negative bias, or that only a small fraction of metallic Co forms during EXAFS measurements. More importantly, these findings suggest that additional work is needed to further understand the electrochemical processes in these promising materials. The experiments establish the electrochemical mechanisms occurring in Co and Co-V LH in aqueous electrolyte under both negative and positive applied bias. Under applied negative bias, we identify mechanisms for cation exchange (V insertion on Co site) and phase change (OH−removal to form metallic Co). Under positive bias, we observe electrochemical anion insertion-anions are drawn into the interplanar spaces of the LHs under positive bias, and driven out under reverse bias. We also observe evidence of slow dissolution of Co under positive bias. Our data suggests that Co LH enables anion insertion electrochemistry within the potential limits of water stability, while larger potentials are needed for anion insertion in other Co-containing LHs (e.g., Co3V LDH). With further refinement to prevent dissolution, enhance ion insertion rates, and improve stability, LHs based on this work could be designed to be paired with a cation insertion electrode material and used for energy efficient electrochemical desalination. The mechanistic understanding of layered hydroxide electrochemistry we establish also has far-reaching implications in other fields. Doping LHs to shift band edge positions and impact defect energy levels provides a means to enhance desired (photo)electrocatalytic pathways. Similarly, pairing two anion insertion processes which occur at different potentials in LHs allows for the fabrication of an anion-based battery for energy storage. Our work predicts that one LH structure with different levels of anion content could be used as both the anode and cathode in such a device, however, pairing two LHs is also possible. Furthermore, the controlled release of anions using (photo)electrochemical stimulus has potential use in biomedical applications-allowing a pathway for spatially-controlled delivery of therapeutic polyanions, including DNA or RNA fragments. Example II—In Situ Measurement and Quantum Simulations of a LDH as an Anion Intercalation Electrode for Battery-Inspired Water Desalination In situ measurement and quantum simulations were performed for a LDH as an Anion Intercalation Electrode for water desalination develop a fundamental understanding of the electrochemical properties of LDHs through the combination of electrochemistry, in situ X-ray experiments and modeling. Using Mg0.66Al0.33(OH)2as a model system, the proposed experimental and computational work can uncover the fundamental anion incorporation characteristics of these materials under applied bias, while potentially providing a readily adaptable methodology for studying other systems in the future. Mg0.66Al0.33(OH)2as Model LDH System: Mg0.66Al0.33(OH)2will be used as the model system for this study due to its simple synthesis, including known methods for its nanoparticle synthesis, the ability for it to intercalate CO32−, Cl−, and other anions, the large negative standard reduction potentials of Mg2+and Al3+, and for the wealth of experimental characterization on Mg0.66Al0.33(OH)2. Indeed, the first experimental study in1982showing interlayer spacing changes with intercalated anions were performed on this system. Nanoparticle synthesis of Mg0.66Al0.33(OH)2will be carried out according to the methods from Xu et al. This synthesis expands on the standard coprecipitation technique for LDH synthesis and will take advantage of current expertise and experimental capabilities for aqueous-based synthesis techniques at NIST Boulder. Concisely, this method involves the reaction of MgCl2with AlCl3in an aqueous NaOH solution under vigorous stirring, followed by centrifuge separation and hydrothermal treatment. It has been shown that the hydrothermal treatment conditions following reaction affect the resulting nanoparticle size. By adjusting the hydrothermal treatment temperature and time, the mean nanoparticle diameter of Mg0.66Al0.33(OH)2can be tuned continuously from 40 nm up to 300 nm. Characterization of Nanoparticulate Mg0.66Al0.33(OH)2: Following nanoparticle synthesis, the composition and particle size distribution of the synthesized nanoparticulate Mg0.66Al0.33(OH)2will be measured using a range of tools available at NIST Boulder's Precision Imaging Facility. These include transmission electron aberration corrected microscopy (TEAM), scanning helium ion microscopy (SHIM), and atom probe tomography (APT). TEAM and SHIM micrographs will be processed to quantify particle size distribution in the synthesized Mg0.66Al0.33(OH)2powders. Additionally, both electron diffraction in the TEAM, and elemental composition from APT will be used to verify formation of Mg0.66Al0.33(OH)2. These same characterization techniques will be used following electrochemical cycling to measure the changes in the Mg0.66Al0.33(OH)2.FIG.20shows and over of a study of anion intercalation in an Mg0.66Al0.33(OH)2 layered double hydroxide using quantum simulations and in situ HE-XRD and XAFS. In situ Observation of Electrochemical Anion Insertion/Extraction in Mg0.66Al0.33(OH)2: In order to understand structural changes in the layered double hydroxides and chemical environment of intercalated ions under applied bias, in situ HE-XRD and in situ XAFS will be performed. Electrochemical measurements will be carried out in custom cells optimized for in situ HE-XRD and XAFS measurements on NIST's Beamline for Materials Measurement (BMM) at the National Synchrotron Light Source II (NSLS-II) in Brookhaven National Laboratory and under the guidance of several researchers at NIST Boulder who currently conduct in situ HE-XRD and XAFS experiments for various nanoparticle materials. In order to make electrochemical measurements, nanoparticulate Mg0.66Al0.33(OH)2will be applied to an electrically conductive metal current collector using a binder. Synchrotron measurements will be performed with the electrochemical cell at a fixed potential after sufficient time for equilibration. This will provide higher resolution data as compared to cyclic voltammetry or other dynamic cycling techniques. To mimic electrochemical cycling, the fixed potential will be adjusted and snapshots of the system will be measured at different states of charge. The electrolyte used for electrochemical measurements will be an aqueous sodium salt electrolyte where the counter-ion to sodium is the anion to be studied for electrochemical intercalation in the LDH. Initially the carbonate anion will be studied due to its easy compatibility with most construction materials. Chloride, which is more relevant to CDI, will also be studied after modifying the electrochemical cell to remove any metal which is incompatible with chloride solutions. HE-XRD and XAFS have been used widely to study the electrochemical processes taking place in cation intercalation materials for lithium ion batteries. Prior in situ studies on LiMn2O4, LiSeSx, LiMn3O4, LixSi, and other electrode materials have demonstrated the ability to clearly identify changes in crystallinity, interatomic distances, and atomistic environment during electrochemical cycling. These techniques provide unsurpassed understanding of the mechanisms of charge storage during electrochemical cycling for cation intercalation materials, but have not previously been used to study LDHs. Here, we propose the first use of HE-XRD and XAFS for in situ study of an anion intercalation material. Using XAFS, the local coordination of the anion to either Mg or Al, as well as the distance between the anion and Mg/Al centers can be observed directly under an applied bias. Additionally, the crystalline peaks in the LDH, including those corresponding to interlayer spacing in the LDH, can be observed using HE-XRD during electrochemical cycling. The interlayer spacing is expected to change during insertion/extraction of anions and can be accurately measured with HE-XRD. HE-XRD will provide long-range crystal structure information during cycling, which, coupled with the local anion environment from XAFS will give a precise description of the atomic structure, and will provide insight for computational modeling. Furthermore, XAFS data measured near the absorption edge (XANES analysis) will allow for electronic structure determination near the Fermi level. This analysis will be paired with quantum simulations to understand the fundamental basis for the observed equilibrium potentials for anion insertion/extraction (vide infra). Coupled with electrochemical measurements, HE-XRD and XAFS will allow us to directly observe the insertion and extraction of anions into the LDH structure and the corresponding changes in electronic structure under an applied bias. Quantum Simulations of Mg0.66Al0.33(OH)2: Computational modelling of Mg0.66Al0.33(OH)2will provide a fundamental basis for understanding measured electrochemistry and synchrotron characterization results. Quantum mechanical calculations will be performed using the VASP on NIST's Raritan cluster. Bulk calculations will be corrected for surface and near-surface behavior characteristic of the measured nanoparticles by using pH and band-bending corrections. In situ HE-XRD and XAFS measurements will provide data on interlayer spacing, crystallinity, and atomistic environment changes under an applied bias to inform and be compared with computational results. Calculations will be performed in two stages for efficiency and accuracy. The accuracy and speed of calculations depends in part on the selected exchange-correlation functional. Specifically, equilibrium lattice parameters and band-gaps of Al and Mg-containing materials have been shown to be more accurate with the Heyd-Skusery-Ernzerhof (HSE) functional versus the than Perdew-Burke-Ernzerhof (PBE) functional, but the HSE functional is more computationally demanding than the PBE functional. So, initial calculations will be performed with PBE, while more accurate refinement calculations will be performed with HSE. From the results of these quantum mechanical simulations, a fundamental description of anion insertion/extraction will be established. As described in prior work by the applicant, the equilibrium potential for anion insertion/extraction will depend on the electronic structure of the unintercalated host material and the interaction behavior of the anion with the host. Anion-host interaction behavior is expected vary depending on the interlayer spacing of the host and the type of intercalated anion. Thus, a range of experimentally relevant interlayer spacings and anions will be studied computationally and the corresponding changes in the electronic structure and equilibrium potential will be determined. These computational results are expected to reflect XANES measurements and provide a fundamental basis for understanding anion intercalation. One application relates to the use of LHs for energy storage. Another application relates to the use of LHs for desalination. In one embodiment, PLH in situ synthesis embedding LH/LDHs into a porous support. The support may be nanoporous, mesoporous, or microporous. In one embodiment, the pores are >10 nm in order to accommodate the LH nanoparticles and allow for ion/solvent movement through the pores. In one particular embodiment, the porous network would contain a majority of pores between 15 and 200 nm to accommodate the particle size distribution of the LH nanoparticles, with a fraction (i.e., 10-50%) of pores consisting of larger microporous channels to allow for diffusion to the smaller porous network. The support material, in one embodiment, is an electrically conductive material such as carbon. In one method of fabricating PLH embedded in a porous support, the conductive support is synthesized in a solution of LH/LDH nanoparticles, such as shown inFIG.18. The LH nanoparticle size can be tuned by adjusting synthesis parameters, (less 3+ ion leads to smaller particles while longer hydrothermal treatment of LH particles at elevated temperature leads to larger LH) and tune the hydrogel porous network by adjusting hydrothermal formation conditions (higher temperature and longer time lead to smaller pores). Thus, the LH particle size and hydrogel pore size can be matched to improve ionic and electronic transport properties. As an example, LH hydrothermal formation at 125° C. for 2 hours followed by hydrogel hydrothermal formation at 100° C. for 4 hours In a first step, an LDH slurry is synthesized as described above. The LDH slurry is mixed with a graphene oxide (GO) aqueous solution and then sonicated to form a mixed solution. The mixed solution undergoes hydrothermal co-assembly to form a hybrid hydrogel in the solution. The hybrid hydrogel has a porous network with the LDH material disposed therein. The LDH and support hybrid material may be extracted such as by freeze-drying. In one method of fabricating PLH embedded in a porous support, the PLH material is synthesized within a conductive support as shown inFIG.19. A conductive support is added to the precursor solution of NaOH prior to injection of the salts to form the LHs material. The LH material is synthesized within the conductive porous material. In this case the conductive support can have a smaller uniform pore size (e.g., 20 nm) with a tight pore size distribution to maximize surface-area to volume ratio. The walls of the porous conductive support material may contain nucleation sites (i.e., functional groups, thin (oxy-)hydroxide coating, defects) to facilitate LH formation. In one embodiment, the LH material includes cross-linking between one or more layers. For example, cross linking may be accomplished through the use of polymeric ligands. Materials used to facilitate such crosslinking include, in some embodiments, 1) multifunctional organic molecules with two or more —OH reactive/complexing groups (e.g., thiols, acyl chlorides, carboxylic acids, etc.), 2) metal organic precursors with a metal in a valence state >1 (e.g., metal carbonyls, metal halides, metal alkylamides, metal diketonates), and 3) Polymerization reactions. In another embodiment, a LH material is used as a flow electrode. For example, LH nanoparticles may be a flow electrode. For such embodiment, the particles can be larger LH particles themselves could be larger, or LH particles could be incorporated into larger particles (as described above). Smaller LH particles should give rise to faster charging and higher efficiency because it limits the length scale over which bulk ion diffusion must take place. In one embodiment, as particulate flow electrodes, the LH or LH containing particles are blended with the electrolyte to make an anode-electrolyte mixture, or anolyte. LH anolyte is pumped from a reservoir through one half (the anolyte chamber) of a flow cell which comprises a metal current collector and an ion-conducting boundary which interfaces with the cathode-electrolyte or catholyte chamber of the flow cell, which has an analogous construction. A bias is either (1) applied across the anolyte and catholyte current collectors to charge the cell or (2) drawn from the current collectors to power a load during discharge. For energy storage only, the LH anolyte can be (1) paired with an LH catholyte to make an anion based battery or (2) paired with a cation-based catholyte to make a cation-anion hybrid cell. In order to perform water desalination or other industrial ion removal process (in addition to energy storage), one or more electrolyte flow chambers can be added between the catholyte chamber and anolyte chamber. With one electrolyte flow chamber, ions are removed from the influent electrolyte and are incorporated into the catholytes and anolytes during charging. A second flow cell can be connected with the same anolyte and catholyte streams and used to discharges the anolyte and catholyte and produce a stream of concentrated ions. Using two electrolyte flow chambers, the LH anolyte flows through both the catholyte and anolyte flow chambers, and under applied bias cations and anions collect in one of the flow chambers, leaving the other flow chamber with low ion concentrations. In another embodiment, the isolated LHs are provided as a 2-d material. For example, isolated Single or Few Layer LH/LDHs (i.e., 2D) can be utilized for surface redox reactions. Single layer or few layer LHs are exfoliated, for example by anion exchange with sequentially larger anions to drive the layers apart. The advantage of a single or few layer LH is that the electrochemical anion complexation can occur at the top surface of the LH, eliminating (or reducing) slow anion diffusion through the interplanar space of bulk LH particles, providing higher rate and higher efficiency devices. These single/few layer LHs can be used in each of the above embodiments. For example, single layer LHs can be cross-linked onto conductive supports or used as anolytes or catholytes in flow batteries. In one embodiment, the few layer means 5 layers or less. As used herein, the singular forms “a”, “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, the term “a member” is intended to mean a single member or a combination of members, “a material” is intended to mean one or more materials, or a combination thereof. As used herein, the terms “about” and “approximately” generally mean plus or minus 10% of the stated value. For example, about 0.5 would include 0.45 and 0.55, about 10 would include 9 to 11, about 1000 would include 900 to 1100. It should be noted that the term “exemplary” as used herein to describe various embodiments is intended to indicate that such embodiments are possible examples, representations, and/or illustrations of possible embodiments (and such term is not intended to connote that such embodiments are necessarily extraordinary or superlative examples). The terms “coupled,” “connected,” and the like as used herein mean the joining of two members directly or indirectly to one another. Such joining may be stationary (e.g., permanent) or moveable (e.g., removable or releasable). Such joining may be achieved with the two members or the two members and any additional intermediate members being integrally formed as a single unitary body with one another or with the two members or the two members and any additional intermediate members being attached to one another. It is important to note that the construction and arrangement of the various exemplary embodiments are illustrative only. Although only a few embodiments have been described in detail in this disclosure, those skilled in the art who review this disclosure will readily appreciate that many modifications are possible (e.g., variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters, mounting arrangements, use of materials, colors, orientations, etc.) without materially departing from the novel teachings and advantages of the subject matter described herein. Other substitutions, modifications, changes and omissions may also be made in the design, operating conditions and arrangement of the various exemplary embodiments without departing from the scope of the present invention. While this specification contains many specific implementation details, these should not be construed as limitations on the scope of any inventions or of what may be claimed, but rather as descriptions of features specific to particular implementations of particular inventions. Certain features described in this specification in the context of separate implementations can also be implemented in combination in a single implementation. Conversely, various features described in the context of a single implementation can also be implemented in multiple implementations separately or in any suitable subcombination. Moreover, although features may be described above as acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a subcombination or variation of a subcombination. | 64,827 |
11858827 | DETAILED DESCRIPTION Hereinafter, the implementation of the present disclosure and the beneficial effects thereof are described in details by way of specific examples, which is intended to provide a better understanding of the spirit and features of the present disclosure, but cannot be construed as limitation to the scope of implementation of the present disclosure. Example 1 According to the procedure shown inFIG.1, under stirring, 1 g of titanium oxysulfate was dispersed and dissolved into 100 ml of water to form a solution, and then aqueous ammonia at a concentration of 0.05 mol/L was slowly added dropwise to the solution until the solution became neutral, so that titanium oxysulfate was gradually and completely hydrolyzed to form a titanic acid hydrate precipitate. Subsequently, the titanic acid hydrate precipitate was ultrasonically dispersed, washed several times with deionized water, and separated by centrifugation. Thereafter, hydrogen peroxide and lithium hydroxide were dissolved in water to form an aqueous solution having a lithium hydroxide concentration of 0.7 mol/L and a hydrogen peroxide volume fraction of 2.5%. Subsequently, the separated titanic acid hydrate precipitate was dispersed in 100 ml of the above-prepared lithium hydroxide aqueous solution containing hydrogen hydroxide with stirring to form a yellow transparent solution. Next, the above yellow transparent solution was heated to 75° C. and then stirred at constant temperature for 8 hours, and the reaction was stopped and separated to give a white solid. Subsequently, the above white solid was placed in an oven and dried at 60° C. for 20 hours. Then, the dried white solid powder was placed in an oven for annealing at 120° C. for 12 hours so as to remove hydrogen peroxide on the surface of the nanowire. After that, the above low-temperature treated white solid powder was dispersed in 100 mL of pure water and reacted at 100° C. for 5 hours, to give a nanotube hierarchically structured lithium titanate product. The SEM image thereof is shown inFIG.2.FIG.3is a diagram showing the discharging capacity of a lithium ion battery at different charging and discharging rates when the hierarchically structured lithium titanate obtained in the Example 1 is applied to the negative electrode of a lithium ion battery. The lithium ion battery electrode was prepared by using a knife coating process. Firstly, a slurry was prepared in a mass ratio of hierarchically structured sodium titanate microspheres: Super P: polyvinylidene fluoride (PVDF)=7:2:1 in N-methylpyrrolidone (NMP) as solvent. Subsequently, the slurry was uniformly coated on a copper foil with a knife coater, and a model CR2032 button cell was assembled in a glove box by using metallic lithium as a counter electrode, 1 mol/L LiPF6/EC-DMC-EMC (1:1:1) as electrolyte, and Glass Fiber as a separator, and subjected to an electrochemical test. As can be seen fromFIG.3, the materials achieve excellent results in the lithium ion battery performance test, and the battery has a high discharging capacity even at different charging and discharging rates. Example 2 Under stirring, 2 g of titanium sulfate was dispersed and dissolved into 100 ml of water to form a solution, and then sodium hydroxide at a concentration of 0.10 mol/L was slowly added dropwise to the solution until the solution became neutral, so that titanium sulfate was gradually and completely hydrolyzed to form a titanic acid hydrate precipitate. Subsequently, the titanic acid hydrate precipitate was ultrasonically dispersed, washed several times with deionized water, and separated by centrifugation. Thereafter, hydrogen peroxide and lithium hydroxide were dissolved in water to form an aqueous solution having a lithium hydroxide concentration of 0.8 mol/L and a hydrogen peroxide volume fraction of 5%. Subsequently, the separated titanic acid hydrate precipitate was dispersed in 100 ml of the above-prepared lithium hydroxide aqueous solution containing hydrogen hydroxide with stirring to form a yellow transparent solution. Next, the above yellow transparent solution was heated to 85° C. and then stirred at constant temperature for 6 hours, the reaction was stopped and separated to give a white solid. Then, the above white solid was placed in an oven and vacuum dried at 25° C. for 24 hours. After that, the dried white solid powder was placed in an oven for annealing at 120° C. for 12 hours so as to remove hydrogen peroxide on the surface of the nanowire. Subsequently, the above low-temperature treated white solid powder was dispersed in 100 mL of pure water containing 40% ethanol and reacted at 120° C. for 6 hours, to give a nanotube hierarchically structured lithium titanate product. The SEM image thereof is substantially the same asFIG.2. Example 3 Under stirring, 5 g of titanium tetrachloride was dispersed and dissolved into 100 ml of water to form a solution, and then potassium hydroxide at a concentration of 0.10 mol/L was slowly added dropwise to the solution until the solution became neutral, so that titanium tetrachloride was gradually and completely hydrolyzed to form a titanic acid hydrate precipitate. Subsequently, the titanic acid hydrate precipitate was ultrasonically dispersed, washed several times with deionized water, and separated by centrifugation. Thereafter, hydrogen peroxide and lithium hydroxide were dissolved in water to form an aqueous solution having a lithium hydroxide concentration of 0.6 mol/L and a hydrogen peroxide volume fraction of 4%. Subsequently, the separated titanic acid hydrate precipitate was dispersed in 200 ml of the above-prepared lithium hydroxide aqueous solution containing hydrogen hydroxide with stirring to form a yellow transparent solution. Next, the above yellow transparent solution was heated to 95° C. and then stirred under constant temperature for 4 hours, the reaction was stopped and separated to give a white solid. Then, the above white solid was placed in an oven and vacuum dried at 80° C. for 12 hours. After that, the dried white solid powder was placed in an oven for annealing at 150° C. for 6 hours so as to remove hydrogen peroxide on the surface and inside of the nanowire. Subsequently, the above low-temperature treated white solid powder was dispersed in 200 mL of an aqueous solution containing 0.01 mol/L nitric acid and reacted at 140° C. for 2 hours, to give a nanotube hierarchically structured lithium titanate product. The SEM image thereof is substantially the same asFIG.2. Example 4 Under stirring, 3 g of titanium isopropoxide was dispersed 100 ml of an aqueous solution for direct hydrolysis to form a titanic acid hydrate precipitate. Subsequently, the titanic acid hydrate precipitate was ultrasonically dispersed, washed several times with deionized water, and separated by centrifugation. Thereafter, hydrogen peroxide and lithium hydroxide were dissolved in water to form an aqueous solution having a lithium hydroxide concentration of 0.8 mol/L and a hydrogen peroxide volume fraction of 5%. Subsequently, the separated titanic acid hydrate precipitate was dispersed in 100 ml of the above-prepared lithium hydroxide aqueous solution containing hydrogen hydroxide under stirring to form a yellow transparent solution. Next, the above yellow transparent solution was heated to 80° C. and then stirred under constant temperature for 4 hours, the reaction was stopped and separated to give a white solid. Subsequently, the above white solid was placed in an oven and vacuum dried at 70° C. for 15 hours. Then, the dried white solid powder was placed in an oven for annealing at 200° C. for 1 hour so as to remove hydrogen peroxide on the surface and inside of the nanowire. After that, the above low-temperature treated white solid powder was dispersed in 150 mL of an aqueous solution containing 0.1 mol/L lithium hydroxide and reacted at 150° C. for 1.5 hours, to give a nanotube hierarchically structured lithium titanate product. The SEM image thereof is substantially the same asFIG.2. Example 5 Hydrogen peroxide and lithium hydroxide were first dissolved in water to form 100 ml of an aqueous solution having a lithium hydroxide concentration of 0.9 mol/L and a hydrogen peroxide volume fraction of 3%. Under stirring, 1 g of titanium oxysulfate was slowly added to the above aqueous solution with stirring to form a yellow transparent solution. Next, the above yellow transparent solution was heated to 70° C. and then stirred under constant temperature for 8 hours, the reaction was stopped and separated to give a white solid. Subsequently, the above white solid was placed in an oven and vacuum dried at 60° C. for 20 hours. Subsequently, the dried white solid powder was placed in a tube furnace for annealing at 150° C. for 3 hours under a nitrogen atmosphere to remove hydrogen peroxide on the surface and inside of the nanowire. After that, the above low-temperature treated white solid powder was dispersed in 100 mL of pure water and reacted at 100° C. for 5 hours, to give a nanotube hierarchically structured lithium titanate product. The SEM image thereof is substantially the same asFIG.2. Example 6 Hydrogen peroxide and lithium hydroxide were first dissolved in water to form 100 ml of an aqueous solution having a lithium hydroxide concentration of 0.6 mol/L and a hydrogen peroxide volume fraction of 2%. Under stirring, 1 g of tetrabutyl titanate was slowly added to the above aqueous solution with stirring to form a yellow transparent solution. Next, the above yellow transparent solution was heated to 80° C. and then stirred under constant temperature for 5 hours, the reaction was stopped and separated to give a white solid. Subsequently, the above white solid was placed in an oven and vacuum dried at 60° C. for 20 hours. Then, the dried white solid powder was placed in a tube furnace for annealing at 150° C. for 3 hours under a nitrogen atmosphere to remove hydrogen peroxide on the surface and inside of the nanowire. After that, the above low-temperature treated white solid powder was dispersed in 100 mL of pure water containing 40% ethanol and reacted at 120° C. for 3 hours, to give a nanotube hierarchically structured lithium titanate product. The SEM image thereof is substantially the same asFIG.2. Example 7 The nanotube hierarchically structured lithium titanate prepared in Example 1 was separated, placed in an oven, and dried at 120° C. for 24 hours. Subsequently, the dried nanotube hierarchically structured lithium titanate was separated by washing several times with deionized water and then placed in a 0.01 mol/L nitric acid solution for hydrogen ion exchange. After the hydrogen ion exchange, it is washed several times with deionized water until the pH of the washing liquid was near neutral, and then separated and dried, to give a nanotube hierarchically structured titanic acid. Example 8 The nanotube hierarchically structured lithium titanate prepared in Example 1 was separated, placed in an oven, and dried at 150° C. for 12 hours. Subsequently, the dried nanotube hierarchically structured lithium titanate was separated by washing several times with deionized water and then placed in a 0.05 mol/L hydrochloric acid solution for hydrogen ion exchange. After the hydrogen ion exchange, it is washed several times with deionized water until the pH of the washing liquid was near neutral, and then separated and dried, to give a nanotube hierarchically structured titanic acid. Example 9 The nanotube hierarchically structured lithium titanate prepared in Example 1 was separated, placed in an oven, and dried at 200° C. for 4 hours. Subsequently, the dried nanotube hierarchically structured lithium titanate was separated by washing several times with deionized water and then placed in a 0.1 mol/L acetic acid solution for hydrogen ion exchange. After the hydrogen ion exchange, it is washed several times with deionized water until the pH of the washing liquid was near neutral, and then separated and dried, to give a nanotube hierarchically structured titanic acid. Example 10 The nanotube hierarchically structured lithium titanate prepared in Example 7 was placed in a muffle furnace and annealed at 400° C. for 4 hours, to obtain a nanotube hierarchically structured titanium oxide. The SEM image thereof is shown inFIG.4.FIG.5is a diagram showing the rate of photocatalytic degradation of methylene blue with the nanotube hierarchically structured titanium oxide in this example. The test was carried out under the conditions in which 50 mg of the hierarchically structured titanium dioxide product prepared in this example was dispersed in a 10 mg/L methylene blue solution, with the diagram showing the rate of photocatalytic degradation of methylene blue by irradiation with a 3 watt LED UV lamp. Under the same test conditions, P25 was used as a reference substance. It can be seen fromFIG.5that the performance of the material prepared in this example in photocatalytic decomposition of an organic substance is better than that of the existing commercialized product P25, and is promising for application in photocatalytic decomposition of organic pollutants. Example 11 The nanotube hierarchically structured titanic acid prepared in Example 7 was placed in a muffle furnace and annealed at 600° C. for 3 hours to obtain a nanotube hierarchically structured titanium oxide. The SEM image thereof is substantially the same asFIG.4. Example 12 The nanotube hierarchically structured titanic acid prepared in Example 7 was dispersed in 100 mL of pure water and reacted at 180° C. for 6 hours to obtain a nanotube hierarchically structured titanium oxide. The SEM image thereof is substantially the same asFIG.4. Example 13 The nanotube hierarchically structured titanic acid prepared in Example 7 was dispersed in 100 mL of a nitric acid solution having a concentration of 0.01 mol/L and reacted at 150° C. for 12 hours to obtain a nanotube hierarchically structured titanium oxide. The SEM image thereof is substantially the same asFIG.4. Example 14 The nanotube hierarchically structured titanic acid prepared in Example 7 was dispersed in 100 mL of an aqueous ammonia solution having a concentration of 0.01 mol/L and reacted at 120° C. for 24 hours to obtain a nanotube hierarchically structured titanium oxide. The SEM image thereof is substantially the same asFIG.4. | 14,442 |
11858828 | DETAILED DESCRIPTION OF THE INVENTION Unless indicated otherwise, the indefinite articles “a” and “an” are synonymous with “at least one” or “one or more.” Unless indicated otherwise, definite articles used herein, such as “the,” also include the plural of the noun. The terms “comprising,” “consisting essentially of,” “consisting of,” and their related forms (e.g. comprises, etc), have their ordinary and customary meaning under U.S. patent law and are within the scope of the present invention. Unless indicated otherwise, the terms “method(s)” and “process(es)” are synonymous. Unless otherwise indicated, the elements of methods or processes described herein are not necessarily performed in the order in which the process elements are listed. Unless otherwise indicated, the term “nano” as used herein has its ordinary and customary meaning of being on the order of 1×10−9, with, for example, a “nanometer” being on the order of 1×10−9m. Embodiment One One embodiment of the present invention relates to an array of transition metal tubular architectures, wherein the transition metal tubular architectures are comprised of a transition metal oxide, sulfide, or selenide, and wherein transition metal tubular architectures are less than 100 nm in length. In preferred embodiments, the transition metal tubular architectures are at least partially crystalline. The transition metal tubular architectures are one-dimensional structures; as used herein, the term “one-dimensional” relates to the length dimension of the nanotubes. Accordingly, as used herein, the term “sub-100 nm” refers to transition metal tubular architectures that are less than 100 nm in length. The tubular architectures are preferably hollow nanotubes. In some embodiments of the present invention, a distribution of transition metal tubular architectures exists within the array where architectures of different lengths are present. The transition metal tubular architectures can be, independently, from 50 to less than 100 nm in length, preferably from 60 to 90 nm in length, more preferably from 60 to 80 nm in length, and even more preferably from 65 to 75 nm in length, e.g, 70 nm in length. The variance in these length values is ±10 nm, more preferably ±5 nm, more preferably ±3 nm, more preferably ±1 nm, and most preferably ±0.5 nm. All real numbers between these minimum and maximum values are disclosed herein. In these embodiments, at least 80% of the architectures, e.g. hollow transition metal oxide, sulfide, and/or selenide nanotubes, are less than 100 nm in length, preferably at least 85%, more preferably at least 90%, and most preferably at least 95% of the nanotubes are less than 100 nm in length. The “distribution of metal tubular architectures” can be referred to as an array of metal tubular architectures. All real numbers between these minimum and maximum values are disclosed herein. In another embodiment, 100% of the transition metal tubular architectures are less than 100 nm in length. As used herein, the transition metal of the transition metal tubular architectures comprises all transition metals of the periodic table of elements. Preferred transition metals comprise, but are not limited to, Scandium, Yttrium, Titanium, Zirconium, Vanadium, Niobium, Tantalum, and Dubnium. Most preferably, the transition metals comprise, but are not limited to, Yttrium, Titanium, Zirconium, with Titanium being the most preferred transition metal. The transition metal tubular architectures are comprised preferably of oxides of the transition metals listed above. At least one of the transition metals described above can be present in the transition metal tubular architectures. Preferably, one transition metal is the predominate transition metal present in the transition metal tubular architectures, meaning that at least 51 mol % of the transition metals in the transition metal tubular architectures is one transition metal listed above. In preferred embodiments, at least 75 mol % of the transition metals in the transition metal tubular architectures is one transition metal listed above, more preferably at least 80 mol %, more preferably at least 85 mol %, more preferably at least 90 mol %. In another preferred embodiment, one transition metal listed above represents 100 mol % of the transition metal present as the transition metal of the transition metal tubular architecture. In one embodiment the transition metal can include alloys of the metals listed above. All real numbers between these minimum and maximum values are disclosed herein. In preferred embodiments, the transition metal tubular architectures of the present invention are at least partially crystalline, where the partial crystallinity can be determined by analytical techniques such as X-ray diffraction. The terms “partially crystalline” and “partial crystallinity” as used herein means that the resultant metal tubular structures show by standard characterizations such as x-ray diffraction (or other characterizations noted below) signatures of at least one polycrystalline phase. In these embodiments, the transition metal tubular architectures are characterized by crystal structures and exhibit facets in their crystal structures. The facets can be the {001}, {004}, {101}, {105}, {200}, and {211} facets. The facets are determined by, for example, X-ray diffraction (XRD) pattern analysis of the transition metal tubular architectures, and facets correspond to diffraction peaks determined from XRD analyses. For example, in the embodiment where the transition metal tubular architecture is a titanium oxide nanotube and a distribution of nanotubes is present, all nanotubes being sub 100 nm in length, the nanotubes are characterized by diffraction peaks at 25.3°, 37.7°, 47.8°, 53.8°, and 54.9° (2Θ) in the XRD pattern analysis, corresponding to the (101), (004), (200), (105), and (211) facets, respectively. The transition metal tubular architectures of the present invention have been analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and diffuse reflectance spectra, which show the presence of crystallinity in the transition metal tubular architectures of the present invention. The transition metal tubular architectures can be doped with other elements from the periodic table of elements, so long as the dopant can be incorporated into the transition metal tubular architectures. Examples of dopants include, but are not limited to, Boron, Aluminum, Gallium, Indium, Carbon, Silicon, Germanium, Tin, Nitrogen, Phosphorus, Arsenic, Antimony, Oxygen, Sulfur, Selenium, Tellurium, Vanadium, Niobium, Tungsten, Copper, Silver, and Gold. Embodiment Two Another embodiment of the present invention relates to methods of making an array of transition metal tubular architectures, wherein the transition metal tubular architectures are comprised of a transition metal oxide, sulfide, or selenide, and wherein transition metal tubular architectures are less than 100 nm in length as in Embodiment One. These methods comprise oxidation of a transition metal in the presence of fluid medium that comprises an electrolyte, an acid, and a polymer. In preferred embodiments, the oxidation takes place during a galvanic anodization, where the fluid medium preferably surrounds an electrode on which anodization takes place. The composition of the fluid medium, described below, can influence the length of the transition metal tubular architectures, and the composition of the fluid medium herein is such that transition metal tubular architectures having the lengths described above, e.g. from 50 to less than 100 nm in length and the preferred values and variances given above are obtained. The fluid medium can be a solvent, such as organic solvents. Non-limiting examples include water, alcohols, and amines, with specific non-limiting examples including methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, and formamide. Mixtures of these solvents can be used, where the proportions are not particularly limited so long as oxidation and nanotube growth occurs. In some embodiments of the present invention, the solvent comprising the fluid medium is either solely formamide or a mixture of formamide and an alcohol such as ethylene glycol. Without wishing to be bound to a particular theory, increasing the relative amount of the alcohol, from 0 vol % to 50 vol %, preferably results in shorter nanotubes. All real numbers between these minimum and maximum values are disclosed herein. Non-limiting examples of volume ratios include 50:50 formamide:alcohol, 60:40 formamide:alcohol, 65:35 formamide:alcohol, 70:30 formamide:alcohol, 75:25 formamide:alcohol, 80:20 formamide:alcohol, 85:15 formamide:alcohol, 90:10 formamide:alcohol, and 95:5 formamide:alcohol. In preferred embodiments, an increase in fluid medium viscosity leads to an increase in nanotube length. As used herein, galvanic anodization relates to methods of oxidizing a metal with an electrochemical cell. Preferably, at least one electrode is substantially comprised of the transition metal that forms the transition metal tubular architectures of the present invention. In galvanic anodization, at least two electrodes are present in a fluid medium as part of the electrochemical cell, where the fluid medium comprises an electrolyte, an acid, and a polymer. As used herein, unless otherwise indicated, the term “substantially” means at least 85 mol % of the transition metal tubular architectures. The oxidation reactions that form the transition metal tubular architectures as disclosed herein can be carried out for any length of time sufficient to form the transition metal tubular architectures, and the oxidation time period can change the length of the nanotubes. Generally, increased oxidation times leads to increased nanotube length. Accordingly, it is preferred to perform oxidation long enough to form transition metal tubular architectures having the lengths described above, e.g. from 50 to less than 100 nm in length and the preferred values and variances given above. Non-limiting examples of oxidation time from 30 minutes to 200 minutes, preferably from 45 minutes to 180 minutes, e.g. 180 minutes. In some embodiments, an electrode is the anode and another electrode is the cathode, where the anodic cell and the cathodic cell comprise a fluid medium and the cells are isolated from each other. In these embodiments, an electrolyte bridge connects the anodic cell or cells to the cathodic cell or cells. In other embodiments, an electrode is the anode and another electrode is the cathode, where the anodic cell and the cathodic cell each comprise a fluid medium and each cell is isolated from each other. In these embodiments, a polymeric, electrolyte membrane separates the anodic cell or cells from the cathodic cell or cells. As used herein, unless otherwise indicated, the electrolyte is not particularly limited unless the electrolyte is insufficient to promote the oxidation of the metal. In preferred embodiments, the electrolyte comprises at least one a halide of an alkali metal (Li, Na, K, Rb, Cs, Fr) or alkaline earth metal (Be, Mg, Ca, Sr, Ba, Ra), a carbonate or bicarbonate of an alkali metal or alkaline earth metal, quaternized nitrogen compounds of halides, ammonium halides. As used herein, halides refer to a fluoride, a chloride, a bromide, and/or an iodide. In preferred embodiments, the electrolyte comprises a fluoride salt. In the most preferred embodiments, the electrolyte is NH4F. The amount of electrolyte is not particularly limited so long as the oxidation of the transition metal(s) proceeds. In preferred embodiments, the amount of electrolyte, relative to the entire amount of the fluid medium, is from 0.01 to 5 wt %, more preferably from 0.1 to 3 wt %, more preferably from 0.5 to 1.5 wt %. In the most preferred embodiments, the amount of electrolyte is from 0.75 to 1.1 wt %, such as 1 wt %. All real numbers between these minimum and maximum values are disclosed herein. In some embodiments, the amount of electrolyte can change the thickness of the walls of the transition metal tubular architectures. The amount is not particularly limited, preferably it is present in the amounts described above, so long as the oxidation of the transition metal(s) proceeds and suitable wall thicknesses are achieved. The wall thicknesses can be from 3 nm to 10 nm, preferably from 3 nm to 5 nm, and the variances of thickness can be ±0.05 nm, preferably *0.01 nm. All real numbers between these minimum and maximum values are disclosed herein. The fluid medium can comprise one of the above-described electrolytes or the fluid medium can comprise at least two of the above-described electrolytes. Preferably, oxidation occurs after the fluid medium is prepared by a user, directly or through machine aided processes. The polymer present in the fluid medium is not particular limited so long as the oxidation proceeds and transition metal tubular architectures are obtained. In preferred embodiments, the polymer is polyvinylpyrrolidone (PVP). Without wishing to be bound to a particular theory, the polymer is believed to promote the formation of the crystalline structure of transition metal tubular architectures. In preferred embodiments, the amount of polymer, relative to the entire amount of the fluid medium, is from 0.01 to 5 wt %, more preferably from 0.1 to 3 wt %, more preferably from 0.5 to 1.5 wt %. In the most preferred embodiments, the amount of polymer is from 0.75 to 1.1 wt %, such as 1.1 wt %. All real numbers between these minimum and maximum values are disclosed herein. The molecular weight of the polymer is not particular limited so long as the oxidation of the transition metal proceeds and crystalline transition metal tubular architectures are obtained. In preferred embodiments, the molecular weight of the polymer is from 20,000 g/mol to 1,000,000 g/mol, more preferably from 30,000 g/mol to 800,000 g/mol, more preferably from 35,000 g/mol to 650,000 g/mol. All values between these minimum and maximum values are suitable for the invention. In some embodiments, the molecular weight has values of ±1000 g/mol. In some embodiments, the polymer is a PVP having a molecular weight of 40,000 g/mol, an example of this polymer being 40,000 g/mol PVP from Loba Chemie. The fluid medium can comprise one of the above-described polymers or the fluid medium can comprise at least two of the above-described polymers. The acid present in the fluid medium is not particular limited so long as the oxidation proceeds and transition metal tubular architectures are obtained. Non-limiting examples of the acid include hydrochloric acid, hydrobromic acid, acetic acid, formic acid, trichloroacetic acid, oxalic acid, sulfurous acid, phosphoric acid, and nitrous acid. Most preferably, the acid is acetic acid. The acid can be added to the fluid medium in the form of aqueous concentrations of the acid, for example, from 0.01M to 5M, more preferably from 0.1M to 1M. The amount of the acid or aqueous concentration thereof is not particularly limited so long as the pH of the fluid medium is sufficient for oxidation to proceed and transition metal tubular architectures are obtained. In preferred embodiments, the amount of acid or aqueous concentration thereof in the fluid medium is from 0.01 to 5 wt %, more preferably from 0.1 to 3 wt %, more preferably from 0.1 to 1.5 wt %. In the most preferred embodiments, the amount of acid or aqueous concentration there is from 0.1 to 0.5 wt %, such as 0.35 wt %. All real numbers between these minimum and maximum values are disclosed herein. The pH of the fluid medium for these concentrations is preferably from 2 to 6.9, more preferably from 3 to 6, even more preferably from 3 to 5, for example, 4. When the transition metal of the transition metal tubular architectures is comprised of titanium, preferably in an amount of at least 50 mol % relative to 100 mol % of the transition metals, and titanium oxide is formed during oxidation, the pH of the fluid medium is preferably from 3 to 5. All real numbers between these minimum and maximum values are disclosed herein. The fluid medium can comprise one of the above-described acids or aqueous concentrations thereof or it can comprise at least two of the above-described acids or aqueous concentration thereof. The temperature of the reaction environment in which the oxidation reaction takes place is not particularly limited so long as the oxidation proceeds and transition metal tubular architectures are obtained. The amperage, in the case of anodization, is from 5 to 30 milliamps (“mA”), more preferably from 7 to 25 mA, more preferably from 10-20 mA, more preferably from 10-15 mA and the temperature of oxidation should be set at a value that does not promote significant amperage fluctuations. Amperage fluctuation is preferably ±1.0 mA, more preferably ±0.5 mA, even more preferably ±0.1 mA. All real numbers between these minimum and maximum values are disclosed herein. In preferred embodiments of the present invention, amperage is set between the range of 5 to 30 mA, as described above, by ramping the voltage applied to the oxidation reaction, e.g., during galvanic anodization, from 0 to 50 V. All real numbers between these minimum and maximum values are disclosed herein. As used herein, the term “ramping” refers to a change from one voltage value to another, for example increasing the voltage from 0 V to 50 V overtime. Ramping can increase the voltage or decrease the voltage over time. Ramping can also be carried out in one, two, or more stages, where stage one exhibits ramping between at least two voltage values, stage two exhibits ramping between at least two other voltage values, and this ramping occurs for each stage. The ramping per stage can be an increase in voltage or a decrease in voltage, or both. In the most preferred embodiments, the voltage is ramped in one, two, or more stages so that the amperage during oxidation stays between 5 to 30 mA. Preferably, the ramping for each stage occurs at a rate of from 1 to 10 V/min, preferably from 1.5 to 8 V/min, more preferably from 1.6 to 7 V/min, where this rate can be positive for an increase in voltage and negative for a decrease in voltage. All real numbers between these minimum and maximum values are disclosed herein. In some embodiments, the voltage applied during oxidation as described above can influence the length, diameters and wall thicknesses of the transition metal tubular architectures. In general, greater voltages lead to higher nanotube growth rates and longer nanotubes, and longer oxidation times generally lead to longer nanotubes. The diameters are not particularly limited, so long as the transition metal tubular architectures form. Oxidation time, such as anodization time, can affect the wall thicknesses. In general, longer oxidation times result in greater diameters and thinner walls. The diameters can be from 5 to 50 nm, preferably from 10 to 40 nm, more preferably from 15 to 30 nm, e.g. 20 nm, and the variances of diameters can be ±5 nm, preferably ±3 nm, most preferably ±1.5 nm. All real numbers between these minimum and maximum values are disclosed herein. The wall thicknesses can be from 3 nm to 10 nm, preferably from 3 nm to 5 nm, and the variances of thickness can be ±0.05 nm, preferably ±0.01 nm. All real numbers between these minimum and maximum values are disclosed herein. The temperature of the reaction environment in which oxidation occurs should be a temperature in which the current minimally fluctuates during the oxidation reaction. In preferred embodiments, the temperature of the reaction environment in which the oxidation reaction takes place is from −50° C. to 30° C., more preferably from −25° C. to 30° C., even more preferably from −5° C. to 27° C. All values included within these ranges are suitable for the invention. In one embodiment, these temperatures are controlled by thermal contact of the electrolytic cell to a temperature controlled bath. In some embodiments, temperature of the reaction environment is room temperature. In other embodiments, the temperature of the reaction environment is 0° C. and can fluctuate from this temperature during oxidation by ±0.5° C., more preferably ±0.1° C. Without wishing to be bound to a particularly theory, it is believed that temperature fluctuations, particularly at temperatures at or above room temperature, can result in large current fluctuations during the oxidation reaction. Such large current fluctuations can reduce the crystallinity of the transition metal tubular architectures. In one embodiment, the large current fluctuations are preferably mitigated by controlling the temperature of the environment in which oxidation takes place. The way in which the current fluctuations are controlled is not particularly limited, so long as current fluctuations are controlled. In some embodiments, the oxidation reaction is carried out in an electrochemical cell that is immersed in a fluid medium set to a temperature of −50° C. to 30° C., more preferably from −25° C. to 30° C., even more preferably from −5° C. to 27° C., with all real numbers included within these ranges disclosed herein. Non-limiting examples of the fluid medium include a liquid water bath and an ice bath. Alternatively, the current can be controlled by a current controlled voltage source, which controls the current and limits fluctuations in the current across the anodic cell and the cathodic cell. An example of current controlled voltage source is a current control unit known in the art. In some embodiments, the methods further comprise cleaning electrodes of the electrochemical cell with ultrasonic vibration prior to being placed in the electrochemical cell. The cleaning with ultrasonic vibration preferably occurs in the presence of a solvent such as acetone. The frequencies of sonic vibration can be at greater than or equal to 20 kHz. In some embodiments, the methods further comprise annealing the oxidized metal after the oxidation, which normally takes place by galvanic anodization, to form the transition metal tubular architectures. This annealing can take place at room pressure, under vacuum, or under pressure, so long as the annealing is not inhibited. The temperature of annealing is preferably from 200° C. to 600° C., where the time period for annealing is not particularly limited. The temperature can be changed during annealing, where the increase or decrease of the temperature can occur at a rate of from 0.5 to 5° C./min, with all real numbers between these minimum and maximum values Annealing can take place in oxygen or air. In the present invention, for those embodiments where zirconium is the transition metal, the cell solution present during oxidation does not necessarily include PVP. In other embodiments of the processes disclosed herein, the processes further comprising doping the transition metal tubular architectures with other elements from the periodic table of elements, so long as the dopant can be incorporated into the transition metal tubular architectures. Examples of dopants include, but are not limited to, Boron, Aluminum, Gallium, Indium, Carbon, Silicon, Germanium, Tin, Nitrogen, Phosphorus, Arsenic, Antimony, Oxygen, Sulfur, Selenium, Tellurium, Vanadium, Niobium, Tungsten, Copper, Silver, and Gold. The process element of doping the transition metals can be carried out in several ways. In one embodiment, the dopant is added to the fluid medium in the form of a salt, so long as the salt is sufficiently miscible in the fluid medium and the dopant can be incorporated into the architectures. In another embodiment of this doping, the transition metal tubular architectures, after they are made, are immersed in a fluid containing a dopant and the solution is heated and another anodization is performed. Embodiment Three Another embodiment of the present invention relates to methods of splitting water in the presence of an array of transition metal tubular architectures, wherein the transition metal tubular architectures are comprised of a transition metal oxide, sulfide, or selenide, and wherein transition metal tubular architectures are less than 100 nm in length according to Embodiment One. Unless otherwise indicated, the phrase “an array of transition metal tubular architectures of sub-100 nm in length” used in this embodiment refers to the an array of transition metal tubular architectures, wherein the transition metal tubular architectures are comprised of a transition metal oxide, sulfide, or selenide, and wherein transition metal tubular architectures are less than 100 nm in length according to Embodiment One. As used herein, the term “splitting water” refers to oxidation of oxygen and reduction of hydrogen in water molecules to produce H2and O2. This process is described as: 2H2O→O2+4H++4e− 4H++4e−→2H2 2H2O→2H2+O2 The method of splitting water comprises contacting a photoanode or a photocathode with light, said photoanode or said photocathode comprising or having an array of transition metal tubular architectures, wherein the transition metal tubular architectures are comprised of a transition metal oxide, sulfide, or selenide, and wherein transition metal tubular architectures are less than 100 nm in length according to Embodiment One on a surface of the photoanode or the photocathode, said photoanode or photocathode being immersed in water. The light of this contacting is not particularly limited, so long as it provides energy to the photoanode or photocathode sufficient to split water. The wavelength of light suitable for use is from 10 nm to 1,000,000 nm, and the wavelength applied to the photoanode or photocathode can be a single wavelength or a spectrum of wavelengths such as sunlight. The device in which water splitting occurs is not particularly limited, so long as the photoanode or photocathode has present thereon an array of transition metal tubular architectures of sub-100 nm in length according to the present invention. Preferably, the device comprises the photoanode or photocathode described above, which comprises an array of transition metal tubular architectures of sub-100 nm in length according to the present invention present on a surface of the photoanode or photocathode. The device also comprises a counter anode that is connected to the photoanode or photocathode by any connection medium capable of forming a circuit between the photoanode or photocathode and the counter electrode. The counter electrode comprises any material that allows the counter anode to function in the device and participate in water splitting. One example is a counter anode that comprises platinum. Platinum is preferably at least 75% atomic percent of the counter anode in terms of material of which the counter anode is comprised. Additional electrodes can be included in the device as necessary. One example is a Ag/AgCl electrode, useful as a reference electrode. The device comprises water to immerse the photoanode or photocathode. In the devices of the present invention, the array of transition metal tubular architectures of sub-100 nm in length function as a semiconductor material, which preferably is contacted by light and provides energy to the device for splitting water. In embodiments of the present invention, the semiconductor material can further comprise at least one of Si, GaAs, GaP, InP, CdS, CdSe, CdTe, and ZnO, present in an amount of no greater than 15 mol %, relative to the total number of moles of the semiconductor material. The array of transition metal tubular architectures of sub-100 nm in length is present on at least 50% of the surface area of the photoanode, preferably at least 60% of the surface area, more preferably at least 75% of the surface area, even more preferably at least 90% of the surface area, and most preferably 100% of the surface area of the photoanode. All real numbers between these minimum and maximum values are disclosed herein. The devices can be used by those of ordinary skill in the art to extract molecular hydrogen and/or molecular oxygen by known or useful techniques available in the art. Embodiment Four Another embodiment of the present invention relates to a device that comprises an array of transition metal tubular architectures, wherein the transition metal tubular architectures are comprised of a transition metal oxide, sulfide, or selenide, and wherein transition metal tubular architectures are less than 100 nm in length according to Embodiment One. Unless otherwise indicated, phrases such as “an array of transition metal tubular architectures of sub-100 nm in length,” “the transition metal tubular architectures,” and “transition metal tubular architectures of sub-100 nm in length” used in this embodiment refers to the an array of transition metal tubular architectures, wherein the transition metal tubular architectures are comprised of a transition metal oxide, sulfide, or selenide, and wherein transition metal tubular architectures are less than 100 nm in length according to Embodiment One. Non-limiting examples of devices which can utilize the transition metal tubular architectures described above include drug delivery devices, lithium-ion batteries, photoelectrochemical devices, dye-sensitized solar cells (DSSCs), metal oxide field-effect transistors (MOSFETS), and hydrocarbon processing devices. In drug delivery devices, the nanotubes can be loaded with drugs and injected in the body, where they can release the drug. In lithium-ion batteries, the transition metal tubular architectures that are sub-100 nm in length are useful as anode materials for thin film lithium ion batteries. The transition metal tubular architectures can also be used as an active lithium ion storage material. The dye catches photons of incoming light and uses their energy to excite electrons. The dye then injects this excited electron into the titanium dioxide. The electron is conducted away by the sub 100 nm nanotubes titanium dioxide. A chemical electrolyte in the cell then closes the circuit so that the electrons are returned back to the dye. In hydrocarbon processing devices, the transition metal tubular architectures that are sub-100 nm in length are useful as catalysts during reactions that oxidizing hydrocarbons or produce hydrocarbons. One example is the use of the transition metal tubular architectures that are sub-100 nm in length as catalysts in reactions that convert carbon dioxide into natural gas and/or methane. EXAMPLES Example 1: Preparation and Isolation of Sub-100 nm Nanotubes of Titanium Dioxide (TiO2) Pure titanium foil samples (1 cm×1.5 cm) were first ultrasonically cleaned with acetone, followed by ethanol, then water for 20 minutes each. The anodization was performed in a two-electrode electrochemical cell, with the titanium foil as the working electrode and platinum foil as the counter electrode. Samples were anodized in electrolytes containing 1% NH4F (Sigma-Aldrich, ≥98%) mixed with 1.1 wt % Polyvinylpyrrolidone (M.W.˜40,000 g/mol, Loba Chemie) and 0.75 wt % H2O in a formamide-based electrolyte using galvanostatic anodization method for 2.5 hours at 0° C. The voltage was increased from 0 V to 36.5 V over the course of anodization so that the amperage remained between 16 mA to 28 mA during anodization. SeeFIGS.4aand4b, which show voltage ramping and current change during anodization, respectively. The pH of the electrolyte was controlled by the addition of 0.1 M acetic acid to the solution. Prior to anodization, the electrolyte was stirred for 1.15 h at 100° C. After anodization, the samples were rinsed thoroughly with distilled water. The as-anodized samples were crystallized by air annealing at 200° C., 350° C., 400° C., 450° C., and 500° C. for 2.5 h with a heating rate of 1° C./min. FIG.1shows the scanning electron microscopy (SEM) images of the fabricated sub-100 nm TiO2tubular structures before and after annealing.FIG.1ashows the SEM image of the as-anodized TiO2nanotubes with an average pore diameter of 20±3 nm and an average length of 70±10 nm. Note that previous attempts of galvanostatic anodization of titanium foil resulted in either porous nanostructures or long nanotubes (several microns). It is noteworthy to mention that, regardless of the anodization time (30-200 min), the resulting nanotubes were identical in terms of morphology, especially the tube length. Note also that the nanoarchitectures are reproducible whether the anodization is carried out at room temperature or in ice medium, yet the current is easier to control in the ice medium. Note also, as described above, the composition of the fluid medium can influence the length of the transition metal tubular architectures permitting a range of sub-100 nm TiO2tubular structures to be obtained varying from 5 nm to near 100 nm in length by variances in the composition of the fluid medium to those compositions detailed above. To further investigate the morphology of the sub-100 nm TiO2tubular structures, they were pealed-off the titanium foil and examined under the transmission electron microscope (TEM). The tubular shape of the as-anodized sub-100 nm structures was confirmed as shown inFIG.1b.FIG.1cshows the HR-TEM image of the as-anodized nanotubes, which reveals its partial crystallinity. The TEM and the HR-TEM images of the nanotubes annealed at 400° C. are shown inFIG.1e,f, respectively. The inset in Figure if demonstrates the selected-area electron diffraction (SAED) pattern of the annealed nanotubes. The lattice distance shown in Figure if is 0.4 nm, corresponding to the anatase phase. Note that the nanotubes preserve their morphology after annealing, revealing their structural stability. To get an insight into the mechanism of formation of the sub-100 nm tubular architectures, titanium foil was anodized for only 5 min. It was found that long nanotubes are first formed. Beneath the layer of long nanotubes lays the layer of interest of the sub-100 nm tubes. The voltage ramping caused the layer of long nanotubes to fall, exposing the layer of the sub-100 nm tubes, as shown in Figure Sc. Without wishing to be bound to a particular theory, it is believed the thicknesses of the array (i.e., the length of the sub-100 nm tubular architectures) can be controlled by varying the proportions or constituents of the fluid medium such as the PVP, the ammonium fluoride, and the water content. For example, if shorter sub-100 nm tubes are desired, lower water contents are used during the overall anoxidation time. In that case during the formation of the “long nanotubes,” the supply of oxidant to the subcutaneous layer of sub-100 nm tubes is reduced. If longer sub-100 nm tubes are desired, higher water contents are used. In that case, during the formation of the “long nanotubes,” the supply of oxidant to the subcutaneous layer of sub-100 nm tubes is increased. The XRD patterns of the as-anodized and the annealed sub-100 nm TiO2tubular arrays are shown inFIG.2a. The diffraction pattern shows the partial crystallinity of the as-anodized nanotubes fabricated in PVP-rich electrolytes (two diffraction peaks at 2θ=24.9° and 38°), while those fabricated in PVP-free electrolytes are totally amorphous. Therefore, the use of galvanostatic anodization in the presence of PVP not only permits the fabrication of sub-100 nm tubes but also improves the crystallinity of the material. The XRD pattern of the annealed samples confirms the crystallization of the sub-100 nm TiO2architectures in the regular anatase phase with the appearance of the characteristic diffraction peaks at 25.3°, 37.7°, 47.8°, 53.8°, and 54.9°, corresponding to the (101), (004), (200), (105), and (211) facets, respectively 31. Note the growth of the (004) peak intensity with the increase in the annealing temperature. Starting at 400° C., the (004) peak intensity starts to overgrow that of the (101), SeeFIGS.6aand6b. The crystallinity of the as-anodized sample is relatively low and the crystallite size is calculated to be ca. 6 nm according to the Scherrer equation from the broadening of anatase (101) reflection. Annealing at 350° C. and 400° C. greatly enhances the crystallinity of the material, however, with an increase in the crystallite size (ca. 9 nm). To get an insight into the stability of the material upon annealing,FIGS.5dand5hshows the SEM images of the annealed sub-100 nm TiO2nanotubes at temperatures ranging from 350° C. to 600° C. Annealing at temperatures below 600° C. did not seem to affect the morphology of the nanotubes. However, when annealed at 600° C., the structure was destroyed. The protrusions emanating from the underlying titanium support is believed to be the major cause of the material degradation at this temperature. Annealing took place in air. Raman spectroscopy was further used to characterize the as-anodized and the annealed sub-100 nm TiO2tubes, seeFIG.2b. Based on the space group D4h for anatase and assuming site symmetries for the TI and 0 atoms within the unit cell, six Raman-allowed transitions can be assigned (1A1g, 2B1g and 3Eg). Note that four Raman-active modes were observed for our material as Eg (148 cm−1), Big (397 cm−1), A1g (516 cm−1) and Eg (636 cm−1), confirming the formation of anatase phase upon annealing. The as-anodized sample showed two broad bands at 300-350 cm−1and 600-650 cm−1with one sharp peak at 479 cm−1confirming the partial crystallinity of the as-anodized nanotubes, in accordance with the XRD results. The weak and broad band observed at 780-790 cm−1can be assigned as the first overtone of the Big mode. According to the bond length/Raman frequency/covalency correlations, the following relationship between Ti—O bond lengths (R) and Raman frequency (v) shifts was reported: Ti-O=722e−1.54946(R−1.809) (1) The calculated Ti—O bond lengths (2×1.90, 3×2.03 and 2.14 Å) based on the observed Raman bands at 636, 516, and 397 cm−1are consistent with the slightly distorted TiO68−octahedron in anatase (Ti—O bond lengths for bulk anatase are 4×1.9338 Å and 2×1.9797 Å). Also, based on the sharp Raman band at 148 cm−1, the calculated bond length is 2.95 Å, which is consistent with Ti—Ti bonding present in the octahedral chains. X-ray photoelectron spectroscopy (XPS) analysis was performed using a Thermo Scientific K-alpha XPS with an Al anode to investigate the composition of the fabricated sub-100 nm TiO2hollow architectures. Spectra were charge referenced to O is at 532 eV.FIG.2cshows the O1s photoemission spectra, where one signal at 530.87 eV was observed that can be attributed to the lattice oxygen in TiO2.FIG.2dshows the Ti 2p photoemission spectra with two peaks obtained corresponding to Ti 2 p3/2 and Ti 2 p1/2 photoemissions with a spin-orbit splitting of 5.8 eV, confirming that both signals correspond to Ti4+, with the Ti/O molar ratio being close to the stoichiometric proportion. The diffuse reflectance spectra (DRS) of both as-anodized and annealed sub-100 nm TiO2tubular architectures arrays were measured to investigate the optical properties of the fabricated electrodes (seeFIG.3a). The spectra of the as-anodized TiO2sample shows a fundamental absorption edge in the UV region at 378 nm, typical for anatase TiO2with a band-gap energy of ca. 3.2 eV. As the annealing temperature increases, a very slight red shift appears in the spectra reaching 411 nm for the sample annealed at 400° C. Note that the as-anodized sample showed another broad absorption peak extending from 400 to 800 nm, which can be attributed to the existence of defects and trapped holes. This broad peak was diminished with increasing the annealing temperature, indicating that annealing improves the crystallinity and helps eliminating the defects. Example 2: Use of Sub-100 nm Nanotubes from Example 1 in the Photoelectrolysis of Water A photoelectrochemical activity test for water photoelectrolysis using the synthesized sub-100 nm TiO2tube arrays of Example 1 was carried out in a three-electrode electrochemical cell. FIG.3bshows the photocurrent density versus potential in 1 M KOH solution under AM 1.5 illumination (100 mW cm−2) for the as-anodized as well as annealed TiO2nanotubes. The dark current was less than 50 μA cm2for all samples over the displayed potential range. The maximum photocurrent exhibited by the TiO2nanotubes annealed at 400° C. was 0.37 mA cm−2at 0.8 VNHE. Note that this photocurrent is almost 3 times higher than that reported for long nanotubes. The photocell used in this example is a Teflon photocell, where an area of the cell in which the sample is exposed to light is 0.5 m2. The light was focused on this 0.5 m2area. The high photocurrent-to-dark current ratio implies that the majority of the photocurrent is generated only by absorbed photons with no dark-current contribution. Also, the onset potential (−0.87 and −0.85 VNHE for the nanotubes annealed at 350° C. and 400° C., respectively), the light contribution toward the minimum potential needed for water splitting process to take place, is more negative than that reported for long nanotubes (−0.7 to −0.8 VNHE). Therefore, the sub-100 nm tubes require less voltage for water oxidation than the conventional long nanotube counterparts, indicating more favorable photoelectrochemical activity. Without wishing to be bound to a particular theory, it is believed that this photoelectrochemical activity can, in part, be related to the small crystallite size in the fabricated sub-100 nm tubes (6-9 nm). As the particle size decreases, the ratio of surface-to-bulk defects is believed to increase, resulting in strong positive effects from surface defects that are enough to overcome the negative effects from bulk defects, leading to the observed enhancement in photocurrent. Note that the quantization effect cannot be considered for TiO2particles with sizes>3 nm. To assess the stability of the sub-100 nm TiO2tubular structures, the transient photocurrent (J-t) test was carried out under light on/off conditions at constant external bias of 0.8 VNHE, as shown inFIG.3c. The photocurrent of the tested electrodes decay very sharply under light-off conditions without exhibiting pronounced photocurrent tails suggesting that the fabricated photoanodes have excellent carrier transport properties. To better understand the charge carrier collection efficiency in the sub-100 nm TiO2tubes, incident photon-to-current collection efficiency (IPCE) experiments were performed under no applied bias. The experiments were performed in a two-electrode cell with the nanotube array as the working photoelectrode and platinum foil as the counter electrode in 1.0 M KOH solution. The IPCE was calculated using Eq. (2), where λ is the wavelength of the incident light, jphis the photocurrent density under illumination at λ and lois the incident light intensity at λ: IPCE %=|Jph(mA cm−2|×1239.8(V×nm)Io(mW cm−2)×λ(nm)×100 (2) FIG.3dshows the obtained IPCE curves for the as-anodized as well as the annealed sub-100 nm TiO2tubes. The annealed samples showed higher IPCE values compared to the as-anodized sample, reaching 37 to 40% for the sample annealed at 400° C. This can be related to the better crystallinity and the reduced defects upon annealing, in agreement with the Raman and XRD results. Note that the obtained IPCE values are among the highest reported for undoped TiO2under no applied bias. Comparative Example 1: Zirconium Example 1 was repeated but the pure titanium foil samples (1 cm×1.5 cm) were replaced with pure zirconium samples. A porous zirconium oxide layer formed, but sub-100 nm nanotubes of ZrO2were not obtained. Comparative Example 2: Different Polymer Example 1 was repeated but the polymer was changed. Polyvinylpyrrolidone (M.W.˜40,000 g/mol, Loba Chemie) of Example 1 was replaced with Polyvinylpyrrolidone (M.W.˜1,360,000 g/mol, Loba Chemie). The current surged during anodization, leading to decay of the metal and nanotubes were not formed. Comparative Example 3: Polymer Absent Example 1 was repeated but the polymer was absent from the electrolyte solution. Sub-100 nm TiO2nanotubes were obtained, however, these nanotubes were amorphous rather than partially crystalline. | 44,503 |
11858829 | DETAILED DESCRIPTION Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described below, by referring to the figures, to explain aspects. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. Expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list. A dielectric material having a higher dielectric constant than the present one and reducing or minimizing side effects (for example, leakage current) due to reduction of film thickness is beneficial for next-generation semiconductor devices (for example, DRAM). Accordingly, research has been actively conducted to search for next generation dielectric materials with a ternary composition. An example of a next generation dielectric material may be strontium titanate (STO). STO has a relatively high dielectric constant of about 300 but has low bandgap energy of about 3 eV, and thus, a leakage current may increase when a thin film dielectric is formed of STO. In general, the dielectric constant value and the band gap energy value have an inverse relationship, and thus, as a next-generation dielectric material, a ternary paraelectric having a high dielectric constant value of several hundreds and a band gap energy value larger than that of STO is required. Thus, Na2Nb4O11having a monoclinic crystal structure and a dielectric constant of Space group (S.G.) No. 9 of about 193 was discovered. Hereinafter, a method of manufacturing a ternary paraelectric having a Cc structure and physical properties of the ternary paraelectric having a Cc structure formed by the method will be described in detail with reference to the accompanying drawings. For example, the method may be directed to the manufacture of the ternary paraelectric as described above. FIG.1is a flowchart showing operations of a method (hereinafter, a first method) of manufacturing Na2Nb4O11, which is an example of a ternary paraelectric having a Cc structure, according to an embodiment. Referring toFIG.1, the first method includes a material preparation operation S1, a milling operation S2, a drying operation S3, a calcining operation S4, a compacting operation S5, a cold isostatic pressing (CIP) operation S6, a spark plasma sintering (SPS) operation S7, and a re-heat treating operation S8. The first method may be a solid state reaction method. The first method may include a part of a solid phase method (for example, the material preparing operation S1to the CIP operation S6). However, the embodiment is not limited as such, and the first method may be different from the solid phase method. In the material preparing operation S1of the first method, a first precursor and a second precursor may be mixed at a given ratio. The first precursor may be a precursor of Na, and the second precursor may be a precursor of Nb. In an example, the first precursor may be Na2CO3, and the second precursor may be Nb2O5. The first and second precursors may be mixed in a ratio of 1:2. In the milling operation S2, milling includes adding a solvent to a mixture from the previous operation S1. The milling may be, for example, planetary milling. The solvent may be, for example, ethanol. The planetary milling may use revolving and rotating zirconia balls. Through the planetary milling, the mixture from the material preparing operation S1may be pulverized, and thus, the first and second precursors may be uniformly mixed. The milling operation S2may be performed for, for example, about 12 hours. The drying operation S3may be an operation of removing the solvent from the resultant product obtained in the milling operation S2. In the drying operation S3, the solvent may be volatilized by using a heating element like a hot plate, a heating coil, or a lamp. The calcining operation S4is a homogeneous step. In the drying operation S3, the solvent is removed, and a resultant product is in a state in which the first and second precursors are uniformly mixed. In the calcining operation S4, the first and second precursors are chemically bonded to form an ABO type single phase. The calcining operation S4may be performed under a heat treatment atmosphere in which the ABO type single phases are not agglomerated with each other. For example, the calcining operation S4may be performed at a temperature of about 700° C. for about 12 hours in a furnace of an ambient air atmosphere. After the completion of the calcining operation S4, the resultant product is sufficiently cooled and removed from the furnace. For example, the resultant product may be cooled in the furnace until the resultant product reaches a temperature in which the product may be held. The compacting operation S5is an operation of molding the resultant product produced in the calcining operation S4in a mold of a given shape, for example, a pellet shape, by applying pressure. In the compacting operation S5, the pressure applied to the material filled in the mold may be a relatively low pressure, for example, the pressure applied to the material filled in the mold may be applied by a human hand. In this way, the pressure applied to the material filled in the mold in the compacting operation S5may be not large, and thus, the material separated from the mold after the compacting operation S5may include pores. The CIP operation S6includes an operation of compressing the resultant product that has undergone the compacting operation S5at high pressure. As an example, the resultant product (pellet) obtained in the compacting operation S5may be compressed at pressure of 200 MPa or greater. Some of the pores may be removed from the pellet through the CIP operation S6, and a relative density of the pellet that has undergone the CIP operation S6may be about 60% compared to a fully dense example (e.g., a monocrystalline example without voids and defects) of the ternary paraelectric. The SPS operation S7includes an operation of sintering the resultant product of the CIP operation S6at a given temperature while compressing at high pressure. In the SPS operation S7, the resultant product may be compressed with pressure of about 50 MPa. In the SPS operation S7, a sintering temperature may be, for example, about 900° C., but is not limited thereto. In the SPS operation S7, the sintering may be performed for about 5 minutes in a vacuum atmosphere. Through the SPS operation S7, the pores in the resultant product obtained in the CIP operation S6may be removed as much as possible. In another example, the SPS operation S7may include an operation of sintering powder obtained through the calcining operation S4under the condition of temperature and pressure described above after placing the powder into a graphite mold. The re-heating operation S8is to remove defect or oxygen vacancies that may be in the resultant product of the SPS operation S7, and may be, for example, an annealing process. The defect or oxygen vacancies may occur as the SPS operation S7is performed in a reducing atmosphere. The re-heating operation S8may be performed at a higher temperature than the SPS operation S7, for example, may be at about 1000° C. The re-heating operation S8may be performed for about 12 hours under an ambient air atmosphere. For example, the relative density of Na2Nb4O11manufactured by the first method may be 99% or more compared to the fully dense example of Na2Nb4O11not containing a pore. For example, the relative density may be 99.5% or more. FIG.2is a flowchart showing operations of a method (hereinafter, a second method) of manufacturing Na2Nb4O11, which is an example of a ternary paraelectric having a Cc structure, according to another embodiment. Only parts different from the first method inFIG.1will be described. Referring toFIG.2, the second method may include a material preparation operation S11, a milling operation S22, a drying operation S33, a calcining operation S44, a compacting operation S55, a CIP operation S66and a sintering operation S77. The material preparation operation S11to the CIP operation S66may be performed in the same manner as the material preparation operation S1to the CIP operation S6ofFIG.1. The sintering operation S77is an operation of sintering a resultant product (for example, Na2Nb4O11) of the CIP operation S66in a given heat treatment atmosphere. Through the sintering operation S77, pores remaining in the resultant product that has undergone the CIP operation S66may further be reduced. Accordingly, a relative density of the resultant product compared to a fuilly dense example of the target ternary paraelectric (e.g., Na2Nb4O11) may be increased to 90% or more through the sintering operation S77, for example, the relative density of Na2Nb4O11after the sintering operation S77is about 95%. A temperature of the heat treatment atmosphere of the sintering operation S77may be, for example, about 1075° C., but the temperature is not limited thereto. The heat treatment may be maintained for about 12 hours in an ambient air atmosphere. On the other hand, in the first and second methods described above, powder for sintering may be manufactured by a solid phase method, but may be manufactured by other methods besides the solid phase method, for example, a liquid phase method. On the other hand, in Na2Nb4O11manufactured according to the manufacturing methods ofFIGS.1and2, Na may be replaced by another element that belongs to the same Group 1 as Na in the periodic table (e.g., an alkali metal), and Nb may be replaced by another element that belongs to the same Group 5 as Nb. As a result, the manufacturing methods ofFIGS.1and2may be extended to a method of manufacturing a paraelectric material of the type A2B4O11. “A” in A2B4O11may be an element belonging to Group 1 of the periodic table, for example, Na, K, Li or Rb. “B” may be an element belonging to Group 5 of the periodic table, for example Nb, V or Ta. Next, physical characteristics of an example (Na2Nb4O11) of the ternary paraelectric manufactured by using the first method ofFIG.1and the second method ofFIG.2will be described. FIG.3is a graph showing X-ray diffraction characteristics of first Na2Nb4O11(“B”) manufactured by using the method ofFIG.1; second Na2Nb4O11(“A”) manufactured by using the method ofFIG.2; third Na2Nb4O11(“C”) that is derived from a simulation calculation and has a monoclinic system and a space group No. 9; and fourth Na2Nb4O11(“D”) that is derived from a simulation calculation and has a monoclinic system and a space group No. 15. InFIG.3, “A” represents X-ray diffraction characteristics of the second Na2Nb4O11, and “B” represents X-ray diffraction characteristics of the first Na2Nb4O11. “C” and “D” respectively represent X-ray diffraction characteristics of the third Na2Nb4O11and the fourth Na2Nb4O11. Referring toFIG.3, the X-ray diffraction characteristics B and A of the first and second Na2Nb4O11are the same, and the X-ray diffraction characteristics B and A of the first and second Na2Nb4O11are the same as the X-ray diffraction characteristic C of the third Na2Nb4O11. That is, when the peak distributions appearing in the X-ray diffraction characteristics B and A of the first Na2Nb4O11and the second Na2Nb4O11and the peak distributions appearing in the X-ray diffraction characteristic C of the third Na2Nb4O11are compared, it may be seen that the peak distribution appearing in the X-ray diffraction characteristics B and A of the first Na2Nb4O11and the second Na2Nb4O11and the peak distribution appearing in the X-ray diffraction characteristic C of the third Na2Nb4O11are the same. Accordingly, the peaks appearing in the X-ray diffraction characteristics B and A of the first and second Na2Nb4O11may be matched one-to-one with the peaks appearing in the X-ray diffraction characteristic C of the third Na2Nb4O11. On the other hand, it may be seen that the X-ray diffraction characteristics B and A of the first and second Na2Nb4O11are different from the X-ray diffraction characteristics D of the fourth Na2Nb4O11. That is, the peak distribution appearing in the X-ray diffraction characteristics D of the fourth Na2Nb4O11is different from the peak distribution appearing in the X-ray diffraction characteristics B and A of the first Na2Nb4O11and the second Na2Nb4O11. In detail, the peak distribution appearing in the X-ray diffraction characteristic D of the fourth Na2Nb4O11includes peaks that are not present in the peak distribution appearing in the X-ray diffraction characteristics B and A of the first Na2Nb4O11and the second Na2Nb4O11. Accordingly, the peaks appearing in the X-ray diffraction characteristics B and A of the first Na2Nb4O11and the second Na2Nb4O11do not match one-to-one with the peaks appearing in the X-ray diffraction characteristics D of the fourth Na2Nb4O11. The results ofFIG.3denote that the first Na2Nb4O11manufactured by the first method and the second Na2Nb4O11manufactured by the second method both are a monoclinic system and have a single phase in space group No. 9. That is, it may be determined that Na2Nb4O11having the space group No. 9 with the monoclinic system is synthesized by the first and second methods. FIG.4is a graph showing a dielectric constant and a dielectric loss characteristic with respect to frequency change of a ternary paraelectric having a Cc structure according to an embodiment, wherein the ternary paraelectric may be the first Na2Nb4O11manufactured by using the first method ofFIG.1. InFIG.4, the horizontal axis represents applied frequency, the left vertical axis represents dielectric constant, and the right vertical axis represents dielectric loss. The first graph4G1represents dielectric constant, and the second graph4G2represents dielectric loss. Referring toFIG.4, in the case of the first Na2Nb4O11, the dielectric constant tends to be substantially constant regardless of frequency. In a high frequency band (104Hz ˜), the dielectric constant of the first Na2Nb4O11is about 170. FIG.5is a graph showing a dielectric constant and a dielectric loss characteristic with respect to frequency change of a ternary paraelectric having a Cc structure according to another embodiment, wherein the ternary paraelectric may be the second Na2Nb4O11manufactured by using the second method ofFIG.2. InFIG.5, the horizontal axis represents applied frequency, the left vertical axis represents dielectric constant, and the right vertical axis represents dielectric loss. The first graph5G1represents dielectric constant, and the second graph5G2represents dielectric loss. Referring toFIG.5, the dielectric constant of the second Na2Nb4O11has a frequency dependency in a relatively low frequency band (102to 104Hz). However, it may be seen that the dielectric constant of the second Na2Nb4O11is maintained at about 150 in a high frequency band of 104Hz or more. Generally, when measuring an intrinsic dielectric property of a paraelectric, in order to remove a process defect or an effect of space charge, the measurement of the dielectric property is performed in a high frequency band (105-106Hz) Therefore, a dielectric constant value in a high frequency band is important. The results ofFIGS.4and5denote that, in the case of a ternary dielectric manufactured according to the first and second methods, a dielectric constant of at least 150 or above may be constantly maintained in a high frequency band. In an example, the dielectric constant of a ternary dielectric manufactured by the first and second methods may be about 150 to about 250. When dielectric loss in a high frequency band is reviewed, it may be seen fromFIG.4that the dielectric loss of a ternary dielectric manufactured according to the first method is 1% or less. When the second graphs4G2and5G2ofFIGS.4and5are compared, the dielectric loss of the ternary dielectric manufactured according to the second method is greater than that of the ternary dielectric manufactured according to the first method. However, the dielectric loss of the ternary dielectric manufactured according to the second method does not exceed 10%. On the other hand, as shown inFIGS.4and5, the dielectric constant characteristics of the first Na2Nb4O11and the second Na2Nb4O11are different from each other and the dielectric constant values in the high frequency band are also different from each other. This result seems to be due to the difference in relative density of the first Na2Nb4O11and the second Na2Nb4O11. Table 1 summarizes the dielectric constant and dielectric loss characteristics of the first Na2Nb4O11and the second Na2Nb4O11in a high frequency band (105Hz and 106Hz). Table 1 is a result measured at room temperature. TABLE 1105Hz106Hzdielectricdielectricdielectricdielectricsampleconstant Klossconstant KlossFirst Na2Nb4O11173.50.01172.10.003Second Na2Nb4O11154.50.06151.90.009 FIG.6is a graph showing an analysis result of bandgap energy of the first Na2Nb4O11manufactured by the first method ofFIG.1as a ternary paraelectric having a Cc structure according to an embodiment. The analysis results were obtained by using reflection electron energy loss spectroscopy (REELS). InFIG.6, the horizontal axis represents energy loss and the vertical axis represents intensity. Referring to the analysis result ofFIG.6, the bandgap energy of the first Na2Nb4O11is about 3.89 eV, and this value is greater than the bandgap energy (˜3 eV) of STO. In order to prevent a leakage current from occurring in a dielectric for DRAM, a band offset with an electrode, for example, a TiN electrode mainly used in fields, is required to be maintained at 1 eV or more. In the case of STO, a band offset with TiN is about 0.93 eV, and thus, it is difficult to prevent the occurrence of a leakage current. On the other hand, the bandgap energy of the first Na2Nb4O11is greater than that of STO as described with reference toFIG.6. Therefore, in the case of the first Na2Nb4O11, the band offset with the TiN electrode is determined to be 1 eV or more, and thus, the first Na2Nb4O11may be a new dielectric material that may be applied to a semiconductor device. FIGS.7A to7Dare graphs showing hysteresis characteristics of a ternary dielectric having a Cc structure (for example, the first Na2Nb4O11) according to an embodiment. FIG.7Ashows a hysteresis characteristic of a ternary paraelectric when an electric field of −10 kV/cm to +10 kV/cm is applied to the ternary paraelectric. FIG.7Bshows a hysteresis characteristic of a ternary paraelectric when an electric field of −20 kV/cm to +20 kV/cm is applied to the ternary paraelectric. FIG.7Cshows a hysteresis characteristic of a ternary paraelectric when an electric field of −30 kV/cm to +30 kV/cm is applied to the ternary paraelectric. FIG.7Dshows a hysteresis characteristic of a ternary paraelectric when an electric field of −37 kV/cm to +37 kV/cm is applied to the ternary paraelectric. InFIGS.7A to7D, the horizontal axis represents intensity of electric field according to an applied voltage, and the vertical axis represents polarization density. Referring toFIGS.7A to7D, it may be seen that the hysteresis characteristics of the ternary paraelectric according to an embodiment are linear. That is, as the voltage applied to the ternary paraelectric according to an embodiment increases the polarization density of the ternary paraelectric increases. In other words, the polarization density linearly increases in proportion to a voltage applied to the ternary paraelectric. The results may denote that the ternary paraelectric according to an embodiment, that is, the ternary dielectric manufactured by the first method ofFIG.1, is a paraelectric. FIGS.8A to8Dare graphs showing hysteresis characteristics of a ternary dielectric (for example, the second Na2Nb4O11) according to an embodiment. FIG.8Ashows a hysteresis characteristic of a ternary paraelectric when an electric field of −10 kV/cm to +10 kV/cm is applied to the ternary paraelectric. FIG.8Bshows a hysteresis characteristic of a ternary paraelectric when an electric field of −20 kV/cm to +20 kV/cm is applied to the ternary paraelectric. FIG.8Cshows a hysteresis characteristic of a ternary paraelectric when an electric field of −30 kV/cm to +30 kV/cm is applied to the ternary paraelectric. FIG.8Dshows a hysteresis characteristic of a ternary paraelectric when an electric field of −37 kV/cm to +37 kV/cm is applied to the ternary paraelectric. InFIGS.8A to8D, the horizontal axis represents intensity of electric field according to an applied voltage, and the vertical axis represents polarization density. Referring toFIGS.8A to8D, as the voltage applied to the ternary paraelectric is increased, the polarization density of the ternary paraelectric is also increased. That is, a linear proportional relationship appears between the voltage applied to the ternary paraelectric and the polarization density. The result denotes that the ternary dielectric formed by the second method ofFIG.2is also a paraelectric. When the linear property between the graphs ofFIGS.7A to7Dand the graphs ofFIGS.8A to8Dis compared, it may be seen that the linear property of the graphs ofFIGS.7A to7Dis superior to those ofFIGS.8A to8D. This result seems to be due to the difference between the relative density (more than 99%) of the ternary dielectric according to an embodiment and the relative density (more than 95%) of the ternary dielectric according to another embodiment. A disclosed ternary paraelectric (for example, Na2Nb4O11in space group No. 9 that is a monoclinic system) having a Cc structure may have a permittivity greater than 100, a relative density of 90% or more, and a bandgap energy greater than that of the STO. Accordingly, when the disclosed ternary paraelectric is used, it is possible to minimize a leakage current while ensuring a high dielectric constant and thinning of the dielectric. Therefore, when the disclosed paraelectric is applied to DRAM, a leakage current may be reduced while ensuring sufficient capacitance for operating the DRAM. As a result, the use of the disclosed paraelectric may help stabilize an operation of a semiconductor device, such as highly integrated DRAM, and may also help to increase the reliability of the semiconductor device. FIG.9illustrates a structure of a trench capacitor-type dynamic random access memory (DRAM). Referring toFIG.9, on a P-type semiconductor substrate320, a device isolation region may be defined with a field oxide film321, and a gate electrode323and source/drain impurity regions222and222′ may be formed in the device isolation region. A high-temperature oxide (HTO) film may be formed as an interlayer insulating film324. A region not to be a trench may be capped with a trench buffer layer, and a part of the source region322may be open to form a contact portion. A trench is formed in a sidewall of the interlayer insulating film324, and a sidewall oxide film325may be formed over the entire sidewall of the trench. The sidewall oxide film325may compensate for damage in the semiconductor substrate caused by etching to form the trench, and may also serve as a dielectric film between the semiconductor substrate320and a storage electrode326. A sidewall portion of part of the source region322, except for the other part of the source region near the gate electrode323, may be entirely exposed. A PN junction (not illustrated) may be formed in the sidewall portion of the source region by impurity implantation. The trench may be formed in the source region322. A sidewall of the trench near the gate may directly contact the source region322, and the PN junction may be formed by additional impurity implantation into the source region. A storage electrode326may be formed on part of the interlayer insulating film324, the exposed source region, and the surface of the sidewall oxide film325in the trench. The storage electrode may be, for example, a polysilicon layer, and may be formed so as to contact the entire source region322in contact with the upper sidewall of the trench, in addition to the part of the source region322near the gate electrode. The source region322on the outer surface of the upper sidewall of the trench may be enlarged due to the implanted impurities, and thus may more reliably contact the storage electrode326. Next, an insulating film327as a capacity dielectric film may be formed along the upper surface of the storage electrode326, and a polysilicon layer as a plate electrode328may be formed thereon, thereby completing a trench capacitor type DRAM. The ternary paraelectric according to the example embodiments may be used as the insulating film327. As the storage electrode326, the polysilicon layer may be formed on the part of the interlayer insulating film324, the exposed source region322, and the surface of the sidewall oxide film325in the trench. Since the storage electrode326is formed to spontaneously contact, in addition to the part of the source region322near the gate electrode, the entire source region322in contact with the upper sidewall of the trench, the contact area may be enlarged, leading to more reliable contact with the storage electrode326and a significant increase in capacitance of the capacitor. Though illustrated as part of a trench capacitor type DRAM, the example embodiments are not limited thereto. For example, the ternary paraelectric may comprise a insulating film in other DRAM types, or the insulating film in other electronic devices (e.g., the insulating film in a capacitor). It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments. While one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims. | 26,525 |
11858830 | DETAILED DESCRIPTION Embodiments of the present disclosure provide a device for treating water upon upload. The device's water treatment is not chemical or UV-based. Instead, the device incorporates a physical filtration system into a housing that allows the device to travel with the aircraft and that can be used external to an aircraft skin. The device is a passive water treatment. It does not require electricity or power to function. (However, it should be understood that other components of the device described herein may use power for their operation, such as the germicidal UV light system and/or the filtration management system, described further below.) There is disclosed a device10for water treatment and purification. Specific embodiments find particular use in connection with uploading potable drinking water to an aircraft or other passenger transportation vehicle. The device is designed to be portable. The treatment process is intended to take place at the aircraft water upload stage. As is shown byFIG.1, the device10has body defined primarily by a filter chamber housing12. A filtration monitoring system14is also associated with the filter chamber housing12. Un-filtered water enters the device10at inlet16, is treated by a filter60contained within the filter chamber housing12, and filtered water exits through outlet18. As shown byFIG.2, the inlet16and outlet18may be provided with adapters or fittings may be removable and/or customizable in order to allow the device10to be modifiable for use with different types of water delivery systems. For example, it is possible to provide the device10with a plurality of differently-shaped inlet fitting adapters20, such that the device10can cooperate with different types of water delivery hoses, depending upon the shape of the hose at a particular airport where service is taking place. The inlet fitting adapter20is designed to fit to the water inlet16of treatment filter cylinder housing12. The inlet fitting adapter20may have an adapter end22that cooperates with a water delivery hose via threading, via one or more clamps, dovetail and slot connection, quick disconnect connector, or via any other appropriate connection mechanism. The inlet fitting adapter20may be secured to the filter chamber housing12itself via threads, by a flanged interface, via hydro flow clamps, dovetail and slot connection, quick disconnect connector, or via any other appropriate securement system. There may also be provided an outlet fitting adapter24that may be customized to match the aircraft/vehicle specific connections for the aircraft/vehicle with which it is intended to travel. The outlet fitting adapter24is designed to fit to the water outlet18of treatment filter cylinder housing12in order to allow connection to the aircraft (or other vehicle) water upload panel. Although the device10is primarily designed to travel with the aircraft/vehicle on which it is intended to be used, various differently-sized outlet fitting adapters24may be provided with varied outlet adapter ends26, such that the device may be moved from vehicle to vehicle if desired and used with different vehicle water upload systems. The outlet fitting adapter24may be secured to the filter chamber housing12itself via threads, by a flanged interface, via hydro flow clamps, dovetail and slot connection, quick disconnect connector, or via any other appropriate securement system. In short, the inlet16and the outlet18may be provided with a plurality of differently sized fitting adapters20,24that may be customized to allow a wide range of use options for the device10. In order to provide ease of moving the device10from vehicle to vehicle and/or in order to provide a safe place to store the device10and its accompanying fitting adapters20,24on a specific vehicle with which it is intended to be used, there may be provided a specifically designed carrying case30. One example is illustrated byFIGS.3and4. Case30may enclose a one or more differently shaped adapters20that are configured to cooperate with the inlet16in order to connect the device10to the hose of a water delivery truck and/or one or more differently shaped adapters24that are configured to cooperate with the outlet18in order to connect the device10to the water system panel of the vehicle. The carrying case30may be fitted with space holders32for each assembly component to prevent any movement during transportation. For example, the case30may have a first space holder32ashaped to support the device housing12, one or more space holders32bto support the adapters20,24, one or more space holders32cto support a spare filter cartridge60, and/or space holders to support any other components that may be provided with the device10and desirably stored in the carrying case30. Any desirable configuration may be used. The interior of the case30may be fitted with a rigid liner42that prevents rattling of the stored components. (In an alternate embodiment, the interior of the case may be fitted with a foam (or other appropriate material) that prevents rattling of the stored components.) One or more of the space holders32may be provided with a compartment door36. This may help further protect components contained within a specific space holder. In the example illustrated, a compartment door36is positioned over the space holder32athat supports the device10. The carrying case30may also be provided with a lid to38that may be locked closed in order to secure the carrying case30. The carrying case30may also be fitted with a germicidal UV LED system that can be turned on when the unit is not in use in order to treat components inside the carrying case30so that they are free of any microbial contamination for their next use. For example, it can be important to clean the components of the device between uses in order to prevent bacteria and other microbiological contamination from being transferred to the treated water. During use, the components of the device are in contact with a number of potential sources of contamination, such as workers coordinating water upload, bacteria in the natural environment, bacteria from the local water supply. Appropriately disinfecting components of the device between uses can help ensure that this contamination is removed and that the device is ready for a new use. The UV LED system may include one or more germicidal UV LEDs44positioned at various locations within the carrying case30. In the specific example illustrated, the rigid liner42forms a space holder32awith a compartment door36. As shown, the space holder32ais sized to support the device10(including the device housing12with an inlet fitting adapter20and an outlet fitting adapter24positioned thereon). After use of the device10, it may be desirable to treat the device to ensure that the device, and particularly the adapters20,24are not contaminated for the next use. These space holder32may thus be provided with one or more germicidal UV LED lights44. After use, the device10may be positioned within the space holder32, and the compartment door36closed. A safety switch46may cooperate with the compartment door36such that the door36must be closed in order for the germicidal UV LED system to operate. When the door36is opened, the germicidal UV LED light(s) will automatically turn off (In an alternate embodiment, the one or more germicidal UV LED lights are positioned anywhere within the carrying case30and the safety switch46may be associated with the carrying case lid38.) The germicidal UV LED system may be powered externally or internally. In one example, there may be provided a self-charging capacitor that generates electricity. In another example, the carrying case30may be provided with a chargeable battery that supplies the electrical energy for the operation of the LEDs. In a further example, the carrying case30may hook up to aircraft power for re-charging or for electricity. Available power for the UV LED system, the filtration monitoring system14, or any other operating parameters can be reflected on screen40. Referring back toFIG.1, the filtration monitoring system14(which may also be referred to as the FMS) is designed for mobile monitoring of the water quality either entering or exiting the device10. It may be powered in any of the above-discussed ways. The FMS14may monitor the filtration flow rate, flow speed, incoming water quality, filtration quality, time to change the filter per recommended volume of water treated over time, or any other appropriate parameter. The FMS14has a screen48that displays these parameters. In a specific example, the FMS screen48is an LCD screen. The FMS14may have one or more status indicators50, such as status LEDs. Status indicators50may indicate whether the system is on or off, whether battery power is sufficient, or any other parameter. The FMS14may communicate with the aircraft in order to make uploading more efficient. In a specific example, the FMS14may communicate with the aircraft wirelessly via Wifi, Bluetooth, or other appropriate technology. This can allow for remote monitoring of functioning of the device10through a mobile device. Examples for use of the FMS14may be to enable reduced power consumption if the water flowing into the device10is of sufficient quality that flow rate can be increased (which means less contact time of the water with the filter/filtration media). Alternatively, if the water flowing into the device10requires enhanced treatment, the FMS14can lower the flow rate in order to allow increase contact time of the water with the filter/filtration media. In one example, the FMS can communicate with the incoming water supply in order to change the flow rate. This allows the device to be more efficient and effective. This altered flow rate or other parameters (such as device on/off) may be input wirelessly. However, one or more multi-use buttons52may also be positioned on the FMS14. These buttons may be on-off buttons, flow rate management buttons, or any other appropriate control buttons. The filter60contained within the filter chamber housing12may be a passive filter. One specific example relies on the use of a polymer-based material. Other exemplary filter systems include but are not limited to filters using an ion exchange resin, natural polymer beads, small pore size ceramic filters, classic carbon filters such as activated charcoal filters, reverse osmosis filters, mixed media filters, such as filters using sand or other media, filters with a tortuous path, or any other appropriate filter system, or any combination of the above. In one example, the filter60may be friction fit within the filter chamber housing12. Additionally or alternatively, various types of internal connectors may be designed in order to secure the filter60in place within the filter chamber housing12if necessary. For example, there may be a lock and rotate connection between a groove and projection, such as a dovetail or J-lock connection. Additional connection examples include but are not limited to a bayonet fitting, ball and detent connection, snap connection, magnetic connection, or any combination thereof. Other connection options are also possible in considered within the scope of this disclosure. FIG.16illustrates one embodiment of water flowing through the disclosed device for treatment. Arrows indicate the direction of water flow. The darkened arrows indicate unfiltered water, and the lightened arrows indicate treated, filtered water. Pressure from the incoming water source forces movement of the water through the system. In a further embodiment, a dual cylinder system70may be provided. The dual system70has more than one intra-connected water filter cartridge housing12. Examples are illustrated byFIGS.5-7. In the dual systems70shown, there are two filter cartridge housings12aand12billustrated. However, it should be understood that any number of appropriate filter cartridge housings12may be used. For example, a single filter cartridge housing12may be used with the flow control unit72. This example is illustrated byFIG.8.FIG.9illustrates two side-by-side filter cartridge housings12a,12bconnected via a single flow control unit72. It is also possible for more than two filter cartridges12to be used. In various examples, three, four, five, six, seven, or even more housings12may be provided in association with a single flow control unit72. One example illustrating the use of three housings12a,12b,12cis illustrated byFIG.10. The flow control unit72is illustrated in more detail byFIG.7. As shown, the flow control unit72has an inlet fitting adapter20and an outlet fitting adapter24, similar to those described above. Flow unit72is also shown having an FMS14, similar to that described above. Water to be treated flows into the inlet adapter20, is caused to flow through filters housed by filter cartridge housings12aand12b, and exits through the outlet adapter24.FIG.17Aillustrates one embodiment of water flowing through the disclosed dual chamber system, with the filters connected in series.FIG.17Billustrates one embodiment of water flowing through the disclosed dual chamber system, with the filters connected in parallel. Arrows indicate the direction of water flow. The darkened arrows indicate untreated water, and the lightened arrows indicate treated water. Pressure from the incoming water source forces movement of the water through the system. To keep the water inlet and outlet areas and fitting adapters free of microbial contamination for the reasons outlined above, the cavities for the inlet and outlet may be fitted with germicidal UV light source such as LEDs44. This allows the flow control unit72to provide UV treatment to the adapters20,24. In order for this treatment to take place, one or more UV LEDs44are positioned on a platform76of the flow control unit72. UV shields78are provided for safety. In the embodiment shown, a first UV shield78ais hinged to the platform76at a first pivot point80a. A second UV shield78bis hinged to the other end of the platform76at a second pivot point80b. The first UV shield78arotates about the first pivot point80ain order to close and house the inlet fitting adapter20. The second UV shield78brotates about the second pivot point80bin order to close and house the outlet fitting adapter24. The flow control unit72with the UV shields78in a closed position is as shown byFIGS.5and6. There may be provided a safety switch that requires the UV shields78to be locked in place in order for the LEDs44to be switched-on. This feature prevents accidental expose to UV light source by the user. An upper part of the flow control unit may be provided with a handle82in order to allow ease of carrying of the dual filter system70. This allows the dual filter system70to be a carry-on package, with the user transporting the system70via the handle82. As shown byFIG.11, there may be a storage case84with a plurality of compartments86that are shaped and configured to receive replacement filters60, conduits/hoses88for securing the system to an aircraft, replaceable inlet and outlet fitting adapters20,24, for storing system70, or for storing any other appropriate components. The storage case lid90may also be used to store one or more conduits88. Additionally or alternatively, a light trolley or rolling storage case94may be used for ease of mobility and transportation of a filter system96. One example is illustrated byFIG.12. In this example, the filter system components are individually housed within the case94. For example, the filter cartridge housings12are mounted within the case. Retractable hoses98may be mounted within the case. There may be a retractable hose98afor the inlet (where water to be treated is delivered into the system96) and a separate retractable hose98bfor the outlet (for delivering treated water to the vehicle for upload). It is possible for hoses98to have fixed connections. Alternatively, it is possible for hoses98to have appropriately shaped adapter fittings (20,24) as described above. Rolling case94may be provided with a retractable handle92for ease of transportation. The case94may be provided with an equalization valve to adjust for changes in altitude. Any of the disclosed cases30,84,94may be sized as a carry-on size. FIGS.13-15illustrate connection of a device10and/or a dual filter system70to an aircraft100. In these examples, the aircraft has an aircraft skin102which forms the outer surface of the aircraft. The aircraft skin102is provided with a potable water access panel104. The access panel104encloses a potable water fill inlet106. When the panel104is opened, conduits88may be used to secure one (or more than one) of the devices10,70described herein to the water fill inlet106. InFIGS.13aand13b, a device10is secured directly to the potable water fill inlet106via the device outlet fitting adapter24. (It should be understood that an intermediate conduit may be used between the inlet106and the outlet adapter24if desired.) The adapter24(or an adapter of an intermediate conduit, if used) is secured to the water fill inlet106. A conduit88(also referred to as a water hose) is secured to the inlet adapter20. As water flows from the conduit88and through the device10, it is treated prior to being delivered to the aircraft potable water tank. InFIG.14, a dual system70is secured to the potable water fill inlet106via an intermediate conduit88a. The intermediate conduit88ais then secured to the outlet adapter24of the system70. A water delivery conduit88bis then secured to the inlet adapter20of the system. As water flows from the conduit88b, through the device70, it is treated prior to being delivered to the aircraft potable water tank. Alternatively, a plurality of dual systems70may be attached in sequence, such that water purified to a first level leaving an outlet of a first dual system may be delivered to an inlet of a second dual system. Additionally or alternatively, one or more device(s)10with a single filter cartridge housing12may be used in combination with one or more dual systems70. An example of this configuration is illustrated byFIG.15. In each of these examples, the filtration is a passive filtration that does not require chemicals or UV light treatment of the water itself. The passive filtration occurs outside the aircraft, with the device10or system70being secured to an external water fill inlet106. This is in contrast to prior art systems that require a water treatment device to be permanently mounted on and travel with the vehicle. The present disclosure provides a portable solution for providing potable water filtration. In addition to using any combination of device10or system70, it is also possible to combine use of the passive filtration of this disclosure with one or more active filtration devices, as described in more detail below. In summary, the present disclosure relates to treatment and purification of drinking water prior to upload to the aircraft potable drinking water tank. The device travels onboard the aircraft and flies with the aircraft from one destination to another, while it is safely stored in its housing/case when not in use. The device has the necessary valves, adaptors and fittings for connection and disconnection to drinking water sources, such as water-hoses from a water delivery truck. Necessary valves, adapters and fittings are also provided for connection of the device to the aircraft water in-take panel. During the treatment process, the filtration device or system is located outside the aircraft. Once upload of water is completed, the device is disconnected and stored in its carrying case onboard the aircraft. As described herein, the carrying case may be fitted with germicidal one or more UV LEDs that can be switched on in order to irradiate any microbial species that might have been picked up from the outside environment during the connection and disconnection process. The use of UV LEDs can help safeguard the cleanliness of the parts inside the carrying case and ensures readiness for the next water upload operation. By contrast, existing water treatment systems are primarily permanently fixed/mounted to the water upload location. They do not provide portability or adjustability of adapters and are limited to the facilities given at an airport and resources available on the aircraft flight destination. The disclosed portable water treatment filtration device is used when drinking water is uploaded to the aircraft. Its use is independent of the available facilities in a given airport and its regional water quality and purity. This offers the opportunity to meet the water purity standards per the US EPA and WHO protocols. The device10,70is described as a primarily passive filtration device. However, the device10,70disclosed herein may be used in combination with other upload treatment systems. It is possible to combine use of the disclosed passive filtration device10with other types of filtration devices, such as one or more additional passive filtration devices and/or one or more active filtration devices. The portability of the disclosed device also allows its use to modify the performance of any other water treatment units/devices which are considered as fixed installations on-board the aircraft. For example, the disclosed device10,70can be used in series with other water treatment systems on board the aircraft. In one example, rather than being mounted directly to the water fill inlet106, the disclosed device10,70may be hooked up to an on-board UV or chemical water treatment system. In this configuration, water leaving device10,70is exposed to its passive filtration, and can then undergo active filtration via the other system. This type of supplemental water treatment can have advantage of power saving, reduction in the size and envelope of the device as well as their fit, form and function, and enhanced water filtration treatment. (Non-limiting examples of active filtration devices are UV filtration devices, chemical filtration devices, oxidizers, any other appropriate active filtration system, or any combination thereof.) Non-limiting examples of such active filtration are described above in the assignee's patent portfolio. The synergy between the filtration systems can help improve filtration and increase efficiency. For example, use of the disclosed passive filtration with one or more active filtration systems can help reduce the size of the active filtration system that is mounted on the aircraft. The present assignee also a patent portfolio that is directed to water treatment within the water tank (U.S. Pat. No. 10,266,426), water treatment along or in-line with water distribution lines (U.S. Pat. No. 9,376,333), as well as water treatment at the point of use (U.S. Pat. No. 9,260,323), (e.g., water treatment systems mounted within lavatory cabinets), as well as others. These water treatment technology systems may be used in connection with the present disclosure in order to treat and disinfect water that is held in the water tank on an on-going basis, after it has been treated upon upload using the methods and device10described herein. The subject matter of certain embodiments of this disclosure is described with specificity to meet statutory requirements, but this description is not necessarily intended to limit the scope of the claims. The claimed subject matter may be embodied in other ways, may include different elements or steps, and may be used in conjunction with other existing or future technologies. This description should not be interpreted as implying any particular order or arrangement among or between various steps or elements except when the order of individual steps or arrangement of elements is explicitly described. It should be understood that different arrangements of the components depicted in the drawings or described above, as well as components and steps not shown or described are possible. Similarly, some features and sub-combinations are useful and may be employed without reference to other features and sub-combinations. Embodiments of the invention have been described for illustrative and not restrictive purposes, and alternative embodiments will become apparent to readers of this patent. Accordingly, the present invention is not limited to the embodiments described above or depicted in the drawings, and various embodiments and modifications may be made without departing from the scope of the claims below. | 24,539 |
11858831 | DETAILED DESCRIPTION OF THE EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. However, the technical spirit of the present disclosure is not limited to the embodiments, but may be realized in different forms. The embodiments introduced here are provided to sufficiently deliver the spirit of the present disclosure to those skilled in the art so that the disclosed contents may become thorough and complete. When it is mentioned in the specification that one element is on another element, it means that the first element may be directly formed on the second element or a third element may be interposed between the first element and the second element. Further, in the drawings, the thicknesses of films and areas are exaggerated for efficient description of the technical contents. Further, in the various embodiments of the present disclosure, the terms such as first, second, and third are used to describe various elements, but the elements are not limited to the terms. The terms are used only to distinguish one element from another element. Accordingly, an element mentioned as a first element in one embodiment may be mentioned as a second element in another embodiment. The embodiments illustrated here include their complementary embodiments. Further, the term “and/or” in the specification is used to include at least one of the elements enumerated in the specification. In the specification, the terms of a singular form may include plural forms unless otherwise specified. In the specification, the terms “including” and “having” are used to designate that the features, the numbers, the steps, the elements, or combinations thereof described in the specification are present, and may be understood that one or more other features, numbers, step, elements, or combinations thereof may be added. Further, in the specification, “connected to” is used to mean a plurality of elements are indirectly or directly connected to each other. Further, in the following description of the present disclosure, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present disclosure rather unclear. FIG.1is a view illustrating a desalination apparatus using a solvent extraction scheme according to an embodiment of the present disclosure.FIG.2is a view illustrating a fresh water extracting process performed by the desalination apparatus using a solvent extraction scheme according to the present disclosure.FIG.3is a view illustrating a salt concentrating process performed by the desalination apparatus using a solvent extraction scheme according to the embodiment of the present disclosure. Referring toFIG.1, the desalination apparatus using a solvent extraction scheme according to the embodiment of the present disclosure may include a functional solvent supply module110, a source water supply module120, a mixing module200, a first separation module300, a heating module350, a second separation module400, a salt crystallization module500, a cooling module550, a salt storage tank600, a post-treatment module710, a fresh water storage tank720, a first heat exchanger810, and a second heat exchanger820. Hereinafter, the elements will be described in detail. The source water supply module120may supply source water to the mixing module130. According to the embodiment, the source water may include salt of a first concentration and water (H2O). For example, the concentration of salt ions contained in the source water may be 0.2 M to 1.0 M. For example, the source water may be seawater, industrial waste water, and the like. Hereinafter, it will be assumed that the source water is seawater for convenience of description. The source water may be discharged through a source water supply module outlet120b. The source water supply module outlet120bmay be connected to one end of a source water supply passage20. An opposite end of the source water supply passage20may be connected to the mixing module130. That is, after being discharged through the source water supply module outlet120b, the source water may be supplied to the mixing module200through the source water supply passage20. The functional solvent supply module110may supply a functional solvent to the mixing module200. According to an embodiment, the solubility of the functional solvent in water may vary according to temperature. For example, the functional solvent may include at least one of dipropylamine, ethylheptylamine, dibutylamine, and ethylbutylamine. The functional solvent may be discharged through a functional solvent supply module outlet110b. The functional solvent supply module outlet110bmay be connected to one end of a functional solvent supply passage10. An opposite end of the functional solvent supply passage10may be connected to the mixing module200. That is, after being discharged through the functional solvent supply module outlet110b, the functional solvent may be supplied to the mixing module200through the functional solvent supply passage10. The mixing module200, as described above, may receive the source water and the functional solvent from the source water supply module120and the functional solvent supply module110, respectively, to mix them. In detail, the mixing module200may receive the source water and the functional solvent through a mixing module inlet200a. According to the embodiment, the mixing module200may include an agitator210. The agitator210may be disposed in the interior of the mixing module200. The source water and the functional solvent may be mixed through the agitator210. According to the embodiment, the speed of the agitator may be controlled. In detail, the speed of the agitator may be controlled to 100 rpm to 500 rpm. That is, the source water and the functional solvent may be mixed through the agitator operated at a speed of 100 rpm to 500 rpm. Unlike this, when the speed of the agitator is controlled to less than 100 rpm, the water contained in the source water may not be dissolved in the functional solvent in the first separation module300, which will be described below. Meanwhile, when the speed of the agitator is controlled to more than 500 rpm, water layers may not be easily formed between the functional solvent, in which the water has been dissolved, and the source water, from which the water has been removed, in the first separation module300, and thus, as a result, the crystallized salt ions may not be easily extracted. The mixture water, in which the source water and the functional solvent are mixed, may be discharged a mixing module outlet200b. The mixing module outlet200bmay be connected to one end of a mixture water supply passage30. An opposite end of the mixture water supply passage30may be connected to the first separation module300. That is, after being discharged through the mixing module outlet200b, the mixture water may be supplied to the first separation module300through the mixture water supply passage30. The first separation module300may receive the mixture water from the mixing module200. In detail, the first separation module300may receive the mixture water discharged from the mixing module200and provided along the mixture water supply passage30, through a first separation module inlet300a. In the mixture water introduced into the first separation module300, the water contained in the source water may be dissolved in the functional solvent. To achieve this, the first separation module300may maintain a first temperature. For example, the first temperature may be 15° C. to 30° C. As the water contained in the source water is dissolved in the functional solvent, the mixture water may be separated to the functional solvent, in which the water has been dissolved, and the source water, from which the water has been removed. The source water, from which the water has been removed, may include salt of a second concentration. The second concentration may be higher than the first concentration. A mechanism, in which the mixture water is separated to the functional solvent, in which the water has been dissolved, and the source water, from which the water has been removed, will be described in more detail with reference toFIG.2. Referring toFIG.2, the mixture water, as illustrated inFIG.2, may be in a state, in which the functional solvent FS and the source water (saline water) are mixed. When the mixture water is provided into the first separation module300having the first temperature, the functional solvent FS contained in the mixture water may dissolve the water through hydrogen bonds with the water (H2O) contained in the source water. That is, the water molecules contained in the source water may travel from the source water to the functional solvent FS. Accordingly, the mixture water, as illustrated inFIG.2, may be separated to the functional solvent, in which the water has been dissolved, and the source water (brine), from which the water has been removed. Furthermore, the source water, from which the water has been removed, may have a smaller amount of water as compared with the source water supplied from the source water supply module120. Accordingly, the source water, from which the water has been removed, may include salt of a second concentration that is higher than the first concentration. The functional solvent, in which the water has been dissolved, and the source water, from which the water has been removed, may form water layers. The functional solvent, in which the water has been dissolved, and the source water, from which the water has been removed, may be separated by the differences of densities and polarities thereof. In order to improve the separation efficiency of the functional solvent, in which the water has been dissolved, and the source water, from which the water has been removed, the first separation module may include a first partition wall310. According to the embodiment, the density of the first partition wall310may be higher than the density of the functional solvent, in which the water has been dissolved, and may be lower than the density of the source water, from which the water has been removed. Accordingly, the first partition wall310may be disposed between the functional solvent, in which the water has been dissolved, and the source water, from which the water has been removed, to improve the separation efficiency of the functional solvent, in which the water has been dissolved, and the source water, from which the water has been removed. The functional solvent, in which the water separated from the mixture water in the first separation module300has been dissolved, may be discharged through a first separation module solvent outlet300c. The first separation module solvent outlet300cmay be connected to one end of a functional solvent supply passage40for the functional solvent, in which the water has been dissolved. An opposite end of the functional solvent supply passage40for the functional solvent, in which the water has been dissolved, may be connected to the second separation module400. That is, after being discharged through the first separation module solvent outlet300c, the functional solvent, in which the water has been dissolved, may be supplied to the second separation module400through the functional solvent supply passage40. The source water, from which the water separated from the mixture water in the first separation module300has been removed, may be discharged through a first separation module source water outlet300b. The first separation module source water outlet300bmay be connected to one end of the source water supply passage60for the source water, from which the water has been removed. An opposite end of the source water supply passage60for the source water, from which the water has been removed, may be connected to the salt crystallization module500. That is, after being discharged through the first separation module source water outlet300b, the source water, from which the water has been removed, may be supplied to the salt crystallization module500through the source water supply passage60for the source water, from which the water has been removed. The second separation module400may receive the functional solvent, in which the water has been dissolved, from the first separation module300. In detail, the second separation module400may be discharged from the first separation module300to receive the functional solvent, in which the water has been dissolved, provided along the functional solvent supply passage40for the functional solvent, in which the water has been dissolved, through a second separation module inlet400a. The functional solvent, in which the water introduced into the second separation module400has been dissolved, may be separated to the water and the functional solvent. The separation of the functional solvent, in which the water has been dissolved, may be performed at a second temperature. The second temperature may be higher than the first temperature. For example, the second temperature may be 60° C. to 80° C. A mechanism for separating the water and the functional solvent from the functional solvent, in which the water has been dissolved, will be described in more detail with reference toFIG.2. Referring toFIG.2, as described above, the solubility of the functional solvent in the water may vary according to temperature. Accordingly, when the functional solvent, in which the water has been dissolved, is heat-treated at the second temperature that is higher than the first temperature, the solubility of the functional solvent in the water may vary. In detail, the solubility of the functional solvent in the water when the functional solvent, in which the water has been dissolved, is heat-treated at the second temperature, may be decreased as compared with the solubility of the functional solvent in the water, which is contained in the mixture water provided into the first separation module300having the first temperature. As a result, when the functional solvent, in which the water has been dissolved, is heat-treated at the second temperature, the solubility of the functional solvent in the water is relatively decreased so that the water may be separated from the functional solvent, in which the water has been dissolved. The water and the functional solvent may form water layers. The water and the functional solvent may be separated by the differences of the densities and the polarities thereof. In order to improve the separation efficiency of the water and the functional solvent, the second separation module may include a second partition wall410. According to the embodiment, the density of the second partition wall410may be higher than the density of the functional solvent and lower than the density of the water. Accordingly, the second partition wall410may be disposed between the functional solvent and the water to improve the separation efficiency of the functional solvent and the water. The heating module350may increase the temperature of the functional solvent, in which the water discharged from the first separation module300has been dissolved. The functional solvent, in which the water, the temperature of which has been increased by the heating module350, has been dissolved, may be provided to the second separation module400. In more detail, the heating module350may increase the temperature of the functional solvent, in which the water discharged from the first separation module300has been dissolved, to the second temperature. To achieve this, the heating module350may be disposed between the first separation module300and the second separation module400. The salt crystallization module500may receive the source water, from which the water has been removed, from the first separation module300. In detail, the salt crystallization module500may receive the source water discharged from the first separation module300and, from which the water provided along the source water supply passage60from the source water, from which the water has been removed, through a first salt crystallization module outlet500a. The salt ions in the source water, from which the water introduced into the salt crystallization module500has been removed, may be crystallized and the salt crystals may be extracted. The crystallization of the salt ions may be performed through a method for providing seeds after the source water, from which the water has been removed, is cooled. The seeds may crystallize the salt of the second concentration contained in the source water, from which the water has been removed. For example, the seeds may be biochar, sand, and the like. A mechanism for crystallizing the salt ions in the source water, from which the water has been removed, will be described in more detail with reference toFIG.3. Referring toFIG.3, in the source water, from which the water introduced into the salt crystallization module500has been removed, as illustrated inFIG.3, a plurality of sodium ions (Na+) and a plurality of chloride ions (Cl−) may be disposed in the water to be spaced apart from each other. Thereafter, when the source water, from which the water has been removed, is cooled, the sodium ions (Na+) and the chloride ions (Cl−) are coupled to each other to form sodium chloride (NaCl) salt ions as illustrated inFIG.3. The chloride ions, as illustrated inFIG.3, may be crystallized by the seeds. Referring toFIG.1again, the cooling module550may provide the cooling water to the salt crystallization module500. According to the embodiment, the cooling water may circulate along the outside of the salt crystallization module500. Accordingly, the source water, from which the water introduced into the salt crystallization module500has been removed, may be cooled. According to the embodiment, the cooling module550may include a cooling water inlet500aand a cooling water outlet500b. The cooling water outlet500bmay be connected to one end of a cooling water supply passage72. An opposite end of the cooling water supply passage72may be connected to a second salt crystallization module inlet500b. Accordingly, the cooling water discharged from the cooling module550may be supplied to the salt crystallization module500through the cooling water supply passage72. After circulating along the outside of the salt crystallization module500, the cooling water supplied to the salt crystallization module500may be discharged through a second salt crystallization module outlet500d. The second salt crystallization module outlet500dmay be connected to one end of a cooling water discharge passage74. An opposite end of the cooling water discharge passage74may be connected to the cooling water inlet500a. Accordingly, the cooling water discharged from the salt crystallization module500may be supplied to the cooling module550through the cooling water discharge passage74. That is, after being discharged from the cooling module550, the cooling water may circulate to be introduced into the cooling module550again via the cooling water supply passage72, the salt crystallization module500, and the cooling water discharge passage74. The salt storage tank600may receive the crystallized salt ions from the salt crystallization module500. In detail, after being discharged to a first salt crystallization module outlet500c, the salt ions separated from the source water, from which the water has been removed, and crystallized by the salt crystallization module500may be introduced into a salt storage tank inlet600cthrough a crystallized salt ion supply passage62. The salt storage tank600may store the provided crystallized salt ions. The source water, from which the crystallized salt ions have been extracted, may be provided to the source water supply module120through a source water recovery passage (not illustrated). The source water recovery passage (not illustrated) may connect the salt crystallization module500and the source water supply module120. That is, the source water, from which the water provided to the salt crystallization module500has been removed, may be separated salt ions and the source water, from which the crystallized salt ions have been extracted. In this case, the crystallized salt ions may travel to the salt storage tank600and be stored in the interior of the salt storage tank600and the source water, from which the crystallized salt ions have been extracted, may travel to the source water supply module120to be recycled as the source water supplied to the mixing module200. Subsequently, referring toFIG.1, the post-treatment module710may receive the water from the second separation module400. In detail, the post-treatment module710may be discharged from the second separation module400, and may be provided with the water provided along the fresh water supply passage80. The post-treatment module710may remove the marginal functional solvent contained in the water. For example, the post-treatment module710may remove the marginal functional solvent contained in the water by using biochar, sand, and the like. Thereafter, the water, from which the functional solvent has been removed, may be provided to and stored in the fresh water storage tank720. The functional solvent thermally separated from the second separation module400may be recovered to the functional solvent supply module110through a functional solvent recovery passage50. To achieve this, the functional solvent recovery passage50may connect the second separation module400and the functional solvent supply module110. That is, one end of the functional solvent recovery passage50may be connected to the second separation module400, and an opposite end of the functional solvent recovery passage50may be connected to the functional solvent supply module110. According to an embodiment, the functional solvent recovery passage50may include first to third functional solvent recovery passages52,54, and56. The first functional solvent recovery passage52may connect the second separation module400and the first heat exchanger810. The second functional solvent recovery passage54may connect the first heat exchanger810and the second heat exchanger820. The third functional solvent recovery passage56may connect the second heat exchanger820and the functional solvent supply module110. That is, the first functional solvent recovery passage52, the first heat exchanger810, the second functional solvent recovery passage54, the second heat exchanger820, and the third functional solvent recovery passage56may be disposed between the second separation module400and the functional solvent supply module110. The first heat exchanger810may exchange heat between the functional solvent, in which the water discharged from the first separation module300has been dissolved, and the functional solvent thermally separated from the second separation module400. In detail, the first heat exchanger810may transfer heat from the thermally separated functional solvent that travels through the first functional solvent recovery passage52to the functional solvent, in which the water has been dissolved, which travels through the functional solvent supply passage40for the functional solvent, in which the water has been dissolved. The thermally separated functional solvent that travels through the first functional solvent recovery passage52may be in a state in which it is heated by the heating module350. Meanwhile, the functional solvent, in which the water has been dissolved, which travels through the functional solvent supply passage40for the functional solvent, in which the water has been dissolved, may be a state before it is heated by the heating module350. For example, the temperature of the thermally separated functional solvent that travels through the first functional solvent recovery passage52may be 60° C. to 80° C. Meanwhile, the temperature of the functional solvent, in which the water has been dissolved, which travels through the functional solvent supply passage40for the functional solvent, in which the water has been dissolved, may be 15° C. to 30° C. Accordingly, the first heat exchanger810may transfer heat from the thermally separated functional solvent that travels through the first functional solvent recovery passage52having a high temperature to the functional solvent, in which the water has been dissolved, which travels through the functional solvent supply passage40having a low temperature for the functional solvent, in which the water has been dissolved. As a result, as the first heat exchanger810increases the temperature of the functional solvent, in which the water in a state before it is heated by the heating module350has been dissolved, consumption of energy for increasing the temperature of the functional solvent, in which the water has been dissolved, by the heating module350may be reduced. That is, the first heat exchanger810may improve the energy efficiency of the heating module350. The second heat exchanger820may exchange heat between the cooling water that cooled the salt crystallization module500, and the functional solvent thermally separated from the second separation module400and recovered to the functional solvent supply module110. In detail, the second heat exchanger820may transfer heat from the thermally separated functional solvent that travels through the second functional solvent recovery passage54to the cooling water that travels through the cooling water discharge passage74. The temperature of the thermally separated functional solvent that travels through the second functional solvent recovery passage54may be higher than the temperature of the cooling water that travels through the cooling water discharge passage74. Accordingly, the second heat exchanger820may transfer heat from the thermally separated functional solvent that travels through the second functional solvent recovery passage54having a high temperature to the cooling water that travels through the cooling water discharge passage74having a low temperature. As a result, the second heat exchanger820may decrease the temperature of the thermally separated functional solvent recovered to the functional solvent supply module110. Accordingly, the second heat exchanger820may improve the energy efficiencies of the functional solvent supply module110and the mixing module200by decreasing the temperature of the functional solvent provided from the functional solvent supply module110to the mixing module200. The desalination apparatus using a solvent extraction scheme according to the embodiment of the present disclosure may include a source water supply module120configured to supply source water including salt of a first concentration and water, a functional solvent supply module110configured to supply a functional solvent, of which the solubility in water varies according to temperature, a mixing module200configured to mix the source water from the source water supply module120and the functional solvent from the functional solvent supply module110, a first separation module300configured to receive mixture water, in which the source water and the functional solvent are mixed, from the mixing module, and dissolve the water contained in the source water in the functional solvent, a salt crystallization module500configured to receive the source water including salt of a second concentration that is higher than the first concentration, from which the water has been removed, from the first separation module300, and a second separation module400configured to receive the functional solvent, in which the water has been dissolved, from the first separation module300, and thermally separate the water and the functional solvent at a second temperature that is higher than the first temperature. Accordingly, unlike an existing seawater desalination process that has performed desalination by using distillation or reverse osmosis, energy and costs that are consumed in an operation process may be significantly reduced as a pre-treatment process for seawater or energy for changing the phase of seawater to vapor are not necessary. Until now, the desalination apparatus using a solvent extraction scheme according to the embodiment of the present disclosure has been described. Hereinafter, a desalination method using a solvent extraction scheme according to an embodiment of the present disclosure will be described. FIG.4is a flowchart illustrating a desalination method using a solvent extraction scheme according to an embodiment of the present disclosure. Referring toFIG.4, the desalination method using a solvent extraction scheme according to the embodiment may include an operation S100of supplying source water and a functional solvent, an operation S200of mixing the source water and the functional solvent, a first separation operation S300, and a second separation operation S400. Hereinafter, the respective operations will be described. Furthermore, it is apparent that the desalination method using a solvent extraction scheme according to the embodiment may be performed by the desalination apparatus using a solvent extraction scheme according to the embodiment, which has been described with reference toFIG.1. In the operation S100, the source water and the functional solvent may be supplied to the mixing module. According to the embodiment, the source water may include salt of a first concentration and water (H2O). For example, the concentration of salt ions contained in the source water may be 0.2 M to 1.0 M. For example, the source water may be seawater, industrial waste water, and the like. The solubility of the functional solvent in water may vary according to temperature. For example, the functional solvent may include at least one of dipropylamine, ethylheptylamine, dibutylamine, and ethylbutylamine. In the operation S200, the source water and the functional solvent may be mixed. According to the embodiment, the source water and the functional solvent may be mixed through the agitator operated at a speed of 100 rpm to 500 rpm. Unlike this, when the speed of the agitator is controlled to less than 100 rpm, the water contained in the source water may not be dissolved in the functional solvent in the operation S300, which will be described below. Meanwhile, when the speed of the agitator is controlled to more than 500 rpm, water layers may not be easily formed between the functional solvent, in which the water has been dissolved, and the source water, from which the water has been removed, in the first separation operation S300and thus, as a result, the crystallized salt ions may not be easily extracted. In the operation S300, the mixture water, in which the source water and the functional solvent are mixed, may be provided, and the water contained in the source water may be dissolved in the functional solvent at a first temperature. As the water contained in the source water is dissolved in the functional solvent, the mixture water may be separated to the functional solvent, in which the water has been dissolved, and the source water, from which the water has been removed. The source water, from which the water has been removed, may include salt of a second concentration. The second concentration may be higher than the first concentration. That is, the mixture water, in which the functional solvent and the source water are mixed, is provided to an environment having the first temperature, the functional solvent may dissolve the water through hydrogen bonds with water H2O contained in the source water. That is, the water molecules contained in the source water may travel from the source water to the functional solvent. Accordingly, the mixture water may be separated to the functional solvent, in which the water has been dissolved, and the source water, from which the water has been removed. The functional solvent, in which the water has been dissolved, and the source water, from which the water has been removed, may form water layers. The functional solvent, in which the water has been dissolved, and the source water, from which the water has been removed, may be separated by the differences of densities and polarities thereof. In the operation S400, the functional solvent, in which the water has been dissolved, may be provided, and the water and the functional solvent may be thermally separated at a second temperature that is higher than the first temperature. That is, the functional solvent, in which the water has been dissolved, may be thermally treated to the second temperature and may be separated to the water and the functional solvent. For example, the second temperature may be 60° C. to 80° C. As described above, the solubility of the functional solvent in water may vary according to temperature. Accordingly, when the functional solvent, in which the water has been dissolved, is heat-treated at the second temperature that is higher than the first temperature, the solubility of the functional solvent in the water may vary. In detail, the solubility of the functional solvent in the water when the functional solvent, in which the water has been dissolved, is heat-treated at the second temperature, may be decreased as compared with the solubility of the functional solvent in the water, which is contained in the mixture water provided to the environment of the first temperature in the operation S300. As a result, when the functional solvent, in which the water has been dissolved, is heat-treated at the second temperature, the solubility of the functional solvent in the water is relatively decreased so that the water may be separated from the functional solvent, in which the water has been dissolved. The water and the functional solvent may form water layers. The water and the functional solvent may be separated by the differences of the densities and the polarities thereof. The functional solvent thermally separated in the second separation operation S400may be recovered and may be reused in the operation S100. The desalination apparatus according to the embodiment may further include, after the first separation operation S300, an operation of crystallizing salt ions of a second concentration. In detail, the operation of crystallizing the salt ions of the second concentration may be performed through a scheme of receiving the source water, from which the water separated in the first separation operation has been removed, cooling the source water, and providing seeds. For example, the seeds may be biochar, sand, and the like. A detailed mechanism for crystallizing the salt ions may be the same as the mechanism for crystallizing salt ions, which is performed in the salt crystallization module described with reference toFIG.3. Accordingly, a detailed description thereof will be omitted. The salt ions crystallized in the operation of crystallizing the salt ions of the second concentration may be stored in the storage tank. Meanwhile, the source water, from which the salt ions crystallized in the operation of crystallizing the salt ions of the second concentration may be recovered, and may be reused in the operation S100. Until now, the desalination apparatus and the desalination method using a solvent extraction scheme according to the embodiment of the present disclosure have been described. Hereinafter, detailed experimental examples and characteristic evaluation results of the desalination apparatus and the desalination method using a solvent extraction scheme according to the embodiments of the present disclosure will be described. FIG.5illustrates pictures for comparing the characteristics of functional solvents used in the desalination apparatus using a solvent extraction scheme according to the embodiment of the present disclosure. FIG.6illustrates a graph for comparing the characteristics of functional solvents used in the desalination apparatus using a solvent extraction scheme according to the embodiment of the present disclosure. Referring toFIG.5, after different functional solvents A to C were prepared and the functional solvents A to C were mixed with source water containing NaCl of a concentration of 0.5 M, states, in which the functional solvents and the source water were mixed, were photographed and are illustrated inFIG.5. The functional solvent A was octylamine, the functional solvent B was dibutylamine, and the functional solvent C was 2-ethylhexylamine. As can be seen fromFIG.5, it could be identified that when the functional solvents A to C were mixed with the source water, all of the functional solvents A to C formed a solvent phase and a brine phase. It is determined that this is because the water contained in the source water containing NaCl of a concentration of 0.5 M was dissolved in the functional solvents A to C, and the phases were classified into the solvent phase, in which the functional solvent and the water were mixed, and the brine phase, in which the water was removed from the source water. Referring toFIG.6, after different functional solvents A to C were prepared and the functional solvents A to C were mixed with source water containing NaCl of a concentration of 0.5 M, the water absorptions (%) and the Cl rejections (%) of the functional solvents A to C were measured and are illustrated. For the water absorptions, the moisture content of the solvent phase when the functional solvent and the source water were mixed to form water layers was measured. The Cl rejections were calculated through Formula 1. ResidualmassofCl-inthebrineInitialmassofCl-inthesalinewater×100〈Formula1〉 As can be seen fromFIG.6, it was shown that the water absorption of the functional solvent A is the highest but it was shown that the Cl rejection of the functional solvent B is the highest. It is determined that it is difficult to apply the functional solvent A (octylamine) to the desalination apparatus using a solvent extraction scheme according to the embodiment as its water absorption is high but its Cl rejection is low. Meanwhile, it is determined that it is suitable to apply the functional solvent B (dibutylamine) to the desalination apparatus using a solvent extraction scheme according to the embodiment as its water absorption is relatively low but its Cl rejection is remarkably high. FIG.7illustrates a graph for comparing changes in characteristics according to the speeds of an agitator included in a mixing module of the desalination apparatus using a solvent extraction scheme according to the embodiment of the present disclosure. Referring toFIG.7, the speeds of an agitator included in the mixing module of the desalination apparatus using a solvent extraction scheme according to the embodiment were controlled to 100 rpm, 300 rpm, 500 rpm, 700 rpm, and 1000 rpm and the water recoveries (%) and the Cl rejections (%) for the cases were measured. The water recoveries and the Cl rejections were calculated as described inFIG.6. The results of the graph illustrated inFIG.7are summarized through Table 1. TABLE 1WaterClCategoryrecovery (%)rejection (%)100 rpm12.4393.04300 rpm15.1392.97500 rpm15.7393.15700 rpm18.3189.531000 rpm18.3588.83 As can be seen fromFIG.7and Table 1, it could be identified that the Cl rejections were scarcely different when the speeds of the agitator is 100 rpm, 300 rpm, and 500 rpm, but the Cl rejections were significantly decreased at 700 rpm and 1000 rpm. It is determined that this is because, as described with reference toFIG.1, water layers were not easily formed between the functional solvent, in which the water had been dissolved, and the source water, from which the water had been removed, when the agitation speed is two high. That is, it can be identified that, when the desalination apparatus using a solvent extraction scheme according to the embodiment is used, the speed of the agitator included in the mixing module needs to be controlled to 100 rpm to 500 rpm. FIG.8illustrates a graph for comparing characteristics according to the number of reuses of source water separated from a salt crystallization module included in the desalination apparatus using a solvent extraction scheme according to the embodiment of the present disclosure. Referring toFIG.8, the weight (salt recovery, mg) of the crystallized salt ions acquired from the salt crystallization module (repetition 1) included in the desalination apparatus using a solvent extraction scheme according to the embodiment, the weight of the crystallized salt ions acquired by reusing (repetition 2) the source water separated from the salt crystallization module included in the desalination apparatus using a solvent extraction scheme according to the embodiment, the weight of the crystallized salt ions acquired by reusing (repetition 3) two times the source water separated from the salt crystallization module included in the desalination apparatus using a solvent extraction scheme according to the embodiment, and the weight of the crystallized salt ions acquired by reusing (repetition 4) three times the source water separated from the salt crystallization module included in the desalination apparatus using a solvent extraction scheme according to the embodiment were measured and are illustrated. The results of the graph illustrated inFIG.8are summarized through Table 2. TABLE 2RepetitionRepetitionRepetitionRepetitionCategory1234Salt6.486.486.917.56recovery As can be seen throughFIG.8and Table 2, it could be identified that in the desalination apparatus using a solvent extraction scheme according to the embodiment, the concentration of the salt ions increased as the number of reuses of the source water separated from the salt crystallization module increased, and thus the weight of the salt ions also increased. After mixing the functional solvent, of which the solubility in water varies according to temperature, with the source water, the desalination apparatus using a solvent extraction scheme according to the embodiment of the present disclosure may derive the solubilities of the functional solvents in the source water through changes in temperature. Accordingly, fresh water may be acquired by removing salt ions from the source water. Accordingly, unlike an existing seawater desalination process that has performed desalination by using distillation or reverse osmosis, energy and costs that are consumed in an operation process may be significantly reduced as a pre-treatment process for seawater or energy for changing the phase of seawater to vapor are not necessary. Although the preferred embodiments of the present disclosure have been described in detail until now, the scope of the present disclosure is not limited to the embodiments and should be construed by the attached claims. Further, it should be understood that those skilled in the art to which the present disclosure pertains may variously correct and modify the present disclosure without departing from the scope of the present disclosure. | 43,140 |
11858832 | The figures are not necessarily to scale. Like numbers used in the figures refer to like components. However, it will be understood that the use of a number to refer to a component in a given figure is not intended to limit the component in another figure labeled with the same number. DETAILED DESCRIPTION Embodiments described herein relate to devices, systems and methods for discriminating between different types of objects. The objects emanate output light in response to an excitation light that is directed toward the objects in a fluid column, such as a flow stream. As used herein the term “emanate” refers to both reflected and fluoresced electromagnetic radiation, such as light. As used herein the term “light” refers to both electromagnetic radiation at wavelengths in the visible spectrum as well as electromagnetic radiation at wavelengths in the infrared and ultraviolet spectrums. Such output electromagnetic radiation may include light reflected or fluoresced directly from an object as well as light reflected or fluoresced by a stain or dye associated the object. In some implementations, cell types are distinguished based on the intensity of the output electromagnetic radiation emanating from the objects. Intensity can be determined as a peak intensity or even as a total intensity, such as the integrated area under an intensity signal. Specific embodiments described herein are directed to distinguishing between X-chromosome sperm cells and Y-chromosome sperm cells. Further embodiments are concerned with distinguishing viable X-chromosome bearing sperm cells from objects other than viable X-chromosome bearing sperm cells, including Y-chromosome bearing sperm cells and non-viable cells of both sexes. It will be appreciated that the approaches of this disclosure can be applied more generally to distinguishing between any objects of different types so long as the output electromagnetic radiation emanating from one object type generates a discernable difference in at least one characteristic when compared to the electromagnetic radiation emanating from another object type. In some examples provided, the fluid column is a flow stream that has a curved boundary or interface where refraction of electromagnetic radiation may occur. For example, the curved boundary of the fluid column may be generally circular in cross section. The fluid column can be bounded by solid walls, such as within a cuvette or within a microfluidic channel, or may be jetted into the air, such as in a jet-in-air flow cytometer. The objects may move along the fluid column through a central core shaped by a sheath fluid that at least partially surrounds the central core. In the case of sperm sorting applications, the central core may comprise a core stream of sample fluid containing sperm cells. The core stream may be conditioned into a generally ribbon shape or may have a generally elliptical cross section for the purpose of orienting aspherical sperm cells. Electromagnetic radiation emanating from the objects encounters at least one optical refraction boundary between the objects and other materials, such as at the interface between the fluid column and air. Due at least in part to the different refractive properties of sheath fluid and air, the light collection efficiency external to the fluid column of light emanating from objects within the column depends upon the position of the objects for such systems. Light collection efficiency that varies with position is detrimental in applications where the light emanating from the objects must be precisely quantified and such precision is limited by random (not directly observable) position fluctuations of the objects. In the case of sex differentiating sperm specifically, such systems seek to differentiate very bright and closely related fluorescence intensities. Sperm cells and sperm nuclei are generally stained with Hoechst 33342 to make such differentiations. Hoechst 33342 is a bright, cell permeable dye that binds selectively with the A-T base pairs in the minor grove of double stranded nuclear DNA. The stoichiometric staining of sperm cells with Hoechst 33342 differentiates X-chromosome and Y-chromosome as having slightly different amounts of nuclear DNA. For example, many domestic animals have about a four percent difference. When sperm cells are properly stained and oriented, this small difference can be distinguished by the fluorescence intensity of the Hoechst 33342 associated with the nuclear DNA of the sperm cells when they are irradiated with an appropriate excitation source, such as a laser operating at or near a wavelength of 355 nm. This four percent difference is difficult to detect for several reasons. First, sperm nuclear DNA resides within the sperm head, which is aspherical or has a paddle-like shape in most species. This asymmetry causes sperm to fluoresce differently out the flat side and more narrow side. Indeed, this fluctuation exceeds the four percent difference in DNA content, meaning sperm must be oriented in order to be differentiated based on nuclear chromosomal content. Orienting geometries tend to produce a core stream having a ribbon shape, or an elliptical cross section. This elliptical cross section provides sperm larger than normal latitude for placement in one axis. The approaches disclosed herein enhance the precision of systems that may be limited by such fluctuations, such as jet-in-air flow cytometers. As described in more detail below, the positional variability of light intensity collected from objects in a fluid column can be addressed with an algorithm that corrects for the dependence of intensity on position. The approaches outlined herein are particularly applicable to flow cytometry. However, the approaches can be applied to any system where light is collected on one side of an interface from objects emanating the light from the other side of the interface, wherein the interface causes a variation in the emanating light ray paths in a manner dependent on the object's position relative to the detector. Approaches herein correct for positional variation within the fluid column thus providing more accurate measurements for distinguishing types of objects. The “jet-in-air” flow cytometer system100illustrated schematically inFIG.1is one type of discrimination system that can be used to discuss the concepts of the disclosure. The “jet-in-air” flow cytometer system100includes a fluid column forming structure that creates a flow stream comprising a fluid column150that jets out of the exit nozzle160of the chamber110at high velocity, e.g., about 20 m/s. The fluid column150expelled from the exit nozzle160can be roughly circular in cross-section and may have a diameter of about 10 μm to about 100 μm in some implementations. In some embodiments, the interior of the chamber110and/or the exit nozzle160are configured with an internal geometry that hydrodynamically orients sperm within the fluid column. As a non-limiting examples the nozzles like those described in U.S. Pat. Nos. 6,782,768 and 6,263,745 may be incorporated for the purpose of orienting sperm and generating the coaxial flow of a fluid column. The fluid column150is composed of a core stream151within a sheath stream152where the arrows inFIG.1indicate the direction of flow of the core and sheath streams151,152. The sheath stream152may have a generally circular cross section, while the core stream has generally elliptical cross section, with a major and a minor axis. Within the chamber110, a sample injection element111introduces the core stream151containing objects171,172which may be of multiple types. The core stream151is bounded by a sheath stream152comprising sheath fluid and shaped by hydrodynamic forces in the chamber110. The sheath stream152at least partially surrounds the core stream151, and the sheath stream152and the core stream151do not substantially mix. The sloping or angled walls115of the chamber110impart forces that shape the core stream151and accelerate objects171,172within the core stream151. The movement of the sheath stream152constrains the objects171,172in the core stream151to move toward the center of the fluid column150when the fluid column150is ejected from the chamber110. The fluid column150delivers the objects171,172to a measurement region175of the fluid column150, e.g., in single file. As the objects pass through the measurement region175of the fluid column150, light from an excitation source180provides excitation light to the objects171,172. The excitation source180can provide light in a broad wavelength band or in a narrow wavelength band. For example, the excitation source180may be a laser. Any laser suitable for producing a response from the object or a dye associated with the object may be employed. Pulsed lasers and continuous wave lasers are each well suited to produce appropriate responses. In some configurations, electromagnetic radiation generated by the excitation source, such as excitation light, may be modified by an optical element181. For example, the excitation light may be focused on the measurement region175by a one or more lenses181. Lenses may be used to focus the excitation electromagnetic radiation into a suitable beam shape focused on the measurement region. Objects172ain the measurement region175emanate light, e.g., scattered or fluorescent light, in response to the excitation source180. Objects of a first type171will emanate output electromagnetic radiation that differs in at least one characteristic as compared to output electromagnetic radiation that emanates from objects of the second type172. For example, in some scenarios, objects of the first type171will emanate light having a higher intensity than the light that emanates from objects of the second type172. An optical collection arrangement190is positioned to collect the output electromagnetic radiation161emanating from the object172awithin the measurement region175that crosses the optical refraction boundary of the fluid column150at the fluid-air interface153. In some embodiments, the optical arrangement190may be configured to modify the output electromagnetic radiation161to provide modified output electromagnetic radiation162that focuses output electromagnetic radiation emanating from the object172ain the measurement region175onto a detector185. In some embodiments, the optical collection arrangement190may include an element that reduces the positional dependence of the output electromagnetic radiation161. The detector185receives the modified output electromagnetic radiation162and, in response, generates an electrical signal representative of characteristics of the modified output electromagnetic radiation. As but an example, the detector185may be a forward fluorescence detector. Of course, other detectors may be incorporated to detect characteristics of interest, such as scatter, decay, phase shifts or other characteristics of interest. As but non-limiting examples, the detector may be a photomultiplier tube (PMT), silicon photomultiplier (SiPM) a photodiode array, or a split detector. In some embodiments, the detector185may represent more than one detectors. In some embodiments, a second position detector may be utilized. In other embodiments a side detector may be employed to detect side scatter or side fluorescence. Still other embodiments may incorporate both a position detector and a side detector in addition to the detector185. In some scenarios, the amplitude of the electrical signal may be different for different object types. The electrical signal is used by an analyzer187to distinguish between different types of objects171,172. For example, the analyzer187may be configured to compare the amplitude of the electrical signal to a threshold to discriminate between objects of the first type171and objects of the second type172. The analyzer187may include one or more analog circuits and/or digital processors for manipulating one or more signals from one or more detectors. As but one example, a side detector may be employed 90 degrees relative to the detector185to detect side scatter or side fluorescence. In the case of sperm sorting, side fluorescence allows the analyzer187to differentiate properly oriented sperm from unoriented sperm. The analyzer187may include a processor188having executable instructions stored thereon. In addition to those instructions198known for the purpose of collecting, comparing and manipulating information from detector signals, the processor may include instructions192for normalizing the intensity value of the output electromagnetic radiation in the represented in the electrical signal from the detector based on the position of the object172ain the fluid column150at the measurement region175. The intensity value may be normalized in any number of ways. As but one example, hand drawn lines or curves may be input by a user into a graphical user interphase based on an initial sampling of data including fluorescence intensities and positional information. The processor188may also include instructions182for discriminating objects.FIG.2shows an x-y plane cross section of the fluid column150in the measurement region175depicted inFIG.1. In the x-y cross section of the measurement region175, the core stream151is elliptical in shape, and the fluid of the core stream151comprises at least one object172asuspended in a buffer solution, which may also be referred to as sample. The sheath stream152substantially surrounds the core stream151. In a particular example used for this discussion in this disclosure, the objects171,172are sperm cells and the system100is implemented to discriminate X-chromosome sperm from Y-chromosome sperm. A focused laser beam generated by the excitation source180irradiates the sperm cell172awithin the measurement region175. The cells171,172are stained with a fluorescent dye, and the excitation electromagnetic radiation causes the cell172awithin the measurement region175to emanate fluorescent output electromagnetic radiation. The purpose of the generally elliptical core stream151is to orient a sperm cell172asuch that the flat sides of the sperm cell are facing to the left and the right as shown inFIG.2. In this orientation, the flat sides of the sperm cell172aface the laser180and the optical collection arrangement190, respectively. When each cell171,172is presented in a similar orientation at the measurement region175, random variability based on orientation can be greatly reduced. However, the elliptical cross section which aids in this orientation also provides significant latitude with respect to the position of the cell within the fluid column150. To obtain the desired orientation, the elliptical core stream151, presents a major axis that parallels the x-axis depicted inFIG.2. The sperm cell172acan take any number of positions along the x-axis within the core stream151.FIG.2shows three representative possible positions for the sperm cell172ain the elliptical core151, although it may be appreciated sperm may be located anywhere in between the depicted positions. In the orientation shown inFIG.2, the first possible position for the sperm cell172ain the core stream151is approximately at the center of the elliptical core151(on the optical axis199of the optical collection arrangement190), a second possible position is at the top of the core stream151(above the optical axis199), and a third possible position is at the bottom of the core stream151(below the optical axis199). A position-dependent refraction of the output light rays emanating from the sperm cell172aoccurs at the fluid-air interface153at the different positions within the core stream151. As used herein terms of relative position such as “top,” “bottom,” “upper,” and “lower” should be understood as descriptive regarding the relationships between depicted features in the figures and not limiting on the claims, especially the position of sperm in a core stream151. When the sperm cell172ais located at the first position and the fluid column150has a circular cross section as shown inFIG.2, the in-plane rays of light emanating from the sperm cell172aare approximately normally incident on the fluid-air interface153. Rays that emanate from points of the sperm cell172aaway from its center, or rays that emanate out of the plane of the figure, are not exactly normally incident on the interface153; these rays are not considered in this simplified discussion, but one of ordinary skill in the art can see how the discussion could be generalized to include them. Thus, to the extent any refraction of light occurs at the fluid-air interface153it occurs in a more uniform manner with respect to the detector185. The diagram ofFIG.3shows uniform light refraction of the output electromagnetic radiation298emanating from a sperm cell172aas the electromagnetic radiation crosses the interface153when the sperm cell172ais at the 1st position within the elliptical core151shown inFIG.2. Correspondingly, the in-plane density of the light rays298exiting the fluid column150inFIG.3is uniform with respect to ray angle. Uniform angular density of light rays corresponds to uniform radiance as a function of ray angle. In contrast, when a sperm cell172ais off the optical axis199and is nearer to the top or bottom of the elliptical core151, e.g., at the 2nd and 3rd positions of the elliptical core151shown inFIG.2, at least some of the output rays emanating from the sperm cell172aencounter the fluid-air interface153at an oblique angle. These output rays are refracted in a non-uniform fashion at the fluid-air interface153in contrast to the normal incidence scenario described above. The most oblique rays are the most severely refracted. Refraction of the light rays causes the radiance distribution of the fluorescent light exiting the fluid column150across the fluid-air interface153to become non-uniform and to vary with position of the cell172aalong the x axis. That is, this refraction changes the radiance distribution of output electromagnetic radiation emanating from sperm cell172aoutside of the fluid column150. For example, when the cell172ais located off the optical axis199, e.g., at the 2nd or 3rd positions shown inFIG.2, the density of light rays and thus the radiance on the air side of the interface153is higher at positive or negative ray angles, respectively, with respect to the optical axis199when compared to the radiance on the air side of the interface153at angles parallel to the optical axis199or at negative or positive ray angles, respectively. Positive and negative refer to the sign of the ray angle γ inFIG.5.FIG.4is a diagram illustrating light rays299emanating from a cell172aand exiting the fluid column150through the fluid-air interface153when the cell172ais located at the 2nd position of the elliptical core151. In this scenario, the density of light rays, or radiance, at positive ray angles is greater than the density of the light rays parallel to optical axis199or at negative ray angles. For an optical system with a predetermined numerical aperture (NA), the amount of light collected by the system from cells of the same type (e.g., the collection efficiency) may vary depending on whether the cell is in the first position or the second position. The positional dependence of the system collection efficiency leads to inaccuracies in determining cell type. With reference toFIG.5, an analytical formula for the light ray density as a function of ray angle γ and sperm position x is determined using Snell's law, where γ is the angle of a light ray, with respect to the optical axis, emanating from the object after refraction at the fluid-air interface. This analysis considers only rays within, or tangential to, the two-dimensional cross-section of the flow stream. We wish to solve for the density of the light rays with respect to the angle γ, which we can use to determine the density of rays at the entrance pupil of an optical collection system for each sperm position x. This can be written: Iγ(γ) (1) For our purposes we can assume that the sperm cell emanates light uniformly in all directions, so the density of emanated light rays with respect to the angle θ is: Iθ(θ)=1/π (2) that is, uniformly distributed from θ=−π/2 to θ=π/2. By geometrical analysis: θ=tan-1(cos∅-xsin∅)(3)∝=π/2-∅-θ;and(4)γ=π/2-∅-β,(5) wherein the angles γ, θ, ϕ, α, β, and the distance x are shown inFIG.5. As the flow stream has index of refraction n, Snell's law yields another relation between the angles: sin β=nsin ∝ (6) The density of light rays external to the interface I_β (β) is related to the density of light rays internal to the interface I_α (α) by the following formula, with T(α) representing the average, across both polarizations, of the transmission through the interface: Iβ(β)=I∝(∝)T(∝)❘"\[LeftBracketingBar]"d∝dβ❘"\[RightBracketingBar]"(7) The transmission is related to the Fresnel reflection coefficients for s- and p-polarization, R_s (α) and R_p (α), with the following formulas: T(∝)=1-R(∝),(8)R(∝)=Rs(∝)+Rp(∝)2,(9)Rs(∝)=❘"\[LeftBracketingBar]"cos∝-ncosβcos∝+ncosβ❘"\[RightBracketingBar]"2,and(10)Rp(∝)=❘"\[LeftBracketingBar]"cosβ-ncos∝cosβ+ncos∝❘"\[RightBracketingBar]"2.(11) Using Eq. (7) with the above and the following additional relations: I∅(∅)=Iθ(θ)❘"\[LeftBracketingBar]"dθd∅❘"\[RightBracketingBar]",(12)I∝(∝)=I∅(∅)❘"\[LeftBracketingBar]"d∅d∝❘"\[RightBracketingBar]",and(13)Iγ(γ)=Iβ(β)❘"\[LeftBracketingBar]"dβdγ❘"\[RightBracketingBar]",(14) we have an expression for the density of rays with respect to γ: Iγ(γ)=Iθ(θ)❘"\[LeftBracketingBar]"dθdγ❘"\[RightBracketingBar]"T(γ)(15) Now, the optical collection arrangement's NA is given by the sine of the maximum ray angle γ_0, so we can solve for this angle in terms of NA: γ0=sin−1(NA) (16) Finally, the relative collected light intensity, as a function of sperm position x, is given by integrating Eq. (15) from −γ0to γ0and normalizing by that integral value at x=0: RelativeIntensity=∫-γ0γ0Iγdγ∫-γ0γ0Iγ(x=0)dγ.(17) Using the formula for ray density distribution of Eq. (15), the angular dependence of ray density (radiance) for different sperm positions can be plotted as inFIG.6. InFIG.6, each of the lines represents the density of rays as a function of angle γ for a given sperm position x, where the angle γ is in radians. The plots correspond to a series of positions that lie in a range symmetric about x=0, (corresponding to graph404inFIG.6), which is where the ray density (radiance) is uniform as a function of angle. When x is positive (e.g., 2nd position inFIG.2, corresponding to graph402), relative radiance is higher for positive ray angles γ and lower for negative ray angles γ, and the opposite is true when x is negative (e.g., 3rd position inFIG.2, corresponding to graph403). If the numerical aperture of the collection optics (optical collection arrangement190inFIGS.1and2) is large, e.g., approaching one, the variation in collected optical intensity with respect to position for light emanating from an object within the elliptical core is relatively small. This is because essentially all light emanating from the object and directed to the right would be collected by the collection optics, regardless of the exact ray direction, and the total amount of emanating light is invariant to object position (given uniform excitation). In contrast, a small numerical aperture results in a relatively large collected intensity variation with respect to object position, because changes in object position affect the radiance distribution, and a small numerical aperture implies only a portion of this changing radiance distribution is collected. Practical systems may have NAs that are significantly less than one, e.g., less than 0.5, or less than 0.3. The family of graphs provided inFIG.7illustrates the relative intensity of light collected from an object, as a function of object position x, through collection optics with different NAs.FIG.6illustrates the range of angles γ captured by the different numerical apertures ofFIG.7. In the family of graphs ofFIG.7, graph412illustrates the relative intensity with respect to position along the x axis for collection optics (e.g., optical collection arrangement190shown inFIGS.1and2) having a numerical aperture (NA) of 0.2; graph414shows the relative intensity with respect to position along the x axis for collection optics having an NA of 0.4; graph416shows the relative intensity with respect to position along the x axis for collection optics having an NA of 0.6; graph418shows the relative intensity with respect to position along the x axis for collection optics having an NA of 0.8; and graph419shows the relative intensity with respect to position along the x axis for collection optics having an NA of 0.9. It is clear fromFIGS.6and7that collection optics having smaller NAs produce a larger variation in collected light intensity with respect to object position when compared to collection optics having larger NAs. Additionally, collection optics with larger NAs collect light rays having a wider range of refraction angles than collection optics having smaller NAs, and therefore have a higher overall collection efficiency. With respect to sperm discrimination or sorting application in particular, it can be understood that the elliptical major axis of the core stream151(FIGS.1and2) may be about 50 μm in length, providing sperm about 25 μm in latitude to move in either direction. Referring back toFIG.7, it can be seen a NA of 0.2 only captures about 90% of an objects relative intensity when the object is about 17 μm off center. Similarly, a NA of 0.4 captures only 92% of the relative intensity for objects that are about 17 μm off center and a NA of 0.6 captures a little more than 94% of the relative intensity at the same position. It may be further appreciated that the NA of collection optics for a sperm sorter may be between about 0.3 and 0.6. WhileFIG.7illustrates the benefit of increasingly large numerical apertures, such numerical apertures are increasingly expensive and have a shallower field of depth, meaning the larger aperture must be placed closer to the nozzle. There is, however, a limit on how close the collection optics can be placed in sperm sorting applications. In typical sperm sorting instruments, the apertures may be between about 0.5 and 0.6. Embodiments described herein correct for the positional dependency on measured intensity allowing lower numerical aperture collection optics to perform like higher numerical aperture collection optics. Sperm located in the core stream151at positions approaching the 2nd and 3rd positions ofFIG.2, therefore, emanate a significantly lower overall intensity of electromagnetic radiation that is ultimately detected for analysis and discrimination. Indeed, the core stream151may have an elliptical major axis that is about 50 μm in length at high event rates (in the magnitude of 60,000 events per second and greater). Some sperm will be off center by 20 μm or even up to about 25 μm either side of the 1st position. In the context of extremely bright and closely related fluorescence signals, this variation can overshadow the roughly 4% difference in stained nuclear DNA differentiating X-chromosome bearing sperm from Y-chromosome bearing sperm. Furthermore, increasing the number of events at a given sperm concentration within a sample of buffer requires increasing the volume of sample per unit time in the fluid column passing through the measurement region. Increasing the number of events detected per second in this manner also increases the elliptical cross section of the core stream within the fluid column, including the length of the major axis. As a natural consequence, and as those of skill in the art are aware, generally increasing the sorting speed by increasing the flow rate of sample decreases the sensitivity of sperm sorting equipment. Therefore, embodiments described herein not only improve sperm sorting precision at customary speeds, but may also provide for sperm sorting at increased overall speed in terms of throughput without suffering losses in fidelity. An approach for identifying objects traveling in a fluid column in the presence of positional variation is illustrated in the flow diagram ofFIG.8. The process includes creating510a fluid column containing objects at differing positions within the fluid column. The fluid column may be a coaxial stream of fluid created by a jet-in-air flow cytometer. Such a fluid column may comprise a core stream with an elliptical cross section having a major axis along which objects may be positioned. The core stream may be coaxially contained within a sheath stream. In some embodiments the fluid column may have an air-fluid interface whereby refraction occurs. In other embodiments the fluid column may be formed within a cuvette or a microfluidic channel. In such cases there may be a liquid-glass interface and possibly a glass-air interface and emanating light may be refracted twice. Such twice refracted light is expected to benefit greatly from the angular dependency correction of certain embodiments. The process continues by generating520excitation electromagnetic radiation and directing530the excitation electromagnetic radiation toward objects in the fluid column at a measurement region. Objects within the fluid column emanate output electromagnetic radiation in response to the excitation electromagnetic radiation at the measurement region. The output electromagnetic radiation is collected540from the objects in the fluid column, including objects having different position within the fluid column at a measurement region and a detector generates550an electrical signal responsive to the intensity of the output electromagnetic radiation collected by the optical arrangement. Next, an analyzer or other suitable means normalizes560the intensity represented by the output signal based on the position of the object in the fluid column. The normalization may be performed by means of a correction, whereby signals generated off the central axis, such as toward and including the second and third positions ofFIG.2, are amplified by an appropriate correction factor based on their position. The magnitude of appropriate correction factors can be seen inFIG.7. Once normalized by correction the method continues by discriminating570a first type of object from other objects. The discrimination may take place in a flow cytometer analyzer and may include one or more additional manipulations. For example, univariate histograms may be generated illustrating a distribution of fluorescence intensities. Bivariate histograms may also be generated with the corrected signal and with further calculated values. Such corrected and calculated values may be compared against gating regions in a flow cytometer analyzer or compared against look-up-tables to discriminate a first type of object from other types of objects. As exemplary objects sperm may be discriminated as either X-chromosome bearing or Y-chromosome bearing sperm. Further, sperm may be stained with a DNA selective dye in addition to a secondary quenching dye. A quenching dye typically permeates membrane compromised sperm cells, such as dead or dying sperm cells, and greatly reduces the fluorescence produced by the DNA selective dye associated with those compromised cells. Such quenched cells are effectively removed from the closely related populations undergoing discrimination/sorting. In this way a system can discriminate live or viable sperm cells from dying or compromised sperm cells. The system may also discriminate viable X-chromosome bearing sperm from all remaining cells, Y-chromosome bearing sperm from all remaining cells, or even simultaneously viable X-chromosome bearing sperm and Y-chromosome bearing sperm from all other sperm cells. FIG.9illustrates a first embodiment of the discrimination system substantially similar to the discrimination system depicted inFIGS.1and2in which output electromagnetic radiation161emanating from an object172alocated in the measurement region is collected by an optical collection arrangement190. The optical collection arrangement190may include a collection lens that focuses a modified output electromagnetic radiation onto a detector185. In the depicted embodiment, the detector functions to both measure a characteristic of the modified output electromagnetic radiation as well as a position detector186for determining the position of the object172awithin the core stream151of the fluid column150. The detector185suitable for determining both a characteristic of the modified output electromagnetic radiation162and for determining the location of the object172ain the measurement region may comprise split detectors or a detector array of PMTs, SiPM, pin photodiodes or the like. These detectors may be located in the image plane of the object or in the Fourier plane to determine the position of the object. In the image plane the detectors directly measure the position of the object, whereas in the Fourier plane the position information will be extracted from the lateral intensity distribution (e.g. the left-right asymmetry). Flow cytometry applications often require very sensitive (down to single photon counting) and fast (objects are moving with ˜20 m/s through 10 μm) detectors. Detectors with the requisite speed and sensitivity are typically those detectors that provide an internal gain. In photomultiplier tube (PMT) or a silicon photomultiplier (SiPM), also known as pixelated avalanche photodiode, a single photon creates a cascade of up to about 106 electrons. Both detector types are commercially available as detector arrays. SiPM may be better suited for use in detector arrays suitable for determining the position of the object because they are fabricated by standard techniques on silicon wafer. Some detector, such as SiPMs may be particularly well suited to be placed in a Fourier plane in order to distribute light over a larger area of the detector. FIG.10illustrates an alternative embodiment in which a beam splitter191, or other suitable optics, redirect a fraction of the power of the modified output electromagnetic radiation162. The majority of the modified output electromagnetic radiation162is directed to and focused on the detector185. In this embodiment the detector185comprises a first detector176for detecting a characteristic of interest. The first detector176may be any detector conventionally suited to quantify the particular characteristic of interest. In typical flow cytometer applications photodiodes, photomultiplier tubes (PMTs) and silicon photomultipliers may be particularly well suited to detect scattered or fluoresced electromagnetic intensity. The beam splitter191may comprise a dielectric mirror197, however those of skill in the art will appreciate other suitable optical components such as cube beam splitters, prism beam splitters and the like may be used for redirecting a portion of the modified output electromagnetic radiation162power. Regardless of the manner in which the output power is split, a first beam fraction164is directed along a first path to the detector and a second beam fraction165is directed along a different path to a second detector173in the form of a position detector177. The position detector can be a camera, a position sensitive device (“PSD”) such as an isotropic sensor or a charged coupled device (CCD), split detectors, a detector array of PMTs, SiPM, pin photodiodes or the like. Turning toFIG.11, a simulation was performed illustrating the viability of a split detector for determining positional information in a flow cytometry system. The simulation employed a split SiPM detector comprising 3 mm SiPM detectors mounted side by side. The edge at which the detectors met was calibrated as a central x coordinate position, simulating the beam axis of an interrogation laser as well as the symmetric center of a fluid column. A 1.5 mm spot size was swept across the split detectors from an x position between about −12 mm to 12 mm and the relative intensity was measured by each detector was recorded. A first graph601illustrates the relative intensity recorded for the beam spot from one of the detectors from x positions ranging from about −12 mm to about 12 mm, where the x position corresponds to a plane of the SiPM detector. A graph602illustrates the corresponding relative intensity detected by the other detector for the beam spot in a range of x positions from about −12 mm to about 12 mm. As can be seen, the positional difference in the two detectors results in differing measured intensities based on the x position of the 1.5 mm spot. These differences correlate to position and can be translated through processing means to approximate positional information. Noise was included in the simulation, but it was independent of intensity. At max intensity the noise corresponds to 0.8% coefficient of variation. The simulation demonstrated that x position can be determined in a split detector arrangement based on the relative intensity detected by each SiPM in a split detector arrangement. Those of skill in the art can appreciate, embodiments of the present invention are not limited to this configuration and that other detector configurations suitable for determining the position of a particle within a fluid column are also contemplated for use herein. As but one example, other detectors may be employed in a split detector arrangement. Those of skill in the art will appreciate that detectors should have low noise, as the combined signals must have a sufficiently low coefficient of variation. FIG.12illustrates the result of an experiment incorporating positional correction for sperm nuclei in a fluid column resulting in significant improvements in differentiating X and Y-chromosome bearing sperm nuclei. Sperm nuclei stained with Hoechst 33342 were processed through a Genesis III sperm sorting instrument manufactured by Cytonome. The instrument was outfitted with a SiPM split detector. Sample and sheath pressure were adjusted to establish an event rate of 35,000 events per second. Nuclei were interrogated with a Coherent Genesis CW-355 laser at an average power of 150 mW. Plot610depicts a bivariate histogram illustrating a sum of fluorescence intensives from each detector in the split detector plotted against the positional delta of nuclei in the fluid column. As previously described, the range of the positional delta represents the major axis of the elliptical core stream along which nuclei may enter the measurement region. A population of X-chromosome bearing nuclei612is seen in a crescent shape. As expected, measured intensities are greatest near a position delta of 0 with reductions curving downward as nuclei move away from the central position. A population of Y-chromosome bearing nuclei614is seen as a second crescent just below the X population and, again, the highest intensities are seen near a position delta of 0 with significant losses in relative intensity as the nuclei move away from the central position. Plot620presents a univariate histogram of the summed fluorescence intensities that corresponds to the intensities charted in plot610. While the distinct population of X-chromosome bearing nuclei612and population of Y-chromosome bearing nuclei614can be seen, a comparison of plot610with plot620makes apparent that off center X-chromosome bearing sperm nuclei increasingly overlap with the well centered Y-chromosome bearing sperm nuclei. Indeed, the peak to valley ratio is calculated at 76.8%. In accordance with embodiments of the invention, a correction factor616is illustrated as a curved line in plot610. The correction factor616illustrates the degree of correction required to the detected fluorescence intensity to remove the variation introduced by the random positions of events. A corresponding correction was applied to the fluorescence sum values depicted in plot630to produce a corrected population of X-chromosome bearing nuclei632and a corrected population of Y-chromosome bearing nuclei634. The corrected population of X-chromosome bearing nuclei632form a generally rectangular shape and no longer demonstrates fluctuation based on the position of the nuclei in the fluid column. A more distinct gap can be seen in plot630between the corrected population of X-chromosome bearing nuclei632and a corrected population of Y-chromosome bearing nuclei634. Plot640illustrates the corresponding univariate histogram, which has a 94% peak to valley ratio between the corrected population of X-chromosome bearing nuclei632and the corrected population of Y-chromosome bearing nuclei634. The stark contrast between plot620and plot640is visually apparent. Furthermore, the difference is a quantifiable with at 17.2 percentage points higher. FIG.13illustrates the results of an example incorporating correction in accordance with embodiments described herein. Live sperm stained with Hoechst 33342 were processed through a Genesis III sperm sorting instrument manufactured by Cytonome. Sample and sheath pressures were adjusted to reach an event rate of 43,000 events per second and the sperm was interrogated with a Coherent Genesis CW-355 laser operated at an average power of 100 mW. Plot710illustrates a bivariate histogram of the summed fluorescence intensity and the relative positions of live sperm in the core stream. Again, the population of X-chromosome bearing sperm712can be seen as a first population above a population of Y-chromosome bearing sperm714. A correction factor716for normalizing the summed intensity values is also depicted in plot710. Plot720illustrates the univariate histogram of uncorrected summed intensities and demonstrates a peak to valley ratio of 75.3% between the population of X-chromosome bearing sperm712and the population of Y-chromosome bearing sperm714. Plot730provides a type of bivariate histogram common in sperm sorting applications. In this case, a corrected forward fluorescence intensity is plotted against a side fluorescence. A forward fluorescence vs side fluorescence histogram is useful for sorting live sperm because the side fluorescence provides information on the orientation of each cell. In contrast, sperm nuclei are sonicated and removed from the aspherical sperm head. As such, orientation is not an issue when sorting sperm nuclei. For this reason, nuclei are easier to sort and are often used to calibrate sperm sorting flow cytometers. Plot730depicts a corrected population of X-chromosome bearing sperm732and a corrected population of Y-chromosome bearing sperm734. Much like the previous example, plot740still correlates in the Y axis to the corrected forward fluorescence of graph730. In the univariate plot of graph740, the corrected population of X-chromosome bearing sperm732and the corrected population of Y-chromosome bearing sperm734can be seen as more distinct peaks having a machine calculated peak to valley ratio of 81.0%. And again, the corrected histogram presents a significant improvement over plot720demonstrating the value of positional correction for live sperm. In another aspect, embodiments described herein may provide systems and methods that substantially ease an alignment process in a flow cytometer. In the case of sperm for example, the measurement region, detectors, and even the structure forming the sheath flow must be properly and precisely aligned in order to generate and collect sufficiently clear signals for differentiating the very bright and closely related X and Y-chromosome bearing sperm populations. Even in a precise and proper alignment, oriented sperm in a fluid column can assume any number positions along the major axis of core stream. As described above with respect toFIGS.3-7, this means that even when the components of the flow cytometer are in perfect alignment, there is an angular dependency to the detected output electromagnetic radiation. This angular dependency introduces noise like variations because the cells may be randomly positioned within the core stream. In commercial sperm sorting applications, technicians typically undertake a number of course adjustments followed by a number of fine adjustments for multiple components in multiple axis in order to align the instrument. Due to the sensitivity of the instrument to each adjustment, the very closely related nature of the detected signals, and the number of possible adjustments, such alignments can be time consuming tasks for technicians operating sperm sorting instruments. When switching between samples machine alignments for commercially sorting sperm can take a few minutes, even up to five minutes. After declogging a nozzle or otherwise removing, replacing or adjusting other components that require calibration, it may take a technician 5 minutes, 15 minutes, and in rare cases as long as 30 minutes in order put an instrument in suitable alignment for commercially sex sorting sperm. FIG.14illustrates the results of an example in which the alignment process is greatly reduced for discriminating sperm nuclei. Sperm nuclei stained with Hoechst 33342 were processed through a Genesis III sperm sorter manufactured by Cytonome. The instrument was fit with an SiPM split detector. The forward fluorescence detection was aligned for less than one minute resulting in a rough alignment. Sperm nuclei were run at an event rate of 33,000 nuclei per second and interrogated with a Coherent Genesis CW-355 laser operated at an average power of 150 mW. Plot810illustrates the bivariate histogram showing the summed forward fluorescence plotted against the position detected by each event by the SiPM. The poor alignment is evident in each of the population of X-chromosome bearing nuclei812and the population of Y-chromosome bearing nuclei814. In poor alignment the crescent shapes are asymmetric and the fluorescence intensity values drop dramatically in the positive x direction as compared to the negative x direction. The population of Y-chromosome bearing nuclei814demonstrate the same skew. The correction factor816is illustrated as a line between the two populations. This correction factor816illustrates the degree of correction that will be performed to summed fluorescence values at each x location. Stated differently, the correction factor816, represents a curved line that will be normalized by correction to a flat line. Each summed fluorescence value at a corresponding x position along line receives the same magnitude of increase or decrease as the correction factor816. The distortion caused by rough alignment is more pronounced in the histogram of fluorescence intensities of plot820, where increased overlap results in a peak to valley ratio of 72.3% between the population of X-chromosome bearing nuclei812and the population of Y-chromosome bearing nuclei814. In plot830, the corrected forward fluorescence summed value is plotted in a bivariate histogram against the detected position of each event. It can be seen, again, that by normalizing the fluorescence intensity values with a correction factor816based on the position of the cells, two clean populations of cells emerge. A corrected population of X-chromosome bearing nuclei832and a corrected population of Y-chromosome bearing nuclei834are more clearly and distinctly grouped in plot830. Importantly, the orthogonal relationship of these populations translates in the univariate fluorescence intensity histogram seen in plot840, where two distinct univariate peaks have a calculated peak to value ratio of 94.4%. In addition to the use of correction, some embodiments disclosed herein include elements that reduce the variation in collected light intensity with respect to object position in a flow stream. Some embodiments described herein can provide modified output light that has less than about a 3%, or less than about a 2%, or even less than about a 1% measured intensity variation for a deviation in position of the object that is less than 60% of a radius of the flow stream away from a center of the flow stream along an axis perpendicular to the optical axis. Many applications are sensitive to intensity measurement errors, which may arise from a variety of sources. Due to the difficulty in reducing intensity fluctuations by precisely controlling the position of objects within the flow stream, it is useful to instead reduce the variation in collected light intensity with respect to object position by careful design of the optical collection arrangement. For applications such as X/Y sperm sorting, it is often the case that two or more cell populations are to be separated based on the difference in measured fluorescence intensity between the populations. If the random position fluctuations lead to fluctuations in collected light intensity that are greater in magnitude than the nominal difference in fluorescence intensity of the two populations, it is not possible to distinguish them with simultaneously high yield and high purity. The fluorescence intensity difference between X and Y sperm cells is typically only a few percent (e.g., ˜4% for bovine sperm). Current sperm sorter systems can in theory achieve high throughput by increasing the flow rate of the core stream, but this has the effect of increasing the width of the core stream. Consequently, there would be a large uncertainty of the sperm position within the core of the flow stream. This position uncertainty and the resultant fluctuations in collected fluorescence intensity limit the maximum throughput of current sperm sorter systems to levels which do not obscure the small fluorescence intensity difference between X and Y sperm. One approach for intensity-position correction may be understood with reference toFIGS.6and7. The brackets inFIG.6highlight regions of integration that correspond to fluorescence collection optics with a given NA. Graphs of the collected intensity variation with respect to object position for the NAs ofFIG.6are provided inFIG.7. InFIG.7, for a given NA, integration over the fluorescence collection region is performed such that the intensity of collected light can be plotted as a function of each sperm position. It is evident fromFIG.7that increasing the NA of the collection optics helps to decrease the influence of object position on the fluorescence intensity gathered via the collection optics. In some embodiments collection optics (e.g., the optical collection arrangement190inFIGS.1and2) may be modified with elements that reduce collected light intensity variation with respect to object position as described above. Such embodiments are described in more detail in U.S. patent application Ser. No. 16/133,531, which is incorporated herein by reference. According to some such embodiments, the collection optics operate by masking certain rays in “angle space”, that is, the collection optics selectively collect, attenuate, and/or block rays from different angles γ in order to achieve a desired intensity vs. position profile. In practice, an “angle space” masking function can be applied at a pupil (e.g., entrance pupil, exit pupil, or aperture stop) of an optical system, where the position of a ray intersection with the pupil plane corresponds to the angle γ. In some embodiments, the collection optical arrangement achieves a desired, e.g., flatter, intensity vs. position profile by preferentially collecting higher angle (pointing away from the optical axis) light rays to the exclusion of certain lower angle light rays. FIGS.15and16illustrate how excluding low-angle refracted rays, at a given NA, causes the intensity-vs-position curve to flatten out. Excluding the low angle rays excludes the rays that produce the most variation in the intensity vs. position profile, whereas the angular variation of radiance at high positive angles tends to cancel the corresponding variation at high negative angles.FIG.15shows plots of the relative radiance vs. ray angle, γ, for different positions of the object along the x axis where the angle γ is in radians. InFIG.15, each graph corresponds to an object position, x, within the core of a flow stream, as indicated inFIG.5. The brackets inFIG.15show the portion of the light rays that will be excluded by the collection optics for each position x, when rays having angle magnitude less than 0.3 rad are excluded (bottom bracket inFIG.15) and when rays having angle magnitude less than 0.4 rad are excluded (top bracket inFIG.15). FIG.16shows the relative collected light intensity vs. position of the object along the x axis when no angles are excluded (graph900), when rays having angles between −0.3 rad and +0.3 rad are excluded (graph903) and when rays having angles between −0.4 rad and +0.4 rad are excluded (graph904). Graph16shows that when lower angle rays are excluded, the relative intensity vs. position graph exhibits less intensity variation with respect to position. FIG.17illustrates the results of an experiment incorporating both a software based positional correction and a hardware based element in the collection light path that reduces collected light intensity variation with respect to object position as described. Sperm nuclei stained with Hoechst 33342 were processed through a Genesis III sperm sorter manufactured by Cytonome. The sperm sorter was fit with an SiPM split detector having a wire placed in the light collection path in order to exclude low collection angle electromagnetic radiation produced from the sperm nuclei. Suitable wires and other elements for blocking low collection angle electromagnetic radiation are described in U.S. patent application Ser. No. 16/133,531. Sample and sheath pressures were adjusted to reach an event rate of 60,000 events per second and the nuclei was interrogated with a Coherent Genesis CW-355 laser operated at an average power of 90 mW. In plot1010it can be seen the wire mitigates some effect of the intensity dependence on nuclei position within the fluid column. There is still however, a significant decrease in relative intensity as nuclei move further in the positive direction along the x axis. A population of X-chromosome bearing nuclei1012and a population of Y-chromosome bearing nuclei1014are seen sagging significantly in the positive direction in the x axis. The corresponding peak to valley ratio calculated from the fluorescence intensity histogram of plot1020is 81.5%. Again, X-chromosome bearing nuclei that are located toward one end of the fluid column are not sufficiently detected. As a result, the summed fluorescence intensity of the nuclei at this end have similar intensity values as centered Y-chromosome bearing nuclei within the population of Y-chromosome bearing nuclei1014. This skew is evident in the univariate histogram of plot1020in the form of a shoulder shifting downward and an exaggerated peak of the population of Y-chromosome bearing nuclei1014. A correction factor1016is illustrated on graph1010. For each position, a correction value is added to the detected fluorescence intensity corresponding correction factor. Plot1030illustrates a bivariate histogram having a corrected population of X-chromosome bearing nuclei1032and a corrected population of Y-chromosome bearing nuclei1034, which are more distinct rectangular populations. Plot1040provides the corresponding univariate histogram of corrected summed intensity values independent of the location of each event. The corrected population of X-chromosome bearing nuclei1032and the corrected population of Y-chromosome bearing nuclei1034are more distinct having roughly equal peaks heights and a peak to valley ratio of 92.6%. The foregoing description of various embodiments has been presented for the purposes of illustration and description and not limitation. The embodiments disclosed are not intended to be exhaustive or to limit the possible implementations to the embodiments disclosed. Many modifications and variations are possible in light of the above teaching. | 56,212 |
11858833 | The electrochemical system contains a diaphragm electrolysis apparatus—electrochemical reactor (1) with coaxially arranged electrodes—of the anode (2), the cathode (3) and the diaphragm (4). The process engineering diagram of anode synthesis of the oxidizing agents consists of the anode compartment (5) of the reactor (1), the inlet of which is connected via the non-return valve (6) to the outlet of the high-pressure metering pump (7), the inlet of which is in turn connected to the filter (8), which is connected to the vessel for dissolving the salt (9), in which the initial salt solution is produced and purified. The outlet of the anode compartment (5) is connected to the separation vessel (10) for separating the gaseous products of the electrochemical anode reactions from the anolyte. The outlet in the lower part of the separation vessel (10) is connected to the inlet of the anode compartment (5) of the electrochemical reactor (1), wherein the anode circuit of the anolyte is thereby closed. The outlet in the upper part of the separation vessel (10) is connected via the non-return valve (11) to the device (12) for dissolving the gaseous products of the electrochemical anode reactions in fresh water. The outlet of the device (12) is connected to the upstream pressure regulator (13), which, during operation of the electrochemical system, ensures that the pressure in the anode circuit of the electrochemical reactor (1) constantly exceeds the pressure in the cathode circuit by building up a regulated predetermined hydraulic resistance in the oxidizing agent solution stream. In the hydraulic line connecting the outlet of the device (12) to the upstream pressure regulator (13), a measurement sensor is arranged for the conductivity capacity of the oxidizing agent solution “χs”. The outlet of the upstream pressure regulator (13) is connected to the inlet of the collection vessel for the oxidizing agent solution (14), which is provided with measurement sensors for the permissible maximum (15) and minimum (16) oxidizing agent solution levels. One of the outlets of the collection vessel for the oxidizing agent solution (14) is connected to the inlet of the vessel (9) for producing and purifying the salt solution, which is located lower than the collection vessel of the oxidizing agent solution (14). The other outlet of the vessel (14) is connected to the inlet of the metering pump (17), which latter is intended for feeding the oxidizing agent solution to the object of use, for example to the point of introduction of the oxidizing agent into the water mains for the purification of drinking water. The water arrives in the device (12) for dissolving the gaseous products of the electrochemical anode reactions via the non-return valve (18) and the heat-exchange system of the anode circuit of the electrochemical reactor (1) from the outlet of the filter (19). In the hydraulic line connecting the outlet of the heat-exchange system of the anode circuit of the electrochemical reactor (1) and the inlet of the non-return valve (18), a measurement sensor is arranged for the conductivity capacity of the water “χw”. The water which has flowed through the heat-exchange device (20) of the cathode circulation circuit is fed, with the addition of catholyte from the separation circulation vessel of the catholyte (21), to the inlet of the filter (19). The catholyte is introduced into the water stream at the outlet from the heat-exchange device of the cathode circulation circuit (20) by means of metering pump (22). In the hydraulic line connecting the outlet of the water and the inlet of the filter (19), a measurement sensor for the conductivity capacity of the outlet water “χi” is arranged upstream of the point of introduction of the catholyte from the separation/circulation vessel of the catholyte (21). Apart from the heat-exchange device (20) for cooling the catholyte and apart from the separation/circulation vessel of the catholyte (21), the cathode circuit of the catholyte comprises the cathode compartment (23) of the electrochemical reactor (1), the circulating pump (24) and the valve (25) for filling the separation/circulation vessel of the catholyte (21) on start-up of the system and supplying purified water on operation of the system. The separation/circulation vessel of the catholyte (21) is provided with an outflow line of the catholyte which forms during operation of the system. The water is fed to the electrochemical system for synthesis of the oxidizing agent solution from the pressurized water supply network via the coarse filter (pre-filter) (26), the solenoid valve (27) and the downstream pressure regulator (28). The electrochemical system for synthesizing the oxidizing agent solution functions as follows. On initial start-up of the electrochemical system (no water or solutions in the system), the vessel (9) is filled with rock salt in the quantity needed for synthesis of the predetermined quantity of oxidizing agent solution, in the maximum consumption ratio of 0.8 gram of salt per 1 liter of oxidizing agent solution. For the production, for example, of 25,000 liters of oxidizing agent solution with a concentration of active substances (hypochlorous and hydroperoxide compounds) of 500 mg/l, the vessel (9) needs to be filled with 20 kilograms of salt. The vessel (9) is filled with softened, purified water, wherein the salt must be completely covered with water. This takes place once, on initial start-up of the system. The port for feeding water to the inlet of the mechanical filter (26) is connected to the pressure line for the fresh water (drinking water). The normally closed solenoid valve (27) is supplied with power by means of a separate switch. The predetermined volumetric flow rate of the water through the system and the predetermined pressure in the anode circuit are adjusted by a downstream pressure regulator (28) and an upstream pressure regulator (13), in accordance with the readings of the manometer M and the external flow meter (not shown on the drawing). Using the valve (25), the separation vessel of the catholyte (21) is filled with water until a water jet exits from the outflow line of the separation vessel (21), the valve is then brought into a position which ensures that water is fed into the separation circulation vessel for the catholyte (21) at a rate of 20-30 drops per minute (determined on the basis of the rate of impingement of drops from the outflow line of the separation vessel for the catholyte (21)). The metering pump (7) is switched on and the anode compartment (5) of the electrochemical reactor (1) is filled with salt solution from the vessel (9). The end of the filling process is established on the basis of an increase in measurement sensor values for the conductivity capacity of the oxidizing agent solution “χs” by roughly twice the measurement sensor values for the conductivity capacity of the water “χw”. Open-loop control of the electrical devices of the system (pumps, power source of the electrochemical reactor) is switched to the automatic control block (not shown on the drawing), which is connected to the measurement sensors for the level of oxidizing agent solution in the collection vessel (14) and the measurement sensors for the conductivity capacity of the conditioned, softened water “χw”, the oxidizing agent solution “χs” and the outlet water “χi”. In the case of a level of oxidizing agent solution in the collection vessel (14) below the measurement sensor (16) or between the measurement sensors (16) and (17), the power source of the electrochemical reactor (not shown on the drawing), the catholyte circulating pump (24), the pump (22) for metered introduction of the catholyte into the fresh water stream and the metering pump (7) for feeding the salt solution into the anode compartment (5) of the electrochemical reactor (1) are switched on. The automatic control block controlling the electrical devices of the electrochemical system ensures closed-loop control of the rate of feed of catholyte by the metering pump (22) into the outlet fresh water on the basis of the signals from the measurement sensor for the conductivity capacity of the water “χw” and “χi” by maintaining the conductivity capacity of the water downstream of the filter (19), which is to be kept by the measurement sensor for the conductivity capacity “χw” at the predetermined value of the measurement range determined by the ratio χw=(1.0-1.5) χi. The automatic control block likewise ensures closed-loop control of the rate of feed of the salt solution by the metering pump (7) into the anode compartment (5) of the electrochemical reactor (1) on the basis of the signals from the measurement sensor for the conductivity capacity “χw” and “χs” by maintaining the conductivity capacity of the oxidizing agent solution “χs” at the predetermined value of the measurement range determined by the ratio χs=(1.5-2.5) km. During plant operation, the following reactions take place in the electrochemical reactor (1). The main reaction in the electrochemical reactor (1) is the liberation of molecular chlorine in the anode compartment (5) and the formation of sodium hydroxide in the cathode compartment (23): NaCl+H2O-e→NaOH+0.5H2+0.5Cl2. At the same time, chlorine dioxide is synthesized with lower current efficiency in the anode compartment directly from the salt solution and the hydrochloric acid which forms in the vicinity of the anode on dissolution of the molecular chlorine (Cl2+H2O↔HOCl+HCl): 2NaCl+6H2O-10e→2ClO+2NaOH+5H2; HCl+2H2O-5e→ClO2+5H·. In the anode compartment of the reactor, ozone is formed by direct water decomposition and by oxidation of the liberated oxygen: 3H2O-6eO3+6H·;2H2O-4e→4H·+O2;⇒O2+H2O−2e→O3+2H·. The active oxygen compound formation reaction proceeds at low current efficiency: H2O-2e→2H·+O·;H2O-e→HO·+H·;2H2O-3e→HO2+3H·. Current efficiency for the formation of chlorine dioxide, ozone, singlet oxygen and hydrogen peroxide rises as the mineral content of the initial aqueous sodium chloride solution falls, reaching 20-30% at a salt concentration in the initial solution in the range 80-150 g/l at an anode density of five to seven thousand amperes per square meter (5000-7000 A/m2). Once the salt content in the initial solution has increased to 250-300 g/l, the current efficiency of the chlorine dioxide, ozone, singlet oxygen and hydrogen peroxide formation reaction falls to 1-2% at an anode density of 5000-7000 A/m2and to 0.1-0.2% at an anode density of 2000-3000 A/m2. Dissolution of the gaseous product of the anodization of the sodium chloride solution in water generally proceeds in a reaction expressed by the following equation: Cl2+H2O↔HOCl+HCl. Hypochlorous acid, the content of which in the solution is limited by the decreasing pH as a result of the formation hydrochloric acid, is known to be a fundamental antimicrobial agent. pH can be modified by introducing alkali metal hydroxide solution, i.e. for example sodium hydroxide. However, this results in the formation of products which are unwanted (sodium chloride) and sparingly reactive (sodium hypochlorite). Sodium hypochlorite as the salt of a weak acid (hypochlorous acid) and a strong base (sodium hydroxide) has 250 to 350 times lower antimicrobial activity than hypochlorous acid. HOCl+HCl+2NaOH→NaOCl+NaCl+H2O. In the event of simultaneous increase in the pH of the oxidizing agent solution with simultaneous increase in the concentration of the hypochlorous acid and removal of the hardness-forming substances and the multivalent metal ions, including iron, the formation of sodium hypochlorite may be avoided by introducing a catholyte containing free hydroxyl groups into the water stream. The catholyte is known to have extraordinarily high chemical adsorption activity in hydrate formation reactions. The elevated reactivity of the catholyte can be explained, among other things, by the large quantity of free hydroxyl groups and dissolved hydrogen present in the catholyte. Interaction of the catholyte and electrolytes present in the water results in the formation of water-insoluble compounds: 3NaOH+AlCl3→Al(OH)3↓+3NaCl;2NaOH+ZnCl2→Zn(OH)2↓+2NaCl; MgCl2+2NaOH→Mg(OH)2+2NaCl;CaCl2+2NaOH(conc.)→Ca(OH)2↓+2NaCl; FeSO4+Ca(OH)2→Fe(OH)2+CaSO4;FeCl2+2NaOH Fe(OH)2↓+2NaCl; Fe2O3·nH2O+NaOH→Fe2O3↓;FeSO4+NaOH→Fe(OH)2↓+Na2SO4; 2FeCl3+6NaOH+(n−3)H2O→Fe2O3nH2O↓+6NaCl; Al2(SO4)3+6NaOHdil.→2Al(OH)3↓+3Na2SO4; AlCl3+3NaOH→Al(OH)3↓+3NaCl. The hydroxides and the flocs formed, particle aggregates of the hydroxides with the adsorbed molecules of organic compounds, the microcolloidal particles and hydrogen bubbles are deposited on the filter (19) and the softened water purified from multivalent metal cations, which has a low concentration of dissolved hydrogen and free hydroxyl groups, flows into the device for dissolving the oxidizing agents (12) which bring about an increase in the concentration of hypochlorous acid in the oxidizing agent solution according to the following reaction: Cl2+H2O+O−↔2HOCl. Depending on the quantity collected in the vessel (14) of the electrochemical system, the oxidizing agent solution is likewise used, apart from for its main purpose, in small quantities as an agent for dissolving the salt in the vessel (9), which oxidatively decomposes the organic admixtures which are originally present in the rock salt and are difficult to remove in conventional methods for producing salt for household use and numerous industrial applications. The oxidized and coagulated foreign organic compounds are retained by the filter (8) at the outlet from the vessel (9). Dissolving the salts with the oxidizing agent solution makes it possible to ensure the microbiological purity of the agent in the salt dissolution vessel. As a consequence, it no longer has to be regularly maintained until the end of the process of dissolving the entire introduced quantity of salt. Prior to feeding into the anode compartment of the electrochemical reactor, there is no need to remove the multivalent metal ions, including heavy metal ions, from the salt solution. All the metal cations which enter the anode compartment as part of the salt solution under the effect of the pressure gradient and the electrical field are removed together with the liquid filter stream into the cathode compartment by means of the porous UV medium of the ceramic diaphragm. In the cathode compartment, the multivalent metal cations are converted into hydroxides and removed from the system via the outflow line from the catholyte separation circulation vessel (21). The electrochemical system was tested comparatively against the prototype of the device constructed according to patent U.S. Pat. No. 7,897,023 B2 and supplemented with an ion exchanger (water softener) and a vessel for dissolving the salt and for producing a salt solution. To permit a more accurate comparative analysis, the water from the ion-exchange softener was used not only to produce the salt solution but also to dissolve the gaseous products of the anode compartment of the electrochemical reactor. The ion-exchange softener was connected to the drinking water pressure line. The device according to the US patent was likewise supplemented with a collection vessel for the oxidizing agent solution. The two comparable systems contained an electrochemical reactor consisting of four electrochemical modular elements (cells) according to patent EP 0 842 122 B1. The aqueous initial salt solution contained 250 g/l sodium chloride, the content of hardness-forming substances in the initial solution was 0.3 mg-eq/l (1 since it corresponds to 0.3566 mg-eq/l in the electrochemical system according to patent U.S. Pat. No. 7,897,023 B2 and 4.5 mg-eq/l in the vessel (9) of the system according to the new technical solution. The reason for the difference was the low content of hardness-forming substances in the water downstream of the ion-exchange softener and the significantly higher content of hardness-forming substances in conventional mains drinking water from which the initial salt solution was originally produced in the electrochemical system according to the new technical solution. The current intensity through the electrochemical reactor in the prototype device was 40 amperes at a voltage of 5 volts. The same values were set for the electrochemical reactor in the electrochemical system according to the new technical solution. 52 g/h of oxidizing agent were accordingly produced in each of the comparison systems. The oxidizing agent solution, which was produced in the prototype system at a rate of 100 l/h, had an oxidizing agent concentration of 500 mg/l, a pH of 2.8 and a total mineral content of 0.86 g/l. The content of hardness-forming substances in the oxidizing agent solution was 0.2 mg-eq/l. On metered introduction of the catholyte which forms during synthesis of the oxidizing agent solution, the pH of the solution at the outlet rose to 6.0 with a simultaneous increase in the mineral content of the solution to 1.5 g/l. The oxidizing agent solution, which is produced at a rate of 100 l/h in the device according to the new technical solution, had a pH of 3.0 at an oxidizing agent concentration of 500 mg/l and a total mineral content of 0.66 g/l. On metered introduction of catholyte into the initial water, the pH of the oxidizing agent solution rose with a simultaneous increase the mineral content to 0.82 g/l. The hardness of the oxidizing agent solution was in the region of 0.8 mg-eq/l, but decreased over the course of 2 hours' operation to 0.6 mg-eq/l. Evaluation of the results of these investigations shows that the introduction of catholyte upstream of the filter (19) substantially reduces the hardness of the water for dissolving the gaseous products of the anodization of the sodium chloride solution and that the introduction of the oxidizing agent solution with a reduced content of hardness-forming substances in the vessel (9) for producing the salt solution substantially reduces the content of hardness-forming substances in the oxidizing agent solution. The two systems each ran continuously for 10 hours daily for 10 days. Samples of the oxidizing agent solutions were taken twice: at the end of the second day of operation of the comparable electrochemical systems (20 hours of operation) and after 10 days (100 hours of operation). The solution from the prototype system exhibited the following values after twenty hours of system operation: pH 6.4; oxidizing agent concentration 480 mg/l; mineral content 1.4 g/l. After ten days, the oxidizing agent concentration in the sample taken (quantity of solution 1 liter) fell to 460 mg/l. The content of hardness-forming substances in the oxidizing agent solution of the prototype was 0.9 mg-eq/l, i.e. the performance of the ion-exchange filter had deteriorated. The solution from the system according to the new technical solution exhibited the following values after 20 hours of system operation: pH 5.9; oxidizing agent concentration 510 mg/l; total mineral content 0.83 g/l. After 10 days, the oxidizing agent concentration in the sample taken (solution sample) was unchanged. The content of hardness-forming substances in the oxidizing agent solution of the prototype was 0.6 mg-eq/l, i.e. the introduction of catholyte into the initial water upstream of the filter allowed purification of the water from hardness-forming substances. The oxidizing agents thus remained in the solution for longer. The solution from the prototype system exhibited the following values after one hundred hours of system operation: pH 6.3; oxidizing agent concentration 470 mg/l; total mineral content 1.4 g/l. After 10 days, the oxidizing agent concentration in the sample taken (quantity of solution 1 liter) fell to 440 mg/l. The content of hardness-forming substances in the oxidizing agent solution of the prototype was 3.8 mg-eq/l, which is obviously related to the significant deterioration in the performance of the ion-exchange filter. The solution from the system according to the new technical solution exhibited the following values after one hundred hours of operation: values: pH 5.9; oxidizing agent concentration 500 mg/l; total mineral content 0.83 g/l. After 10 days' operation, the oxidizing agent concentration in the sample taken (solution sample) was unchanged. The content of hardness-forming substances in the oxidizing agent solution from the system according to the new technical solution was 0.6 mg-eq/l, i.e. the introduction of catholyte into the initial water upstream of the filter allowed effective purification of the water from hardness-forming substances for an extended period. As a result, the oxidizing agents remained in the solution for longer. Examination of the vessel for dissolution of the salt and the production of the salt solution revealed a biofilm of microorganisms in the vessel of the prototype system. Biofilm was completely absent from the vessel (9) of the system according to the new technical solution. This fact is extremely important because, when oxidized in the anode compartment of the electrochemical reactor, the organic substances formed during the activity of the biofilm are capable of having a negative impact on the electrolytic decomposition of the sodium chloride due to the formation of difficult-to-remove impurities on the electrodes and the diaphragm (membrane). REFERENCE SIGNS 1reactor2anode3cathode4diaphragm5anode compartment6non-return valve7high-pressure metering pump8filter9salt10separation vessel11non-return valve12device13upstream pressure regulator14oxidizing agent solutionmaximum level16minimum level17metering pump18non-return valve19filter inlet20heat-exchange device21Catholyte22metering pump23cathode compartment24circulating pump25valve26coarse filter (pre-filter)27solenoid valve28downstream pressure regulator | 21,943 |
11858834 | DETAILED DESCRIPTION Every plant species known is a result of thousands of evolution-adaptation processes that gives its own characteristics and a specific challenge for our society. The electrons activity as well as the molecule structure are not correctly appraised because there is not clear information available—only general knowledge is reduced in a concept of circular orbits around a solid nucleus with different theorical electro-magnetic charges and capabilities—but in fact all this element is a complex phenomena itself (FIG.11). It is important to analyze some of that element composition and the strange capacity to bond with other with electromagnetic interactions that represent the world as we know it. The great variety of known substances is the final of many ways that atoms can be combined. Elements that integrate an atom unit (neutron-proton-electron) are the same structure in the world, the only difference is the location-orbit of each one—all possible combinations structure the reality we know. The electromagnetic equilibrium of each element is a direct reference of the amount of internal unit in the nucleus and the amount of external orbital electrons. Even so, the most external orbit has a defined capacity and the atom can be internally equilibrated but has external units in default that will create an interaction that makes attraction or repulsion phenomena with others (FIG.14), as we can find in complex molecules H2O, CH4, NaCl. That represents all the matter in the universe. Every atom is in permanent motion even as molecules (until a temperature level of zero Kelvins), and that characteristic makes permanent motion and interaction present in organic—inorganic environment. What we can produce with this utility invention is to give an extra capability to the water molecules to interact with the soil molecules for manipulated selection and controlled absorption and transport inside the plant structure. Modern technology to plan and design any kind of engines for energy specific activity is leading the modern industrial developments: electro-magnet use for industry performance, transport options, communications and equipment, and electricity production (electron current) conduction control and final distribution. The present analysis for better use of different engine designs for agriculture control purposes (FIG.15-16). FIG.15A—Solenoid (Transformer) The solenoid design is a rolled wire in a solid structure that when an electric current (electrons current) is connected that current is multiplied increasing in a defined direction all the electron current—(in a car a 24-12 V battery can be through the coil-solenoid-transformer—increase until 20,000 V needed for the spark combustion process). Then, an increased amount can be oriented. In the present utility invention the first step can be to use this engine structure (as electro-magnet is used to hold heavy material). This design has an empty nucleus where the electrons can be oriented giving or reducing electrons current into the water flow transforming the current capacity for energetic interaction. This design can be oriented to the opposite direction modifying the electromagnetic capability of the water in use. The energy level can be controlled at will. FIG.15B—Toroid This design consists in the wire enrolled on a circular structure (as a circle) creating a circular electron current exactly in the enrolled area and a vacuum area in the center of the circle. This vacuum area represents a new phenomenon that can create order or orientation of the molecules (FIG.15-16). As this happens the water molecules activity in the soil elements can be oriented as needed. The final design of this invention allows the modification of the molecule orientation and strength of the water structure and interaction when colliding with the soil molecules. This engine activity is designed to give controlled electro-activity to the water molecule structure defined on the plant genetic code performance. FIG.15C—Electric Basic Design. Separate units acting as electromagnets designed as alternative charges in motion creating circular current of electromagnetic charges (electrons) in a designed direction (FIG.15-16). All the electrons will be oriented in an induced circular current giving an energic active capacity to the water molecules that can interact in the molecule mix of the soil structure. This engine design can modify the final orientation or power to change or modify the water activity. These A-B-C engines combined can be used in both directions separately to have a number of options in hand. The main purpose of this utility invention is to provide a controlled energy device to increase or reduce capacity of the water molecules interaction at an electro-chemical level with soil elements for a guided absorption-transport activity. It is a better option for manipulating all the molecules involved to facilitate the cell-root system in this first step of plant performance. The academic focus of the invention is not just related to the mechanical phenomenon of water molecule orientation for better nutrient absorption by plant roots; it is a complicated structure that needs specific order on a number of elements that do not always occur in nature and that need to be implemented for plant survival and production. Water is a complex molecule with physical, chemical and electromagnetic characteristics, has been under research for the last century for many individuals and institutions and now we have a large data for better conservation and use. To understand the total plant nutrition phenomena some other issues need to be studied: a) Nature of soil composition—there are some nations that have large amounts of rain and rivers but do not have good agriculture results. b) Nutrients from biotic decomposition are not always in disposition. c) Previous agriculture activity changes the bio-chemical soil conditions restricting new crop capability. d) pH values from previous crops and fertilizers used because residuals cannot be removed—some human hand is needed by physical and chemical activities to find a balance (electro-magnetic process). e) climate and temperature figures. All plant biology can be defined as a chemical chain of events with electromagnetic characteristics at each step of the evolution: seeds wake-up to start the process; first growing steps until maturity; flowering and development (complex chemical reactions); skin, root and leaves maturity; genetic reproduction process; aged and final stage. All plants have the same conditions and characteristics as all living creatures (bacteria, virus, fungus and large animals); the main difference is that plants cannot move and spend their lifetime in the same place—but this gives to the plant the capacity to adapt its own DNA code to analyze, select, find nutrients, modify and use them. The following additional analysis complements the above: FIG.2is a plant cell display which can have separate organelles: a nucleus with DNA duplication capacity; an internal structure to take nutrients and use them as the environment requires (temperature and climate conditions); internal organelles to elaborate its own hormones, enzymes, sugars, proteins, vitamins; and its own water-oxygen reservoir as needed. FIG.3shows three different aspects of the plant nutrients access: A.—The usual irrigation process is not the best because the soil porosity capability and the plant root natural development. Normally half of the water used is lost. B.—Different development of the root system relies on the land characteristics. It depends on the water bed location and each plant species can adapt and re-located his own development. Sometimes the root system development is larger than the total external size. C.—General analysis of the root development and function, including detailed cellular development; extension of the root final system to exudation molecules control and mix with the soil conditions; presence of soil bacteria able to catch atmospheric nitrogen for ammonia structure and sugars; soil bacteria to interact with the local molecules, exudation plant residuals to adapt the necessary elements for sequence adsorption, and root constitution to analyze and complete the physico-chemical reactions (electromagnetic activity). At the present time almost all agriculture process is manipulated through fertilizers of different structure. The use of greenhouses represents this manipulation: no soil support is available and external support is provided; no soil biomass and bacteria is present for the nutrient modification; and atmospheric conditions are transformed for better manipulation (light, temperature, humidity). With these and other modifications the natural process is modified with different final results. Knowing the basic elements of the process the entire phenomena and results can be modified. FIG.4shows the basic nutrients absorption process. The upper area's purpose is to illustrate the soil condition where roots have to develop. The molecular composition shown a characteristic electronic and magnetic values: H+−, OH−, Na+, HCO3−CO2+−, H2O+−, NO3, P+, NO2−, K+, Mg+and many more as local condition or previous crop residuals. Some of these residual molecules normally come from the artificial chemical fertilizers preparation that sometimes cannot be adsorbed or dissolved. Most of the chemical residuals remain as salts that cannot be dissolved and modify the soil structure and final pH condition. On the lower area of the figure the cell root cellular structure is shown with the water solutes transport system present: xylem to recover the nutrients and move them to the leaves area, and phloem for general transport distribution of modified nutrients (sugars, enzymes, hormones etc.) for the total distribution of the modified molecules for the plant development (growing, flowering production, survival). As shown inFIG.5the entire nutrient absorption process is only possible by the leaves' chemical activity. Leaves' cell structure encloses a series of gas doors (stomata) when the water content of the nutrients flow is dissolved: Oxygen to the atmosphere and hydrogen recovered for internal processes with negative electromagnetic value. By these stomata doors the plant creates a vacuum phenomenon moving up the water molecules from the soil area relying on the external atmospheric conditions of temperature, humidity, wind. This vacuum process catches the CO2(carbon-dioxide) from the external environment (all living creatures activity), separate the atoms from the molecule for specific function with the carbon and oxygen (metabolic activity). FIGS.18A and18Bare added as graphical explanation. Biologically the water-solute nutrients transport is in permanent activity from the soil environment to the atmospheric area through leaves system. Here the open-close phenomena (stomata activity) is in charge to recover and free the Title: Engines Structure for Water Molecules Impulse, Order and Control for Agricultural Purposes oxygen atom and hydrogen atom for internal use. To attract CO2from outside, it separates the molecule and uses carbon atom as raw material for sugars, proteins, enzymes and hormones—the residual hydrogen from the water molecule and the oxygen atom from that CO2separation—to create a strong electro-magnetic environment for the plant metabolism and the rest for the soil activity. In the lower area the photon energy elements present provide energy and capacity as required. FIG.6Ashows root cell activity. The upper area shows the external root cell wall in permanent contact with the soil elements composition as nutrients available. As the figure shows this root absorb capacity has a passive condition as natural access, and active selective access through electro-magnetic adaptation. Energy transfer occurs where the root modifies the electromagnetic environment. The lower area shows the general intake of nutrient molecules and the return molecules to energy provided to the soil. FIG.6Billustrates root cell activity. More particularly it is a close detail of the soil-root cell relation. FIG.7illustrates water's condition in nature. The H2O molecule in pure condition (distilled water) can only be found in laboratory conditions. In nature a number of molecules and atoms are free. The molecules and atoms illustrated include: H2O, HO, H3O, H2O2, HO2, H3O2, H, H2, O, O2, etc., each of them with specific electromagnetic condition that permanently interact and modify each other's function. This entropy (activity) condition interacts with all the soil molecules and atoms as well as the bacteria capability. All this means that the Physical-chemical (electromagnetic) environment can be always be affected. FIG.8illustrates molecules activity. When the water molecule is moving the soil conditions, many changes can occur in the molecules' configuration. All these changes can be present with reverse modification capability. FIG.9illustrates root cells coordinated activity. Different cell structure for the selection of nutrients exists, some can only transport these molecules from cell to cell (white lines with black outline) and others can only work from outside cell areas. All these conditions depend on the electromagnetic values. Transport of the water molecules lines is performed by xylem and phloem. Xylem (central area of the roof—diamond shape) is the basic transport line to move the water nutrient molecules to the leaves area. Atmospheric conditions can modify the speed of this transport line. Phloem (central area—circle shape) after the nutrients get to the leaves area a number of molecules structure occur—all over the plant areas. This phloem transport system moves all these modified molecules until they can be deposited into the soil to start the process. Essential conditions for plant development include soil, environment, and plant DNA attributes. Soil conditions include texture and porosity, bio-fauna integration, bio-residuals of previous treatment, contaminants such as salinity, fertilizers and fungicides used, chemical molecules' composition, and residual pH. Environment conditions include temperature in each step of the plant development (seed wake-up, growth, flowering reproduction, aging), humidity (aerial and ground), air composition, and water residuals. Plant DNA properties include adaptability for new DNA structure, biological identity with the environment, and each species' structure. FIG.19illustrates water in nature in a graph showing an example of the water pressure and the original source. Hydrogen residuals gives specific classification and as result the agriculture possibilities. FIG.20illustrates pH on soil condition, particularly the range of agriculture utility of water pH condition. The DNA of some plant species has special conditions to modify their structure and adapt its development on 2.8-to-10.5 pH scale conditions. The electric and magnetic range capability of the water can change the final utility use. FIG.21illustrates the water-soil relation. In this scheme can be shown how the physical porosity of the soil can block the water supply and effectiveness. In these conditions the plant development can disappear. FIGS.22,23, and24show the basic irrigation process and the basic elements to act as nutrients. The two first sectors are related as electromagnetic values for the average saturation for an expected crop. Some of these molecules (FIGS.23and24) have specific influence on the plant metabolism. FIG.25illustrates the entire absorption route (xylem). As previously mentioned the absorption process is regulated by the leaves condition and the atmospheric process. The root guides the selection, control and process of the chemical composition of the solutes and guides all this to the rest of the plant. The shoot creates specific conditions to control the absorbed solutes, transferred to the leaves area. The leaves provide gas transpiration metabolism to recover the nutritional molecules as well as the H2O and CO2molecules for the plant metabolism. FIG.28illustrates, chlorophyll-photons interaction. It is absolutely accepted the fact of the chlorophyll molecules are structured over the leaves area. Even though we cannot explain or understand of this structured molecule, we accept the fact that when photons are present the plant metabolism can create glucose and free oxygen from the external CO2and the water available. We have no specific information about these processes or how any model of matrix can structure the chlorophyll molecule and how when the photons are present another matrix can structure the glucose molecule. As this happens in the leaves area, similar activity in different plant areas is shown to create enzymes, proteins, hormones, sugars as each specific plant metabolism requires. A balanced water source and electro-magnetic conditions is not a general rule on every area—any agricultural program will always be conditioned to the bio-chemical characteristics of each location (general climate, biotic and abiotic factors and soil molecules content. After this physiological plant structure review, an analysis of the physics and chemistry of the molecules involved is important. FIG.10is a sketch of atom structure. The upper area is to show that the external electrons move at high speed. In the sketch a hydrogen atom with only one electron is moving at that level that can be a cloud around for the speed of his movement. This will be an extra point of the analysis. The lower area shows that there are different orbit levels with specific capacity. All the known atoms have the same elements as positive charge in the nucleus: protons and neutrons and external electrons with negative charge. The difference in all the known elements is the internal and external orbits design. Some elements are shown for an easy understanding of the internal organization: Hydrogen 1s1 Carbon 1s22s2p2 Nitrogen 1s22s2p3 Oxygen 1s22s2p4 Sulfur 1s22s2p63s2p4 FIG.11illustrates atoms orbits design. This sketch is to show the structure orbit design on every energy level. The complexity of that orbits design shows the big difference of the atoms structure as known in nature.FIGS.12A,12B, and12Cillustrate molecular interactions. This drawing is to show how a molecule can be transformed and divided in some other molecule or free atoms. Each of the figures shows some of these modifications. FIGS.13and27show the internal structure of the oxygen atom, how the electro-magnetic orientation of the internal composition reacts with similar oxygen-hydrogen molecules. The real orbital of the oxygen electrons shows how complex the mutual interaction can be. Most of the external electrons have strong capacity to interact with other atoms and molecules known as Reactive Oxygen Level (ROL). FIG.14illustrates atoms and molecules structure. These figures show each atom's interaction to form different molecules. H2O molecule interacts with every election of the atoms filing the empty places of the external orbits. Hydrogen 1s1Oxygen 1s22s2p4(2 empty areas) CH4and NaCl molecules show the same pattern as each orbital details. FIGS.28and29illustrate atom permanent activity: Einstein verified that all atoms (and molecules) in nature are in permanent movement as the sketch shows, and can be static when absolute O temperature (Kelvin index=−273° C.). This remark shows that any environment is in permanent activity moving the electromagnetic field around. In the lower area is shown the energy sequence when any electron is attempting to move and the energy required for it. The energy each plant uses is the photon permanent activity (FIGS.18A and18B). FIG.20shows wave and lines of electron activity. Academic researchers have been involved to define the basic laws of the electrons activity. We will show some of this research as the basis of the invention. Since Faraday and Maxwell a number of theories show the electron capabilities and behavior. The first drawing shows that the energy wave can be modified when time and electromagnetic energy is present or modified (equations mentioned as reference but are the basis of the modern society: computers, radar, radio, TV communications etc.). Schrödinger uses time as basis of interactions. Feynman postulated unexpected line direction for the energy and the electromagnetic activity. At the bottom of the sketch are some lines of possible paths that any electron follow to interact with others. FIGS.31A and31Billustrate electron energy path. This to show the unpredictable wave line of energy that after photons impulse can follow and line of reaction of the affected electron.FIG.31Ais a theorical view of this activity.FIG.31Bis the real lines of electron activity (Feynman). FIGS.32,33A, and33Billustrate electric and magnetic waves path. These sketches show the orientation and path of the electromagnetic phenomena that affects any molecule or atom permanently. After we define the unpredictable path of the electrons behavior, we can admit the changes pending of any additional energy source, but under these data and controlled energy we can manipulate the final result we look for. All these interactions affect the molecule behavior specially when we know that in the soil a number of elements, bacteria activity and water influence have a permanent activity, creating a specific environment with electromagnetic values. This activity is defined as redox phenomena: reduction oxidation, loss or gain external electrons in a molecular relation. As conclusion: what we know about plants is not total comprehension, but just the best data available—that means is not apparent facts, observations or empirical data that we recorded, because our perceptions are structured by information, previous data, habits of thought, theories—always with possibility of making mistakes, until new data is available. As mentioned previously, plants entire picture is a complex issue—and the purpose is related to analyze the nutrition and plant development. Living individuals need nutrition and each species develops their own differentiated process for selection and ingestion, interval chemical changes, nutrients selection, and nutrients integrated, but if we modify the structure of these basic elements used as nutrients the final result (after the natural process) can be a wonder or can be fatal. When the natural process is disturbed modern medicine can design a specific (patented) formulation of molecules to arrange the normalization needed. The disclosure is related to the fact that the manipulation of the amount of electrons that can be added in both directions, the orientation of the total water molecules and additional activity can create a controlled electro-magnetic environment. As the nutrition solutions are controlled (manipulated) the entire life plant path can be programed: the wake up of the seeds, the biotic-abiotic environment, the total plant development, the productive process, the fruit maturity, and the aging process, not to mention better fertilizer use. The patent protection requested is oriented to the utility use of the academic concept and as result some prototypes can be made, adapted to the soil, external conditions, plant species. The proficiency of the electricity is the key of our modern way of life: utilities at home, office, street, computers, communications, etc. have this common base. Energy production is beyond any imagination, since basic mechanics production until dams, nuclear, wind, sun sources are in use and some new to come. In any case the ultimate phenomena are reduced to produce, orientation, control and electrons acceleration. A number of engines have been designed for decades for any purpose at home, office and industrial: induction engine, cronclad motor, air cooled engine, reciprocating engine, two phase motor, two pole motor, rocket engine, value-in head engine, V motor—cylinder converger, internal combustion engine, jet engine, water cooled motor, air cooled motor, explosion motor, ramjet engine, turbo-prop engine, diesel engine, out-board motor, motor-generator, single-phase motor, propulsion motor, pulse-jet engine, synchronous motor, tractor engine, etc. For any specific intention an engine can be designed. FIGS.15A through16Cshow engine internal flux of electrons. As example of the possibilities in agriculture the sketch shows how these options can operate: FIG.15A.—Induction engine—a copper wire is coiled around a vacuum metal nucleus—where the electro-magnetic environment create an electron flux—our practical prototype can increase or reduce that flux on both direction with electromagnetic effect in the internal used element (in this case water). FIG.15B.—Toroid engine—this particular design is a copper wire coil but in circular mode creating an specific electromagnetic energy current (positive-negative path) to align the electrons current. FIG.15C.—Is a multiple Induction engine design in a circular path. In this option each induction coil creates its own electron-flux—but as they are sequence-aligned the electromagnetic wave creates a circular impulse (washing machine). FIGS.34A and34Bshow some engine designs for electromagnetic impulse.FIG.34Ashows toroid designs with different current as result that can be used for optional purpose.FIG.34B. shows some optional designs for the multiple induction engine where the diversity of electromagnetic waves that can be created can be observed. Basic Considerations The analysis of the theoretical concept is important, regardless of the physical experimentation with the prototype. This model has multiple options based on the basic concept of nature and soil composition; water and nutrient mobilization capacity; pH and salt residues, as a result of previous fertilization and use; climate and temperatures involved; and atmospheric pollution. Electrical conduction coil design generates magnetic fields that are free electrons in a controllable and useful direction. Plant absorption phenomenon and nutrient management is regulated by anion-cation exchange of the environment. In this process, the water and CEe and CECe capacity that it may have, represents the basic solvent-solute operation. The plant cannot realize its development function and production (genetic option) without the previous process; nevertheless, the chemical phenomena chain that allows its development (enzymes, sugars, hormones) will always be linked to the CEe and CECe of the water and liquids involved. The prototype consists of six (6) integrated coils with the following characteristics (2 different types): they control and rectify the voltage involved; by means of a timer, they handle the intensity of electronic fields (electron flow); they have instrumentation that allows the reverse of electron flow, conducting them in both directions; they are designed to arrange the electromagnetic orientation atoms and water molecules, as well as the resulting solutes; and they are designed to manage the electron flow activity. The irrigation water has a CEe present flow electron capacity; and this prototype offers the possibility of manipulating them in numerous options, according to the type of crop and application period; and as a result: the harvest. The absorption process that takes place in the plant root depends on the electronegativity of each metal and nutrients and the possibility that the solute (water) can adapt to plant needs in each phase of its life cycle. The active involvement of this electron movement in the anion-cation absorption phenomenon and use of the soil elements and the active bacteria that make it up must be considered. Involvement and use in the nitrogen cycle and other elements must be considered. Programming must be according to the needs of each genetic type of plant and their adaptation to soil and climate diversity. Programming of the prototype as an example has to be prepared according to the conditions of each type of sowing and the nutritional characteristics in each stage are required; likewise, the type of soil and climate, as it happens with each region that harvests cotton. As a result of this analysis, we can carry out tests and adapt the instrumentation offered by the prototype. As already explained, these analyses are far-reaching, but they are the basis of their real use; especially, in regions where low productivity is transformed into serious food constraints for the population. The main reason for this experimentation is to evaluate the mobility levels and atom conduction that delimit water composition and its affectation in the total agricultural processes. The real expectations of agriculture summarize a complicated network of factors that can be analyzed in stages, including the probiotic quality of the soil; the porosity and chemical composition of the soil; the residues of previous harvests: affectation and salts residues, and resulting pH; the general weather and predictable visibility; pollution; and the quality and volume of water. Considerations (basis and target handle) include elemental atom composition that is included in this study (Elemental Composition table below—the location of the external orbit allows us to estimate the location in the basic oxidation-reduction processes, that is, solute formation); consideration for agricultural effects of the elements that are considered nutrients (macro-micro) and appropriate ion availability (FIGS.22-24and Nitrogen Activity table below); ideal percentages for the ideal harvest (FIG.22); importance in atomic structure and nitrogen activity (Nitrogen Activity table below); importance of evaluating and classifying the composition and condition of the soil porosity (ROS>Oxygen Reactivity) (FIG.21); evaluation of the residual chemical composition of the soil and electromagnetic ductility; and regular water composition for agricultural use with its multiple options—electrostatic reality and residual activity that will affect the elements that can become useful solutes to plants and their productive capacity. The basis of this analysis lies in the basic principle that the composition in atom volume can influence, and if necessary, modify if subjected to a strong electron tide in a positive or negative direction (electron flow activity). The possibility of altering (under control) the physiochemical-electromagnetic characteristic of these elements is a practice with the hopes of managing the total process of agriculture. Embodiments of the engine include an engine that when creating a determined electromagnetic field can face or add free electrons—there is adaptation in order to increase or decrease the flow, as well as to reverse the direction flow; a toroid with peripheral magnetic field that allows aligning the electromagnetic orientation of the material (liquid, solid, gas); and multiple engines that creates a circular current for the activation or reduction. The turning pressure or reverse can be increased. This prototype will allow evaluating each stage and preparing the operation of the crops. It has an independent operation in each case. The second prototype has the three series linked for direct operation, although an evaluation of the other external conditions is suggested. CE-CEC Activity This evaluation will give the option of detailed analysis according to the genetic characteristics of the treated crops and will allow planning the crops according to the external conditions. The evaluation of the biological processes is an option for a future generation of nutrients. The conditions of the use of water can be evaluated and its practical utility can be programed. The improvement and recovery of the soil with excesses and surpluses of non-assimilated previous fertilizers and those with altered pH can be controlled. The studies to evaluate and control the activity of the internal molecular phenomena will be the basis to define the best growth, development, harvest, and survival conditions of the plants, as well as the qualities of the harvest. Verifying the conditions of genetic manipulation (Monsanto-Bayer, Dow Chemical, etc.) and controlling its impact on the direct or secondary consumption population (consumer animals), will be more accessible and controllable. A.N.ELEMENTAL COMPOSITION7N1s22s2p3(−3 ≤ +5)1H1s1(−1 ≤ +1)15P1s22s2p63s2p3(−3, +3, +5)8O1s22s2p4(−2, −1, +2)20Ca1s22s2p63s2p64s2(+2)12Mg1s22s2p63s2(+2)19K1s22s2p63s2p64s1(+1)16S1s22s2p63s2p4(−2, +2, +4, +6)6C1s22s2p25B1s22s2p1(+3)17Cl1s22s2p63s2p5(−1, +1, +3, +4, +5, +7)29Cu1s22s2p63s2p6d104s1(+1, +2)26Fe1s22s2p63s2p6d64s2(+2, +3)25Mn1s22s2p63s2p6d54s2(+2, +4, +7)42Mo1s22s2p63s2p6d104s2p6d55s1(+2, +3, +4, +5, +6)28Ni1s22s2p63s2p6d84s2(+2, +3)30Zn1s22s2p63s2p6d104s2(+2)14Si1s22s2p63s2p2(−4, +2, +4)11Na1s22s2p63s1(+1)17Cl1s22s2p63s2p5(−1, +1, +3, +4, +5, +7) NITROGEN ACTIVITY → OXIDATION DEGREE+5HNO3Nitric Acid+4NO2Nitrogen Dioxide+3HNO2Nitrous Acid+2NONitric Oxide+1N2ONitrous Oxide−1N2H2Diimide−2N2H4Hydrazine NITRITE→ Reduction capNITRATEAMMONIUMInorganic Nitrogen→ Activity by electronDehydrogenaseNitrogenaseUrease Nitrification is performed by soil bacteria, but the process results in residual soil acidity. When ammonium ions are transformed to nitrate, H+IONS are released. Ammonium and oxygen in the presence of nitrifying bacteria are transformed into nitrate, hydrogen, and water: NH4++2O2→NO3−+2H++H2O Common fertilizer with acidic residual include ammonia, ammonium sulfate, ammonium nitrate, and urea. Nitrate sources with no acidic residual include calcium nitrate and potassium nitrate. How to Neutralize Acidity In a soil mix colloid, the addition of calcium carbonate: H+H++CaCO3→Ca+H2O+CO2 In a soil mix colloid, the addition of calcium sulfate: H+H++CaSO4→Ca+2H++SO4}H2SO4(sulfuric acid) Soil Column Study The following outlines an exemplary study useful for determining soil impacts of water treated with the present invention and estimating parameters for use with an engine of the present invention. The soil columns are clear acrylic tubes 4 inches (10 cm) diameter and 24 inches (61 cm) in length, with caps on each end, which are suspended vertically to allow for flow of water. The apparatus used to hang the columns is stored in an indoor storage building connected to the building's earth ground with a multi-strand electrical cable to ensure safety (if electrical power is used). A “Hanford Sandy Loam” will be used for this study. Soil location is known to have a bulk density of approximately 1.5 g/cm3. The collected soil will be analyzed for particle size (amount of sand, silt, and clay), pH, and ECe before loading into the columns. The soil will be dried at 105° C., then ground and sieved through a 2 mm screen. The sieved soil will then have water added to it to increase the volumetric water content of the soil to approximately 6%. At this point, the moist soil will be packed into the soil columns to a depth of 12 inches (30.5 cm) at a bulk density of 1.5 g/cm3. A total of 18 columns will be used in the study. For the study, nine “treated” columns will receive experimentally treated water and nine “control” columns will receive non-treated water. An amount of water equivalent to one acre/inch, (200 ml) will be added to each of the columns two times each week, for the length of the experiment. The leachate will be collected the following day (˜24 hrs. later) and the volume will be recorded. Leachate will be analyzed for pH and ECe. The experiment will run for three weeks. Each week of the study three treated and three un-treated soil columns will be removed from the soil column apparatus, six columns in total will be removed each week. This will allow for analysis of changes in the soil after 2, 4, and 6 acre/inches of water have passed through the soil. Each of the columns will have soil samples taken from the Title: Engines Structure for Water Molecules Impulse, Order and Control for Agricultural Purposes contents, and then each will be analyzed for volumetric water content, pH and ECe. Suggested Theoretical Analysis Prior to the Practical Application Phase 1 Objective #1: Determine the impact and activity that nitrogen and its derivatives signify for the environment: nutrients and practical effects; identify crops. Objective #2: Determine the quantum alteration and modification in the nitrogen atom when subjected to pulsating electron currents, as well as its affectation on the support capacity of nutrients and molecules: crops. Objective #3: Determine the impact on physiochemical soil characteristics regarding agriculture in general and in local identified crops. Nitrogen—Oxidation Degree: ElectronegativityMoleculeIdentification Name+5HNO3Nitric Acid+4NO2Nitrogen Dioxide+3HNO2Nitrous Acid+2NONitric Oxide+1N2ONitrous Oxide−1N2H2Diimide−2N2H4Hydrazine−3NH3Ammonia Bio-edaphic parameters are inorganic nitrogen, dehydrogenase, nitrogenase, urease. Soil reduction potential: nitrite, nitrate, ammonium. Objective #4: Examine the effectiveness and testing of engine design in nitrogen atom modification and its impact on soil before, during, and after each crop development period. Provide evaluation of selected crops. Objective #5: Evaluate soil variations according to the salt contamination degree, contamination in the water recovery process, and contamination by chemical residues of fertilizers and pesticides. ROS [Radioactive Oxygen Species] TypesStructureIDReactivitySinglet oxygenO2(O═O)RadicalHighSuperoxideO2−(:O:O:)RadicalMediumHydrogen PeroxideH2O2(H:O—O:H)Non RadicalLowHydroxyl RadicalHO−(H:O•)RadicalVery HighHydronium IonH3O+(H•H•H:O)Radical Objective #6: Provide analysis of the chemical content in the soil before, during, and after each crop period: rebirth of seed (tree and perennial production cycle); first growth period of the plant (beginning of the reproductive process in trees and perennials); flowering period; maturing and harvesting period; soil recovery period; periodic watering impact: retention, waste; biotic waste and fauna; and: H2ONCO3NO3NH3NH4SucroseSO4H•O•K•Na•Cl•N•S•Mg•B•As•LiSe•S•P•Co•Ni•SiCa•Cr•Co Phase 2 Objective #1: Devise equipment adjustment for the use of soil identification characteristics so as to correct the refractive index, water polarity due to porosity effects or specific composition. Objective #2: Determine the impact and affectation of soil identification characteristics after the use of non-processed natural nutrients proceeding from organic or inorganic origin. Evaluate the modifications registered according to the crops under examination. Evaluate crops whose chemical information and development periods can be determined in accordance with the resulting chemical modifications and conditions: cotton, tobacco, legumes, basic grains, fruit crops, sugarcane, and avocado. Objective #3: Evaluate the balance in the suggested energy levels congruent with the reference equipment. Objective #4: Provide analysis and evaluation for publication and/or contribution. | 39,262 |
11858835 | For simplicity and clarity of illustration, the drawing figures illustrate the general manner of construction, and descriptions and details of well-known features and techniques may be omitted to avoid unnecessarily obscuring the invention. Additionally, elements in the drawing figures are not necessarily drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help improve understanding of embodiments of the present invention. The same reference numerals in different figures denote the same elements. The terms “first,” “second,” “third,” “fourth,” and the like in the description and in the claims, if any, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments described herein are, for example, capable of operation in sequences other than those illustrated or otherwise described herein. Furthermore, the terms “include,” and “have,” and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, device, or apparatus that comprises a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, system, article, device, or apparatus. The terms “left,” “right,” “front,” “back,” “top,” “bottom,” “over,” “under,” and the like in the description and in the claims, if any, are used for descriptive purposes and not necessarily for describing permanent relative positions. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the invention described herein are, for example, capable of operation in other orientations than those illustrated or otherwise described herein. The terms “couple,” “coupled,” “couples,” “coupling,” and the like should be broadly understood and refer to connecting two or more elements or signals, electrically, mechanically and/or otherwise. Two or more electrical elements may be electrically coupled together, but not be mechanically or otherwise coupled together; two or more mechanical elements may be mechanically coupled together, but not be electrically or otherwise coupled together; two or more electrical elements may be mechanically coupled together, but not be electrically or otherwise coupled together. Coupling may be for any length of time, e.g., permanent or semi-permanent or only for an instant. “Electrical coupling” and the like should be broadly understood and include coupling involving any electrical signal, whether a power signal, a data signal, and/or other types or combinations of electrical signals. “Mechanical coupling” and the like should be broadly understood and include mechanical coupling of all types. The absence of the word “removably,” “removable,” and the like near the word “coupled,” and the like does not mean that the coupling, etc. in question is or is not removable. As defined herein, “approximately” can, in some embodiments, mean within plus or minus ten percent of the stated value. In other embodiments, “approximately” can mean within plus or minus five percent of the stated value. In further embodiments, “approximately” can mean within plus or minus three percent of the stated value. In yet other embodiments, “approximately” can mean within plus or minus one percent of the stated value. DETAILED DESCRIPTION OF EXAMPLES OF EMBODIMENTS In one embodiment, a system is disclosed comprising: one or more processors; and one or more non-transitory memory storage devices storing computer instructions configured to run on the one or more processors and perform: generating ozone; and applying the ozone to water; wherein: generating the ozone comprises: controlling a quantity of the ozone generated; and controlling when the ozone is generated. In another embodiment, a method is disclosed which is implemented via execution of computer instructions configured to run at one or more processors and configured to be stored at one or more non-transitory memory storage devices, the method comprising: generating ozone; and applying the ozone to water; wherein: generating the ozone comprises: controlling a quantity of the ozone generated; and controlling when the ozone is generated. In another embodiment, a system is disclosed comprising: a water supply system configured to make water available to a user; and an ozone generator system configured to generate ozone and apply the ozone to the water prior to use of the water by the user; wherein: the water supply system comprises a water generating unit; the ozone generator system comprises an ozone generator control system; and the ozone generator control system is configured to control a quantity of the ozone generated and when the ozone is generated. Turning to the drawings,FIG.1illustrates an exemplary embodiment of a computer system100, all of which or a portion of which can be suitable for (i) implementing part or all of one or more embodiments of the techniques, methods, and systems and/or (ii) implementing and/or operating part or all of one or more embodiments of the memory storage devices described herein. For example, in some embodiments, all or a portion of computer system100can be suitable for implementing part or all of one or more embodiments of the techniques, methods, and/or systems described herein. Furthermore, one or more elements of computer system100(e.g., a refreshing monitor106, a keyboard104, and/or a mouse110, etc.) also can be appropriate for implementing part or all of one or more embodiments of the techniques, methods, and/or systems described herein. In many embodiments, computer system100can comprise chassis102containing one or more circuit boards (not shown), a Universal Serial Bus (USB) port112, a hard drive114, and an optical disc drive116. Meanwhile, for example, optical disc drive116can comprise a Compact Disc Read-Only Memory (CD-ROM), a Digital Video Disc (DVD) drive, or a Blu-ray drive. Still, in other embodiments, a different or separate one of a chassis102(and its internal components) can be suitable for implementing part or all of one or more embodiments of the techniques, methods, and/or systems described herein. Turning ahead in the drawings,FIG.2illustrates a representative block diagram of exemplary elements included on the circuit boards inside chassis102(FIG.2). For example, a central processing unit (CPU)210is coupled to a system bus214. In various embodiments, the architecture of CPU210can be compliant with any of a variety of commercially distributed architecture families. In many embodiments, system bus214also is coupled to a memory storage unit208, where memory storage unit208can comprise (i) non-volatile memory, such as, for example, read only memory (ROM) and/or (ii) volatile memory, such as, for example, random access memory (RAM). The non-volatile memory can be removable and/or non-removable non-volatile memory. Meanwhile, RAM can include dynamic RAM (DRAM), static RAM (SRAM), etc. Further, ROM can include mask-programmed ROM, programmable ROM (PROM), one-time programmable ROM (OTP), erasable programmable read-only memory (EPROM), electrically erasable programmable ROM (EEPROM) (e.g., electrically alterable ROM (EAROM) and/or flash memory), etc. In these or other embodiments, memory storage unit208can comprise (i) non-transitory memory and/or (ii) transitory memory. The memory storage device(s) of the various embodiments disclosed herein can comprise memory storage unit208, an external memory storage drive (not shown), such as, for example, a USB-equipped electronic memory storage drive coupled to universal serial bus (USB) port112(FIGS.1&2), hard drive114(FIGS.1&2), optical disc drive116(FIGS.1&2), a floppy disk drive (not shown), etc. As used herein, non-volatile and/or non-transitory memory storage device(s) refer to the portions of the memory storage device(s) that are non-volatile and/or non-transitory memory. In various examples, portions of the memory storage device(s) of the various embodiments disclosed herein (e.g., portions of the non-volatile memory storage device(s)) can be encoded with a boot code sequence suitable for restoring computer system100(FIG.1) to a functional state after a system reset. In addition, portions of the memory storage device(s) of the various embodiments disclosed herein (e.g., portions of the non-volatile memory storage device(s)) can comprise microcode such as a Basic Input-Output System (BIOS) or Unified Extensible Firmware Interface (UEFI) operable with computer system100(FIG.1). In the same or different examples, portions of the memory storage device(s) of the various embodiments disclosed herein (e.g., portions of the non-volatile memory storage device(s)) can comprise an operating system, which can be a software program that manages the hardware and software resources of a computer and/or a computer network. Meanwhile, the operating system can perform basic tasks such as, for example, controlling and allocating memory, prioritizing the processing of instructions, controlling input and output devices, facilitating networking, and managing files. Exemplary operating systems can comprise (i) Microsoft® Windows® operating system (OS) by Microsoft Corp. of Redmond, Wash., United States of America, (ii) Mac® OS by Apple Inc. of Cupertino, Calif., United States of America, (iii) UNIX® OS, and (iv) Linux® OS. Further exemplary operating systems can comprise (i) iOS™ by Apple Inc. of Cupertino, Calif., United States of America, (ii) the Blackberry® OS by Research In Motion (RIM) of Waterloo, Ontario, Canada, (iii) the Android™ OS developed by the Open Handset Alliance, or (iv) the Windows Mobile™ OS by Microsoft Corp. of Redmond, Wash., United States of America. Further, as used herein, the term “computer network” can refer to a collection of computers and devices interconnected by communications channels that facilitate communications among users and allow users to share resources (e.g., an internet connection, an Ethernet connection, etc.). The computers and devices can be interconnected according to any conventional network topology (e.g., bus, star, tree, linear, ring, mesh, etc.). As used herein, the term “processor” means any type of computational circuit, such as but not limited to a microprocessor, a microcontroller, a controller, a complex instruction set computing (CISC) microprocessor, a reduced instruction set computing (RISC) microprocessor, a very long instruction word (VLIW) microprocessor, a graphics processor, a digital signal processor, or any other type of processor or processing circuit capable of performing the desired functions. In some examples, the one or more processors of the various embodiments disclosed herein can comprise CPU210. In the depicted embodiment ofFIG.2, various I/O devices such as a disk controller204, a graphics adapter224, a video controller202, a keyboard adapter226, a mouse adapter206, a network adapter220, and other I/O devices222can be coupled to system bus214. Keyboard adapter226and mouse adapter206are coupled to keyboard104(FIGS.1&2) and mouse110(FIGS.1&2), respectively, of computer system100(FIG.1). While graphics adapter224and video controller202are indicated as distinct units inFIG.2, video controller202can be integrated into graphics adapter224, or vice versa in other embodiments. Video controller202is suitable for refreshing monitor106(FIGS.1&2) to display images on a screen108(FIG.1) of computer system100(FIG.1). Disk controller204can control hard drive114(FIGS.1&2), USB port112(FIGS.1&2), and CD-ROM drive116(FIGS.1&2). In other embodiments, distinct units can be used to control each of these devices separately. Network adapter220can be suitable to connect computer system100(FIG.1) to a computer network by wired communication (e.g., a wired network adapter) and/or wireless communication (e.g., a wireless network adapter). In some embodiments, network adapter220can be plugged or coupled to an expansion port (not shown) in computer system100(FIG.1). In other embodiments, network adapter220can be built into computer system100(FIG.1). For example, network adapter220can be built into computer system100(FIG.1) by being integrated into the motherboard chipset (not shown), or implemented via one or more dedicated communication chips (not shown), connected through a PCI (peripheral component interconnector) or a PCI express bus of computer system100(FIG.1) or USB port112(FIG.1). Returning now toFIG.1, although many other components of computer system100are not shown, such components and their interconnection are well known to those of ordinary skill in the art. Accordingly, further details concerning the construction and composition of computer system100and the circuit boards inside chassis102are not discussed herein. Meanwhile, when computer system100is running, program instructions (e.g., computer instructions) stored on one or more of the memory storage device(s) of the various embodiments disclosed herein can be executed by CPU210(FIG.2). At least a portion of the program instructions, stored on these devices, can be suitable for carrying out at least part of the techniques, methods, and activities of the methods described herein. In various embodiments, computer system100can be reprogrammed with one or more systems, applications, and/or databases to convert computer system100from a general purpose computer to a special purpose computer. Further, although computer system100is illustrated as a desktop computer inFIG.1, in many examples, system100can have a different form factor while still having functional elements similar to those described for computer system100. In some embodiments, computer system100may comprise a single computer, a single server, or a cluster or collection of computers or servers, or a cloud of computers or servers. Typically, a cluster or collection of servers can be used when the demand on computer system100exceeds the reasonable capability of a single server or computer. In certain embodiments, computer system100may comprise an embedded system. Skipping ahead now in the drawings,FIG.3illustrates a representative block diagram of a system300, according to an embodiment. System300is merely exemplary and embodiments of the system are not limited to the embodiments presented herein. System300can be employed in many different embodiments or examples not specifically depicted or described herein. In some embodiments, certain elements of system300can perform various methods and/or activities of those methods. In these or other embodiments, the methods and/or the activities of the methods can be performed by other suitable elements of system300. As explained in greater detail below, in many embodiments, system300can make available water to a user of system300. For example, in some embodiments, system300can generate the water to make available the water to the user of system300. In these or other embodiments, system300can generate ozone and apply the ozone to one or more substances (e.g., water). In many embodiments, system300can control treatment of the substance(s) (e.g., water) with the ozone, such as, for example, to optimize treatment of the substance(s) (e.g., water) with the ozone. For example, in some embodiments, system300can control a quantity of the ozone generated, and/or when the ozone is generated. Accordingly, in many embodiments, system300can sanitize water made available to a user of system300, such as, for example, to make the water potable. In these or other embodiments, system300can sanitize one or more interior surfaces of a water supply system (e.g., water supply system301(FIG.3)). Generally, therefore, system300can be implemented with hardware and/or software, as described herein. In some embodiments, at least part of the hardware and/or software can be conventional, while in these or other embodiments, part or all of the hardware and/or software can be customized (e.g., optimized) for implementing part or all of the functionality of system300described herein. System300comprises an ozone generator system302. In many embodiments, system300also can comprise a water supply system301. In these embodiments, ozone generator system302can be coupled to water supply system301. In some embodiments, water supply system301can be omitted. Water supply system301can make available water to a user of system300. Accordingly, water supply system301can comprise any suitable system configured to make available water to the user of system300. For example, in some embodiments, water supply system301can comprise a public water supply or a water collector (e.g., a rain collector, a fog net, etc.). In many embodiments, water supply system301can comprise a filter303, a reservoir304, and/or a filter305. In other embodiments, filter303, reservoir304, and/or filter305can be omitted. In many embodiments, water supply system301can generate the water made available to the user of system300. In some of these embodiments, water supply system301can be devoid of a public water supply and/or a water collector (e.g., a rain collector, a fog net, etc.). For example, in some embodiments, water supply system301can comprise a water generating unit306. In some embodiments, filter303, reservoir304, and/or filter305can be part of water generating unit306. In many embodiments, water generating unit306can comprise any suitable system configured to generate water. For example, water generating unit306can comprise an atmospheric water generator and/or a drinking water solar panel. In some embodiments, a drinking water solar panel also can be referred to as a water-from-air solar panel. In some embodiments, the generating unit306can store firmware that is executed by a microcontroller (e.g., which can be integrated into, or in communication with, the generating unit306) to perform some or all of the functions associated with the water generating unit306described herein. In certain embodiments, the generating unit306may lack a hard-drive. In many embodiments, water generating unit306can comprise a heater307, a desiccation device308, and a condenser309. Heater307can be coupled to desiccation device308, desiccation device308can be coupled to condenser309, and condenser309can be coupled to heater307. In some embodiments, water generating unit306can comprise a water generating unit control system310, a blower311, and a circulator312. In many embodiments, water generating unit306can operably move and repeatedly cycle one or more regeneration fluids from heater307to desiccation device308to condenser309and back to heater307(e.g., in a closed loop), such as, for example, by using circulator312, as explained below. Heater307, desiccation device308, and condenser309can be coupled together by any suitable conduits configured to transfer the regeneration fluid(s) among heater307, desiccation device308, and condenser309. Exemplary regeneration fluid(s) can comprise humid air, one or more supersaturated or high relative humidity gases (e.g., a relatively humidity greater than approximately 90%), one or more glycols, one or more ionic liquids, etc. Desiccation device308can comprise an adsorption zone configured to receive a process fluid (e.g., humid air), a desorption zone configured to receive the regeneration fluid(s), and a desiccant element configured to be operably moved and repeatedly cycled between the adsorption zone and the desorption zone to capture (e.g., absorb and/or adsorb) water from the process fluid in the absorption zone and desorb water into the regeneration fluid(s) in the desorption zone. After the processing fluid is received at the adsorption zone of desiccation device308, the processing fluid can be selectively exhausted to the atmosphere around water generating unit306and/or transferred to ozone generator system302to aid in generating ozone, as explained in greater detail below. In some embodiments, the desiccant element can comprise any suitable material or materials configured such that the desiccant element can capture (e.g., absorb and/or adsorb) and desorb water. For example, the material(s) of the desiccant element can comprise one or more hygroscopic materials. In many embodiments, exemplary material(s) for the desiccant element can comprise silica, silica gel, alumina, alumina gel, montmorillonite clay, one or more zeolites, one or more molecular sieves, activated carbon, one or more metal oxides, one or more lithium salts, one or more calcium salts, one or more potassium salts, one or more sodium salts, one or more magnesium 25 salts, one or more phosphoric salts, one or more organic salts, one or more metal salts, glycerin, one or more glycols, one or more hydrophilic polymers, one or more polyols, one or more polypropylene fibers, one or more cellulosic fibers, one or more derivatives thereof, and one or more combinations thereof. In some embodiments, the desiccant element can comprise any suitable form or forms configured such that the desiccant element can capture (e.g., absorb and/or adsorb) and desorb water. For example, the desiccant element can comprise a liquid form and/or a solid form. In further embodiments, the desiccant element can comprise a porous solid impregnated with one or more hygroscopic material(s). In some embodiments, the desiccant element can be configured to capture (e.g., absorb and/or adsorb) water at one or more temperatures and/or pressures and can be configured to desorb water at one or more other temperatures and/or pressures. In some embodiments, the desiccant can be implemented with material(s) and/or form(s), and/or can be otherwise configured such that the desiccant element does not capture (e.g., absorb and/or adsorb) one or more materials toxic to humans, pets, and/or other animals. In many embodiments, heater307can provide thermal energy to the regeneration fluid(s) so that the regeneration fluid(s) are heated upon arriving at desiccation device308. Exposing the desiccant element of desiccation device308to the heated regeneration fluid(s) at the desorption zone of desiccation device308can regenerate the desiccant element of desiccation device308. In some embodiments, heater307can be any suitable device configured to provide thermal energy to the regeneration fluid(s). For example, in many embodiments, heater307can comprise a solar thermal heater. In these embodiments, the solar thermal heater can convert solar insolation to the thermal energy provided to the regeneration fluid(s). Further, in these embodiments, heater307can be part of a solar panel, which can generate electricity to electrically power water generating unit306, water generating unit control system310, blower311, circulator312, ozone generator system302, ozone generator401(FIG.4), ozone generator control system402(FIG.4), and/or blower405(FIG.5). In many embodiments, condenser309can extract the water to be made available to the user of system300from the regeneration fluid(s) received at condenser309from desiccation device308. For example, condenser309can condense water vapor from the regeneration fluid(s) into liquid water to be the water made available to the user of system300. Accordingly, in many embodiments, condenser309can be configured to cool the regeneration(s) fluids by extracting thermal energy from the regeneration fluid(s). In some embodiments, condenser309can transfer thermal energy extracted from the regeneration fluid(s) to the process fluid upstream of desiccation device308and/or to the atmosphere around water generating unit306. In some embodiments, blower311can comprise any suitable device configured to move the process fluid to desiccation device308, and when applicable, to ozone generator system302, as further explained below. For example, in some embodiments, blower311can comprise a pump. In some embodiments, circulator312can comprise any suitable device configured to move the regeneration fluid(s) from heater307to desiccation device308to condenser309, and back to heater307. For example, in some embodiments, circulator312can comprise a pump. In some embodiments, water generating unit control system310can comprise any suitable device configured to control operation of water generating unit306. For example, in many embodiments, water generating unit control system310can control operation of blower311, circulator312and/or desiccation device308. Further, in some embodiments, water generating unit control system310can control operation of condenser309, such as, for example, when condenser309is implemented as an active device. Accordingly, water generating unit control system310can be electrically coupled to blower311, circulator312, condenser309, and/or desiccation device308. In many embodiments, water generating unit control system310can be similar or identical to computer system100(FIG.1). In many embodiments, reservoir304can store water to be made available to the user of system300by water supply system301. Accordingly, reservoir304can comprise any suitable receptacle or container configured to store water. In some embodiments, reservoir304can receive the water stored by reservoir304to be made available to the user of system300from any suitable water source, such as, for example, a public water supply. In these or other embodiments, when water supply system301generates water made available to the user of system300, such as, for example, by water generating unit306, reservoir304can receive and store the water generated by water supply system301. For example, in some embodiments, reservoir304can receive the water extracted from the regeneration fluid(s) of water generating unit306by condenser309. Further, in some embodiments, reservoir304can be coupled to a public water supply and/or water generating unit306, such as, for example, at condenser309. Accordingly, water supply system301can comprise any suitable conduit or conduits configured to transfer water from a public water supply and/or water generating unit306to reservoir304. In many embodiments, filter303can be operable to filter water received by reservoir304, such as, for example, to remove one or more materials (e.g., one or more materials toxic to humans) from the water. Accordingly, filter303can be coupled to reservoir304, such as, for example, between reservoir304and a public water supply of water supply system301and/or water generating unit306. Filter303can comprise any suitable device configured to filter water. For example, filter303can comprise a carbon filter or a stainless steel frit. In some embodiments, filter303can be omitted, including, for example, in embodiments in which reservoir304is omitted. In many embodiments, filter305can be operable to filter the water made available to the user of system300, such as, for example, to remove one or more materials (e.g., one or more materials toxic to humans) from the water. For example, in some embodiments, filter305can filter the water made available to the user of system300immediately before the water is provided to the user of system300, such as, for example, at an output of water supply system301. In further embodiments, when water supply system301comprises reservoir304, filter305can be coupled to reservoir304, such as, for example, at an output of reservoir304. Filter305can comprise any suitable device configured to filter water. For example, filter305can comprise a carbon filter or a stainless steel frit. In some embodiments, filter305can be omitted. In many embodiments, filter305can remove residual ozone from the water made available to the user of system300when ozone is applied to the water, as explained below. For example, when filter305comprises a carbon filter, the carbon filter can capture residual ozone in water passing through filter305, and the residual ozone can react with other organic matter captured in the carbon filter, and/or the residual ozone can react with the carbon filter itself, any mechanism of which can function to remove residual ozone from the water. Ozone generator system302can generate ozone. In many embodiments, ozone generator system302can generate ozone in a controlled manner, such as, for example, when ozone generator system302comprises ozone generator control system402(FIG.4), as explained below. Further, ozone generator system302can apply the ozone generated by ozone generator system302to one or more substances, such as, for example, to sterilize the substance(s). In many embodiments, when system300comprises water supply system301, ozone generator system302can apply the ozone generated by ozone generator system302to the water made available to the user of system300by water supply system301before the user of system300uses (e.g., drinks) the water. Further, in these or other embodiments, when system300comprises water generating unit306, ozone generator system302can apply the ozone generated by ozone generator system302to one or more interior surfaces of water generating unit306, heater307, desiccation device308, and/or condenser309, such as, for example, to sterilize the interior surface(s). In many embodiments, ozone generator system302can be coupled to water supply system301, such as, for example, to apply ozone to the water made available to the user of system300by water supply system301and/or the interior surface(s) of water generating unit306, heater307, desiccation device308, and/or condenser309. Further, in some embodiments, ozone generator system302can be coupled to water generating unit306(e.g., desiccation device308) to receive the process fluid output from desiccation device308. In these or other embodiments, system300can comprise any suitable conduit or conduits configured to transfer the ozone generated by ozone generator system302to water supply system301and/or the process fluid output from desiccation device308to ozone generator system302. In some embodiments, ozone generator system302can be part of water supply system301and/or water generating unit306. In some embodiments, ozone generator system302can apply ozone to (i) the water made available to the user of system300by water supply system301and/or (ii) the interior surface(s) of water generating unit306, heater307, desiccation device308, and/or condenser309at the same time and/or at different times. Accordingly, in these or other embodiments, ozone generator system302can be coupled to water supply system301at multiple locations. For example, in some embodiments, ozone generator system302can be coupled to water generating unit306, such as, for example, at condenser309. In these or other embodiments, ozone generator system302can be coupled to reservoir304. Turning ahead in the drawings,FIG.4illustrates a representative block diagram of ozone generator system302, according to the embodiment ofFIG.3. In many embodiments, ozone generator system302comprises an ozone generator401and an ozone generator control system402. Further, ozone generator system302can comprise an energy source403, a transformer404, a blower405, one or more ozone injectors406, a temperature sensor407, one or more weather event sensors408, one or more ozone sensors411, and/or one or more microbial sensors412. Also, ozone generator system302can comprise a maintenance sensor409and/or a water use sensor410, such as, for example, when system300(FIG.3) comprises water supply system301ofFIG.3(e.g., water generating unit306(FIG.3)). In some embodiments, transformer404, blower405, ozone injector(s)406, temperature sensor407, weather event sensor(s)408, maintenance sensor409, water use sensor410, ozone sensor(s)411, and/or microbial sensor(s)412can be omitted. In many embodiments, ozone generator401can generate ozone from a feed gas including oxygen (e.g., air). Accordingly, ozone generator401can comprise any suitable device configured to generate ozone. In some embodiments, ozone generator401can comprise an ultraviolet ozone generator. In other embodiments, ozone generator401can comprise a corona ozone generator. For example, in these embodiments, in order to generate ozone, ozone generator401can generate an electric field and pass the feed gas through the electric field, thereby causing some diatomic oxygen molecules to dissociate into oxygen atoms that attach to other diatomic oxygen molecules to form ozone. In many embodiments, when system300(FIG.3) comprises water supply system301(FIG.3), when water supply system301(FIG.3) comprises water generating unit306(FIG.3), and when the process fluid used by water generating unit306(FIG.3) includes oxygen, ozone generator405can use the process fluid as the feed gas from which ozone generator405generates ozone. Using the process fluid as the feed gas can be advantageous because the process fluid can be dehumidified by operation of desiccation device308, and dehumidifying the feed gas can be helpful to mitigate or eliminate the formation of nitric acid by ozone generator405, which could corrode ozone generator system302(FIG.3), and when applicable, water supply system301(FIG.3). In many embodiments, blower405can deliver the feed gas to ozone generator401. Further, blower405can push the resulting ozone and remaining feed gas onward to water supply system301(FIG.3). Accordingly, in some embodiments, blower405can comprise any suitable device configured to move the feed gas to ozone generator401, and when applicable, ozone and residual feed gas to water supply system301(FIG.3). For example, in some embodiments, blower405can comprise a pump. Further, blower405can be coupled to ozone generator401, and ozone generator system302can comprise any suitable conduit or conduits configured to transfer the feed gas from blower405to ozone generator401. In some embodiments, when the feed gas comprises the process fluid used by water generating unit306(FIG.3), blower405can receive the process fluid from water generating unit306(FIG.3). In some embodiments, when the feed gas comprises the process fluid used by water generating unit306(FIG.3), blower405can be omitted. In these embodiments, blower311(FIG.3) can operate to provide the functionality of blower405. In the same or other embodiments, blower405can be combined with blower311(FIG.3). In many embodiments, energy source403can electrically power ozone generator401. In some embodiments, energy source403can electrically power ozone generator control system402. Further, in some embodiments, when ozone generator system302comprises blower405, energy source403can electrically power blower405. In many embodiments, energy source403can be electrically coupled to ozone generator401, ozone generator control system402, blower405, and/or transformer404. For example, energy source403can be configured to deliver12volt electricity to blower405and/or transformer404. Meanwhile, transformer404can be configured to transform the electricity provided by energy source403to ozone generator401. For example, transformer404can be configured to transform the electricity provided by energy source403to ozone generator401from 12 volt electricity to 3 kilovolt electricity. In many embodiments, energy source403can comprise any suitable energy source that can electrically power ozone generator401, ozone generator control system402, and/or blower405. In these or other embodiments, when system300(FIG.3) comprises water supply system301(FIG.3), when water supply system301(FIG.3) comprises water generating unit306(FIG.3), and when heater307(FIG.3) is part of a solar panel, as described above, energy source403can comprise the solar panel. In some embodiments, energy source403can be used to electrically power water supply system301(FIG.3), including water generating unit306(FIG.3) and its heater307(FIG.3), condenser309(FIG.3), blower311(FIG.3), circulator312(FIG.3), and/or water generating unit control system310(FIG.3). In many embodiments, ozone injector(s)406can be operable to mix ozone generated by ozone generator401with one or more liquid substances (e.g., the water made available to the user of system300(FIG.3) by water supply system301(FIG.3) to which the ozone is applied, such as, for example, to sterilize the substance(s). Accordingly, ozone injector(s)406can comprise any suitable device(s) configured to mix ozone with one or more liquids. In certain embodiments, the ozone injector(s)406can include one or more spargers, one or more venturis, one or more aspirators and/or other devices that are capable of mixing ozone with one or more liquids. In some embodiments, ozone injector(s)406can be omitted, such as, for example, when none of the substance(s) to which the ozone is applied are a liquid. Although ozone generator302(FIG.3) is illustrated separately from water supply system301(FIG.3) atFIG.3, in many embodiments, when system300(FIG.3) comprises water supply system301(FIG.3), one or more of ozone injector(s)406can be located at water supply system301(FIG.3). For example, one or more of ozone injector(s)406can be located at condenser309(FIG.3), and/or one or more of ozone injector(s)406can be located at reservoir304(FIG.3). In many embodiments, temperature sensor407can measure an ambient temperature proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied (e.g., in real time). For example, when system300(FIG.3) comprises water supply system301(FIG.3), temperature sensor407can measure an ambient temperature proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location of water supply system301(FIG.3) (e.g., in real time). Further, when system300(FIG.3) comprises water supply system301(FIG.3), and water supply system301(FIG.3) comprises water generating unit310(FIG.3), temperature sensor407can measure an ambient temperature proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location of water generating unit310(FIG.3) (e.g., in real time). In some embodiments, temperature sensor407can comprise any suitable device configured to measure an ambient temperature proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied. For example, temperature sensor407can comprise a thermometer. In some embodiments, temperature sensor407can be electrically coupled to ozone generator control system402to provide measurements of the ambient temperature to ozone generator control system402. In many embodiments, weather event sensor(s)408can detect one or more weather events proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied (e.g., in real time). For example, when system300(FIG.3) comprises water supply system301(FIG.3), weather event sensor(s)408can detect weather event(s) proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location of water supply system301(FIG.3) (e.g., in real time). Further, when system300(FIG.3) comprises water supply system301(FIG.3), and water supply system301(FIG.3) comprises water generating unit310(FIG.3), weather event sensor(s)408can detect weather event(s) proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location of water generating unit310(FIG.3) (e.g., in real time). In some embodiments, weather event sensor(s)408can comprise any suitable device or devices configured to detect one or more weather events proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied. Exemplary weather event(s) can include a storm (e.g., a rain storm, a wind storm, a snow storm, an ice storm, a dust storm, etc.) and a toxic air quality condition, etc. In many embodiments, a storm can refer to any event that can cause fluids and/or particles to be deposited on and/or in the substance(s) to which the ozone generated by ozone generator401is to be applied. In these or other embodiments, weather event sensor(s)408can comprise (i) a barometer, such as, for example, to detect changes in atmospheric pressure associated with a rain storm, (ii) a particle sensor, such as, for example, to detect a sandstorm or a toxic particle pollution condition, and/or (iii) one or more gas sensors, such as, for example to detect a toxic gas pollution condition. In some embodiments, weather event sensor(s)408can be electrically coupled to ozone generator control system402to provide notifications of weather events to ozone generator control system402. In other embodiments, temperature sensor407and/or weather event sensor(s)408can be omitted and replaced with information from a third-party weather service, such as, for example, The Weather Company, LLC of Atlanta, Ga., United States of America (www.weather.com). In many embodiments, maintenance sensor409can detect when maintenance has been performed and completed on water supply system301ofFIG.3(e.g., water generating unit310(FIG.3)). Accordingly, in many embodiments, ozone generator system302(FIG.3) can comprise maintenance sensor409when system300(FIG.3) comprises maintenance sensor409. In some embodiments, maintenance sensor409can comprise any suitable device configured to detect when maintenance has been performed and completed on water supply system301ofFIG.3(e.g., water generating unit310(FIG.3)). In some embodiments, maintenance sensor409can automatically detect when maintenance has been performed and completed on water supply system301ofFIG.3(e.g., water generating unit310(FIG.3)). In these or other embodiments, maintenance sensor409can receive an input from a mechanic that the maintenance has been performed and completed on water supply system301ofFIG.3(e.g., water generating unit310(FIG.3)) in order to detect that maintenance has been performed and completed on water supply system301ofFIG.3(e.g., water generating unit310(FIG.3)). In some embodiments, maintenance sensor409can be electrically coupled to ozone generator control system402to provide notifications of completed maintenance events to ozone generator control system402. In many embodiments, water use sensor410can detect when water made available to the user of system300(FIG.3) by water supply system301(FIG.3) has been used. Accordingly, in many embodiments, ozone generator system302(FIG.3) can comprise water use sensor410when system300(FIG.3) comprises water use sensor410. In some embodiments, water use sensor410can comprise any suitable device configured to detect when water made available to the user of system300(FIG.3) by water supply system301(FIG.3) has been used. In some embodiments, water use sensor410can automatically detect when water made available to the user of system300(FIG.3) by water supply system301(FIG.3) has been used. In these or other embodiments, water use sensor410can receive an input from the user of system300(FIG.3) that the water made available to the user of system300(FIG.3) by water supply system301(FIG.3) has been used in order to detect that water made available to the user of system300(FIG.3) by water supply system301(FIG.3) has been used. In some embodiments, water use sensor410can be electrically coupled to ozone generator control system402to provide notifications of water use events to ozone generator control system402. In some embodiments, ozone sensor(s)411can detect and/or measure a concentration of ozone proximal to (e.g., within 2 meters of, within 10 meters of, within50meters of) or at a location where the ozone generated by ozone generator401is to be applied. In some embodiments, ozone sensor(s)411can comprise any suitable device configured to detect and/or measure a concentration of ozone proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied. For example, in some embodiments, ozone sensor(s)411can comprise an airborne ozone detector and/or an oxidation reduction potential electrode. In some embodiments, ozone sensor(s)411can be electrically coupled to ozone generator control system402to provide notifications of detected ozone and/or measurements of ozone concentration to ozone generator control system402. In some embodiments, microbial sensor(s)412can detect and/or measure a concentration of micro-organisms proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied. In some embodiments, ozone sensor(s)411can comprise any suitable device configured to detect and/or measure a concentration of micro-organisms proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied. For example, in some embodiments, microbial sensor(s)412can comprise an impedance sensor. In some embodiments, microbial sensor(s)412can be electrically coupled to ozone generator control system402to provide notifications of detected micro-organisms and/or measurements of micro-organism concentration to ozone generator control system402. In many embodiments, ozone generator control system402can control ozone generator401and/or blower405. By controlling ozone generator401and/or blower405, ozone generator control system402can optimize treatment (e.g., sanitation) of the substance(s) to which the ozone generated by ozone generator401(FIG.4) is applied. In some embodiments, ozone generator control system402can control how much ozone (e.g. a quantity of ozone) that ozone generator401generates and/or when ozone generator401generates ozone. In these or other embodiments, ozone generator control system402can control when blower405provides feed gas to ozone generator401and/or a feed rate with which blower405provides feed gas to ozone generator401. Accordingly, in many embodiments, ozone generator control system402can be electrically coupled to ozone generator401and/or blower405. In some embodiments, ozone generator control system402can control where the ozone generated by ozone generator401is applied. In these embodiments, ozone generator control system402can be electrically coupled to one or more valves configured to selectively permit or impede transfer of ozone from ozone generator system302(FIG.3) to one or more locations. Ozone generator control system402can control the opening and closing of the valve(s) to control where the ozone generated by ozone generator401is applied. Further, ozone generator control system402can be similar or identical to computer system100(FIG.1). In some embodiments, when system300(FIG.3) comprises water supply system301(FIG.3), and when water supply system301comprises water generating unit306(FIG.3), ozone generator control system402can comprise water generating unit control system310(FIG.3), and vice versa. In other embodiments, ozone generator control system402can be separate from water generating unit control system310(FIG.3). Turning ahead now in the drawings,FIG.5illustrates a representative block diagram of ozone generator control system402, according to the embodiment ofFIG.3. In many embodiments, ozone generator control system402can comprise one or more processors501and one or more memory storage devices502. Further, memory storage device(s)502can comprise one or more non-transitory memory storage devices503. Meanwhile, in these or other embodiments, ozone generator control system402comprises a communication system504, an ozone supply system505, and an ozone scheduling system506. In some embodiments, ozone generator control system402can comprise a feed gas supply system507, a feed gas scheduling system508, and/or an ozone target system509. In other embodiments, feed gas supply system507, feed gas scheduling system508, and/or ozone target system509can be omitted. In these or other embodiments, part or all of at least one or more of communication system504, ozone supply system505, ozone scheduling system506, feed gas supply system507, feed gas scheduling system508, and ozone target system509can be part of at least one or more others of communication system504, ozone supply system505, ozone scheduling system506, feed gas supply system507, feed gas scheduling system508, and ozone target system509, and vice versa. In many embodiments, processor(s)501can be similar or identical to the processor(s) described above with respect to computer system100(FIG.1); memory storage device(s)502can be similar or identical to the memory storage device(s) described above with respect to computer system100(FIG.1); and/or non-transitory memory storage device(s)503can be similar or identical to the non-transitory memory storage device(s) described above with respect to computer system100(FIG.1). Further, communication system504, ozone supply system505, ozone scheduling system506, feed gas supply system507, and feed gas scheduling system508can be implemented with hardware and/or software, as desirable. Although communication system504, ozone supply system505, ozone scheduling system506, feed gas supply system507, feed gas scheduling system508, and ozone target system509are shown atFIG.5as being separate from processor(s)501, memory storage device(s)502, and/or non-transitory memory storage device(s)503, in many embodiments, part or all of communication system504, ozone supply system505, ozone scheduling system506, feed gas supply system507, feed gas scheduling system508, and ozone target system509can be stored at memory storage device(s)502and/or non-transitory memory storage device(s)503and can be called and run at processor(s)501, such as, for example, when part or all of communication system504, ozone supply system505, ozone scheduling system506, feed gas supply system507, feed gas scheduling system508, and ozone target system509are implemented as software. In many embodiments, communication system504can provide and manage communication between the various elements of ozone generator control system402(e.g., processor(s)501, memory storage device(s)502, non-transitory memory storage device(s)503, ozone supply system505, ozone scheduling system506, feed gas supply system507, feed gas scheduling system508, ozone target system509, etc.) and manage incoming and outgoing communications between ozone generator control system402, ozone generator401(FIG.4), and blower405(FIG.4). Communication system504can be implemented using any suitable manner of wired and/or wireless communication, and/or using any one or any combination of wired and/or wireless communication network topologies and/or protocols. In many embodiments, communication system504can be part of hardware and/or software implemented for communications between ozone generator control system402, ozone generator401(FIG.4), and blower405(FIG.4). For example, as applicable, communication system504can permit processor(s)501to call (i) software (e.g., at least part of ozone supply system505, ozone scheduling system506, feed gas supply system507, feed gas scheduling system508, ozone target system509, etc.) stored at memory storage device(s)502and/or non-transitory memory storage device(s)503, and/or (ii) data stored at memory storage device(s)502and/or at non-transitory memory storage device(s)503. In many embodiments, ozone supply system505can control how much ozone (e.g. a quantity of ozone) that ozone generator401(FIG.4) generates. In some embodiments, ozone supply system505can selectively activate and deactivate ozone generator401(FIG.4) to regulate how much ozone that ozone generator401(FIG.4) generates. In some embodiments, ozone supply system505can control how much ozone (e.g. a quantity of ozone) that ozone generator401(FIG.4) generates based on an ambient temperature proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied. For example, ozone supply system505can establish and/or adjust (e.g., in real time) how much ozone (e.g. a quantity of ozone) that ozone generator401(FIG.4) generates based on the ambient temperature. In further embodiments, ozone supply system505can receive the ambient temperature from temperature sensor407(FIG.4). Controlling how much ozone (e.g. a quantity of ozone) that ozone generator401(FIG.4) generates based on an ambient temperature proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied can be advantageous because a concentration of ozone in a volume is temperature dependent. For example, as temperature increases, ozone molecules will dissociate more quickly as the ozone molecules collide more frequently. Accordingly, ozone supply system505can increase how much ozone (e.g. a quantity of ozone) that ozone generator401(FIG.4) generates to maintain a desired quantity of ozone. In some embodiments, ozone supply system505can control how much ozone (e.g. a quantity of ozone) that ozone generator401(FIG.4) generates based on detecting a weather event proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied. For example, ozone supply system505can establish and/or adjust (e.g., in real time) how much ozone (e.g. a quantity of ozone) that ozone generator401(FIG.4) generates based on detecting the weather event. In further embodiments, ozone supply system505can receive a notification of the weather event from one or more of weather event sensor(s)408(FIG.4). Controlling how much ozone (e.g. a quantity of ozone) that ozone generator401(FIG.4) generates based on detecting a weather event proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied can be advantageous because weather events (e.g., storms, toxic pollution events, etc.) can affect how much ozone is needed to adequately sterilize the substance(s) to which the ozone is to be applied (e.g., the water made available to the user of system300(FIG.3) by water supply system301(FIG.3) and/or (ii) the interior surface(s) of water generating unit306(FIG.3), heater307(FIG.3), desiccation device308(FIG.3), and/or condenser309(FIG.3)). For example, a dust storm can increase the presence of particles in the substance(s) to which the ozone is to be applied (e.g., the water made available to the user of system300(FIG.3) by water supply system301(FIG.3) and/or (ii) the interior surface(s) of water generating unit306(FIG.3), heater307(FIG.3), desiccation device308(FIG.3), and/or condenser309(FIG.3)). Accordingly, ozone supply system505can increase how much ozone (e.g. a quantity of ozone) that ozone generator401(FIG.4) generates to compensate for the increased presence of particles in the substance(s). In some embodiments, ozone supply system505can control how much ozone (e.g. a quantity of ozone) that ozone generator401(FIG.4) generates such that (i) a concentration of the ozone remains below a maximum concentration value and/or (ii) a CT value of the ozone remains above a minimum CT value when the ozone is applied to the substance(s) to which the ozone is to be applied (e.g., the water made available to the user of system300(FIG.3) by water supply system301(FIG.3) and/or (ii) the interior surface(s) of water generating unit306(FIG.3), heater307(FIG.3), desiccation device308(FIG.3), and/or condenser309(FIG.3)). CT value can refer to a product of the concentration and exposure time of the ozone to the substance(s) to which the ozone is to be applied (e.g., the water made available to the user of system300(FIG.3) by water supply system301(FIG.3) and/or (ii) the interior surface(s) of water generating unit306(FIG.3), heater307(FIG.3), desiccation device308(FIG.3), and/or condenser309(FIG.3)). In many embodiments, the maximum concentration value can be set to a value that prevents ozone from remaining in the water made available to the user of system300(FIG.3) by water supply system301(FIG.3) when the user drinks the water. That is, the maximum concentration value can be set to ensure that any ozone in the water is dissociated before the water is used by the user of system300(FIG.3). For example, in some embodiments, the maximum concentration value can be 0.4 parts per million. In these or other embodiments, the minimum CT value can be set to a value that ensures the ozone is lethal to any toxic or otherwise undesirable organism or organisms (e.g., a virus, a bacterium, an alga, etc.) in the water made available to the user of system300(FIG.3) by water supply system301(FIG.3). For example, in some embodiments, the minimum CT value can be 2. Accordingly, restricting the concentration value and/or CT value of the ozone can ensure the water is safe for the user of system300(FIG.3) to drink. In some embodiments, ozone supply system505can control how much ozone (e.g. a quantity of ozone) that ozone generator401(FIG.4) generates based on detecting ozone and/or an ozone concentration proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied. For example, ozone supply system505can establish and/or adjust (e.g., in real time) how much ozone (e.g. a quantity of ozone) that ozone generator401(FIG.4) generates based on detecting ozone and/or the ozone concentration. In further embodiments, ozone supply system505can receive notifications of detected ozone and/or the ozone concentration from ozone sensor(s)411(FIG.4). In some embodiments, ozone supply system505can control how much ozone (e.g. a quantity of ozone) that ozone generator401(FIG.4) generates based on detecting micro-organisms and/or a micro-organism concentration proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied. For example, ozone supply system505can establish and/or adjust (e.g., in real time) how much ozone (e.g. a quantity of ozone) that ozone generator401(FIG.4) generates based on detecting ozone and/or the micro-organism concentration. In further embodiments, ozone supply system505can receive notifications of detection of micro-organisms and/or the micro-organism concentration from microbial sensor(s)412(FIG.4). In many embodiments, ozone scheduling system506can control when ozone generator401(FIG.4) generates ozone. In some embodiments, ozone scheduling system506can selectively activate and deactivate ozone generator401(FIG.4) to regulate when ozone generator401(FIG.4) generates ozone. For example, in many embodiments, ozone scheduling system506can cause ozone generator401(FIG.4) to generate ozone for one or more periods of time at one or more times of day and on one or more days of the week. In these or other embodiments, ozone scheduling system506can cause ozone generator506to generate ozone for one or more periods of time at one or more regular intervals (e.g., every minute, every quarter hour, every half hour, every hour, etc.). In these or other embodiments, ozone scheduling system506can cause ozone generator401(FIG.4) not to generate ozone for one or more periods of time at one or more times of day and on one or more days of the week, and/or for one or more periods of time at one or more regular intervals (e.g., every minute, every quarter hour, every half hour, every hour, etc.). In some embodiments, ozone scheduling system506can control when ozone generator401(FIG.4) generates ozone based on detecting a weather event proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied (e.g., in real time). For example, in various embodiments, ozone scheduling system506can cause ozone generator401(FIG.4) to generate ozone in response to receiving a notification of a weather event from one or more of weather event sensor(s)408(FIG.4). In further embodiments, ozone scheduling system506can receive the notification of the weather event from one or more of weather event sensor(s)408(FIG.4). Causing ozone generator401(FIG.4) to generate ozone when a weather event is detected proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied can be advantageous because weather events (e.g., storms, toxic pollution events, etc.) can contaminate the substance(s) to which the ozone is to be applied (e.g., the water made available to the user of system300(FIG.3) by water supply system301(FIG.3) and/or (ii) the interior surface(s) of water generating unit306(FIG.3), heater307(FIG.3), desiccation device308(FIG.3), and/or condenser309(FIG.3)). In some embodiments, ozone schedule system506can control when ozone generator401(FIG.4) generates ozone based on detecting that maintenance has been performed and completed on water supply system301ofFIG.3(e.g., water generating unit310(FIG.3)). For example, in various embodiments, ozone scheduling system506can cause ozone generator401(FIG.4) to generate ozone in response to determining that a maintenance event has occurred. In some embodiments, ozone scheduling system506can receive a notification of a maintenance event from maintenance sensor409(FIG.4). Causing ozone generator401(FIG.4) to generate ozone when a maintenance event is detected can be advantageous because maintenance events can contaminate the substance(s) to which the ozone is to be applied (e.g., the water made available to the user of system300(FIG.3) by water supply system301(FIG.3) and/or (ii) the interior surface(s) of water generating unit306(FIG.3), heater307(FIG.3), desiccation device308(FIG.3), and/or condenser309(FIG.3)). In some embodiments, ozone scheduling system506can control when ozone generator401(FIG.4) generates ozone based on detecting a non-use interval of the water made available to the user of system300(FIG.3) by water supply system301(FIG.3). For example, in various embodiments, ozone scheduling system506can cause ozone generator401(FIG.4) to generate ozone in response to determining that a non-use interval has elapsed. A non-use interval can refer to a predetermined period of time since water made available to the user of system300(FIG.3) by water supply system301(FIG.3) has been used. The predetermined period of time can be set to be sufficiently often to prevent contaminants from building up in the water made available to the user of system300(FIG.3) by water supply system301(FIG.3) in between uses. In some embodiments, ozone scheduling system506can receive notification(s) of when water made available to the user of system300(FIG.3) by water supply system301(FIG.3) is used from water use sensor410(FIG.4). Then, ozone scheduling system506can track how much time has elapsed since receiving a most recent notification of when water made available to the user of system300(FIG.3) by water supply system301(FIG.3) is used. In some embodiments, ozone schedule system506can control when ozone generator401(FIG.4) generates ozone based on detecting ozone and/or an ozone concentration proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied. For example, in various embodiments, ozone scheduling system506can cause ozone generator401(FIG.4) to generate ozone in response to detecting ozone proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied. In some embodiments, ozone scheduling system506can receive a notification of detected ozone from ozone sensor(s)411(FIG.4). Further, in various embodiments, ozone scheduling system506can cause ozone generator401(FIG.4) to generate ozone as a function of the ozone concentration and an ozone decomposition rate. In some embodiments, ozone scheduling system506can receive the ozone concentration from ozone sensor(s)411(FIG.4). In some embodiments, ozone schedule system506can control when ozone generator401(FIG.4) generates ozone based on detecting micro-organisms and/or a micro-organism concentration proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied. For example, in various embodiments, ozone scheduling system506can cause ozone generator401(FIG.4) to generate ozone in response to detecting micro-organisms proximal to (e.g., within 2 meters of, within 10 meters of, within 50 meters of) or at a location where the ozone generated by ozone generator401is to be applied. In some embodiments, ozone scheduling system506can receive a notification of detected micro-organisms from microbial sensor(s)411(FIG.4). Further, in various embodiments, ozone scheduling system506can cause ozone generator401(FIG.4) to generate ozone as a function of the micro-organism concentration and a lethality time. In some embodiments, ozone scheduling system506can receive the micro-organism concentration from microbial sensor(s)412(FIG.4). In many embodiments, feed gas supply system507can control when blower405(FIG.4) provides feed gas to ozone generator401(FIG.4). In some embodiments, ozone scheduling system506can selectively activate and deactivate blower405(FIG.4) to regulate when blower405(FIG.4) provides feed gas to ozone generator401(FIG.4). In many embodiments, feed gas supply system507can communicate with ozone supply system505and/or ozone scheduling system506to coordinate control of blower405(FIG.4) providing feed gas to ozone generator401(FIG.4) with control of ozone generator401(FIG.4) by ozone supply system505and/or ozone scheduling system506. In many embodiments, feed gas scheduling system508can control a feed rate with which blower405(FIG.4) provides feed gas to ozone generator401(FIG.4). In some embodiments, ozone scheduling system506can selectively activate and deactivate blower405(FIG.4) to regulate when blower405(FIG.4) provides feed gas to ozone generator401(FIG.4). In many embodiments, feed gas scheduling system507can communicate with ozone supply system505and/or ozone scheduling system506to coordinate control of blower405(FIG.4) controlling a feed rate of feed gas provided to ozone generator401(FIG.4) with control of ozone generator401(FIG.4) by ozone supply system505and/or ozone scheduling system506. In many embodiments, ozone target system509can control to where the ozone generated by ozone generator401is applied. In these embodiments, ozone target system509can control the opening and closing of the valve(s) configured to selectively permit and impede the flow of the ozone generated by ozone generator401to control where the ozone generated by ozone generator401is applied. For convenience, the functionality of system300generally is described herein as it relates particularly to one user, but in many embodiments, the functionality of system300can be extended to multiple users, at the same or at different times. Further, although system300and/or ozone generation system302are discussed with respect to ozone, in other embodiments, one or more other chemicals can be generated, controlled, and applied, such as, for example, to one or more substance(s) (e.g., water). Further still, although the water made available to the user of system300(FIG.3) is generally described herein as being in a liquid form, in other embodiments, the water can be made available to the user of system300(FIG.3) in a solid or gaseous form. Turning ahead now in the drawings,FIG.6illustrates a flow chart for an embodiment of a method600of providing (e.g., manufacturing) a system. Method600is merely exemplary and is not limited to the embodiments presented herein. Method600can be employed in many different embodiments or examples not specifically depicted or described herein. In some embodiments, the activities of method600can be performed in the order presented. In other embodiments, the activities of the method600can be performed in any other suitable order. In still other embodiments, one or more of the activities in method600can be combined or skipped. In many embodiments, the system can be similar or identical to system300(FIG.3). In many embodiments, method600can comprise activity601of providing an ozone generator system. In some embodiments, the ozone generator system can be similar or identical to ozone generator system302(FIG.3).FIG.7illustrates an exemplary activity601, according to the embodiment ofFIG.6. In many embodiments, activity601can comprise activity701of providing an ozone generator. In some embodiments, the ozone generator can be similar or identical to ozone generator401(FIG.4). In many embodiments, activity601can comprise activity702of providing an ozone generator control system. In some embodiments, the ozone generator control system can be similar or identical to ozone generator control system402(FIG.4).FIG.8illustrates an exemplary activity702, according to the embodiment ofFIG.6. In many embodiments, activity702can comprise activity801of providing one or more processors. In some embodiments, the processor(s) can be similar or identical to processor(s)501(FIG.5). In many embodiments, activity702can comprise activity802of providing one or more memory storage devices. In some embodiments, the memory storage device(s) can be similar or identical to memory storage device(s)502(FIG.5). In many embodiments, activity702can comprise activity803of providing a communication system. In some embodiments, the communication system can be similar or identical to communication system504(FIG.5). In many embodiments, activity702can comprise activity804of providing an ozone supply system. In some embodiments, the ozone supply system can be similar or identical to ozone supply system505(FIG.5). In many embodiments, activity702can comprise activity805of providing an ozone scheduling system. In some embodiments, the ozone scheduling system can be similar or identical to ozone scheduling system506(FIG.5). In many embodiments, activity702can comprise activity806of providing a feed gas supply system. In some embodiments, the feed gas supply system can be similar or identical to feed gas supply system507(FIG.5). In some embodiments, activity806can be omitted. In many embodiments, activity702can comprise activity807of providing a feed gas scheduling system. In some embodiments, the feed gas scheduling system can be similar or identical to feed gas scheduling system508(FIG.5). In some embodiments, activity807can be omitted. In many embodiments, activity702can comprise activity808of providing an ozone target system. In some embodiments, the ozone target system can be similar or identical to ozone target system509(FIG.5). In some embodiments, activity Turning now back toFIG.7, in many embodiments, activity601can comprise activity703of providing an energy source. In some embodiments, the energy source can be similar or identical to energy source403(FIG.4). In many embodiments, activity601can comprise activity704of providing a transformer. In some embodiments, the transformer can be similar or identical to transformer404(FIG.4). In some embodiments, activity704can be omitted. In many embodiments, activity601can comprise activity705of providing a blower. In some embodiments, the blower can be similar or identical to blower405(FIG.4). In some embodiments, activity705can be omitted. In many embodiments, activity601can comprise activity706of providing one or more ozone injectors. In some embodiments, the ozone injector(s) can be similar or identical to ozone injector(s)406(FIG.4). In some embodiments, activity706can be omitted. In many embodiments, activity601can comprise activity707of providing one or more sensors. In some embodiments, the sensor(s) can be similar or identical to temperature sensor407(FIG.4), weather event sensor(s)408(FIG.4), maintenance sensor409(FIG.4), and/or water use sensor410(FIG.4). In some embodiments, activity707can be omitted. In many embodiments, activity601can comprise activity708of coupling the blower to the ozone generator. In some embodiments, activity708can be omitted. In many embodiments, activity601can comprise activity709of coupling the ozone generator to the ozone injector(s). In some embodiments, activity709can be omitted. In many embodiments, activity601can comprise activity710of electrically coupling the energy source to the blower, the ozone generator, the ozone generator control system, and/or the transformer. In many embodiments, activity602can comprise activity711of electrically coupling the ozone generator control system to the blower, the ozone generator, and/or the sensor(s). Turning now back toFIG.6, in many embodiments, method600can comprise activity602of providing a water supply system. The water supply system can be similar or identical to water supply system301(FIG.3). In some embodiments, activity602can be omitted.FIG.9illustrates an exemplary activity602, according to the embodiment ofFIG.6. In many embodiments, activity602can comprise activity901of providing a water generating unit. In some embodiments, the water generating unit can be similar or identical to water generating unit306(FIG.3). In some embodiments, activity901can be omitted. In many embodiments, activity602can comprise activity902of providing a reservoir. In some embodiments, the reservoir can be similar or identical to reservoir304(FIG.3). In some embodiments, activity902can be omitted. Turning again back toFIG.6, in many embodiments, method600can comprise activity603of coupling the ozone generator to the water supply system. In some embodiments, activity603can be omitted. Turning ahead now in the drawings,FIG.10illustrates a flow chart for an embodiment of a method1000. Method1000is merely exemplary and is not limited to the embodiments presented herein. Method1000can be employed in many different embodiments or examples not specifically depicted or described herein. In some embodiments, the activities of method1000can be performed in the order presented. In other embodiments, the activities of the method1000can be performed in any other suitable order. In still other embodiments, one or more of the activities in method1000can be combined or skipped. In many embodiments, method1000can comprise activity1001of generating ozone. In some embodiments, performing activity1001can be similar or identical to generating ozone as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, activity1001can be repeated one or more times.FIG.11illustrates an exemplary activity1001, according to the embodiment ofFIG.10. In many embodiments, activity1001can comprise activity1101of controlling a quantity of the ozone generated. In some embodiments, performing activity1101can be similar or identical to controlling a quantity of the ozone generated as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, activity1101can be repeated one or more times.FIG.12illustrates an exemplary activity1101, according to the embodiment ofFIG.10. In many embodiments, activity1101can comprise activity1201of establishing the quantity of ozone generated based on the ambient temperature measured proximal to where the ozone is to be applied to water. In some embodiments, performing activity1201can be similar or identical to establishing the quantity of ozone generated based on an ambient temperature measured proximal to where the ozone is to be applied to the water. In many embodiments, activity1201can be performed after activity1003(FIG.10). In some embodiments, activity1201can be repeated one or more times. In many embodiments, activity1101can comprise activity1202of adjusting the quantity of ozone generated based on the ambient temperature measured proximal to where the ozone is to be applied to the water. In some embodiments, performing activity1202can be similar or identical to adjusting the quantity of ozone generated based on the ambient temperature measured proximal to where the ozone is to be applied to the water. In many embodiments, activity1201can be performed after activity1003(FIG.10). In some embodiments, when activity1101comprises activity1202, activity1201can be omitted, and vice versa. In some embodiments, activity1202can be repeated one or more times. In many embodiments, activity1101can comprise activity1203of controlling the quantity of the ozone generated so that when the ozone is applied to the water, a CT value of the ozone remains above a minimum CT value and a concentration of the ozone remains below a maximum concentration value. In some embodiments, performing activity1203can be similar or identical to controlling the quantity of the ozone generated so that when the ozone is applied to the water, a CT value of the ozone remains above a minimum CT value and a concentration of the ozone remains below a maximum concentration value as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In these or other embodiments, the minimum CT value can be similar or identical to the minimum CT value described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3); and/or the maximum concentration value can be similar or identical to the maximum concentration value described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, activity1203can be repeated one or more times. In many embodiments, activity1101can comprise activity1204of establishing the quantity of ozone generated based on a weather event detected proximal to where the ozone is to be applied to the water. In some embodiments, performing activity1204can be similar or identical to establishing the quantity of ozone generated based on the weather event detected proximal to where the ozone is to be applied to the water. In further embodiments, the weather event can be similar or identical to one of the weather event(s) described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In many embodiments, activity1204can be performed after activity1004(FIG.10). In some embodiments, activity1204can be repeated one or more times. In many embodiments, activity1101can comprise activity1205of adjusting the quantity of ozone generated based on the weather event detected proximal to where the ozone is to be applied to the water. In some embodiments, performing activity1205can be similar or identical to adjusting the quantity of ozone generated based on the weather event detected proximal to where the ozone is to be applied to the water. In many embodiments, activity1205can be performed after activity1004(FIG.10). In further embodiments, when activity1101comprises activity1205, activity1204can be omitted, and vice versa. In some embodiments, activity1205can be repeated one or more times. In many embodiments, activity1101can comprise an activity of establishing the quantity of ozone generated based on detecting present ozone and/or the concentration of present ozone proximal to where the ozone is to be applied to the water. In some embodiments, performing the activity of establishing the quantity of ozone generated based on detecting present ozone and/or the concentration of present ozone proximal to where the ozone is to be applied to the water can be similar or identical to establishing the quantity of ozone generated based on detecting present ozone and/or the concentration of present ozone proximal to where the ozone is to be applied to the water as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, the activity of establishing the quantity of ozone generated based on detecting present ozone and/or the concentration of present ozone proximal to where the ozone is to be applied to the water can be repeated one or more times. In many embodiments, activity1101can comprise an activity of adjusting the quantity of ozone generated based on detecting present ozone and/or a concentration of the present ozone proximal to where the ozone is to be applied to the water. In some embodiments, performing the activity of adjusting the quantity of ozone generated based on detecting present ozone and/or the concentration of present ozone proximal to where the ozone is to be applied to the water can be similar or identical to adjusting the quantity of ozone generated based on detecting present ozone and/or the concentration of present ozone proximal to where the ozone is to be applied to the water as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, the activity of adjusting the quantity of ozone generated based on detecting present ozone and/or a concentration of the present ozone proximal to where the ozone is to be applied to the water can be repeated one or more times. In many embodiments, activity1101can comprise an activity of establishing the quantity of ozone generated based on detecting micro-organisms and/or the concentration of micro-organisms proximal to where the ozone is to be applied to the water. In some embodiments, performing the activity of establishing the quantity of ozone generated based on detecting micro-organisms and/or the concentration of micro-organisms proximal to where the ozone is to be applied to the water can be similar or identical to establishing the quantity of ozone generated based on detecting micro-organisms and/or the concentration of micro-organisms proximal to where the ozone is to be applied to the water as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, the activity of establishing the quantity of ozone generated based on detecting micro-organisms and/or the concentration of micro-organisms proximal to where the ozone is to be applied to the water can be repeated one or more times. In many embodiments, activity1101can comprise an activity of adjusting the quantity of ozone generated based on detecting micro-organisms and/or the concentration of micro-organisms proximal to where the ozone is to be applied to the water. In some embodiments, performing the activity of adjusting the quantity of ozone generated based on detecting micro-organisms and/or the concentration of micro-organisms proximal to where the ozone is to be applied to the water can be similar or identical to adjusting the quantity of ozone generated based on detecting micro-organisms and/or the concentration of micro-organisms proximal to where the ozone is to be applied to the water as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, the activity of adjusting the quantity of ozone generated based on detecting micro-organisms and/or the concentration of micro-organisms proximal to where the ozone is to be applied to the water can be repeated one or more times. Turning now back toFIG.11, in many embodiments, activity1001can comprise activity1102of controlling when the ozone is generated. In some embodiments, performing activity1102can be similar or identical to controlling when the ozone is generated as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, activity1102can be repeated one or more times.FIG.13illustrates an exemplary activity1102, according to the embodiment ofFIG.10. In many embodiments, activity1102can comprise activity1301of generating the ozone for a period of time at a time of day. In some embodiments, performing activity1301can be similar or identical to generating the ozone for a period of time at a time of day as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, activity1301can be repeated one or more times. In many embodiments, activity1102can comprise activity1302of preventing the ozone from being generated for a period of time at a time of day. In some embodiments, performing activity1302can be similar or identical to preventing the ozone from being generated for a period of time at a time of day as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, activity1302can be repeated one or more times. In many embodiments, activity1102can comprise activity1303of generating the ozone for a period of time at a regular time interval. In some embodiments, performing activity1303can be similar or identical to generating the ozone for a period of time at a regular time interval as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, activity1303can be repeated one or more times. In many embodiments, activity1102can comprise activity1304of generating the ozone for a period of time based on detecting the weather event proximal to where the ozone is to be applied to the water. In some embodiments, performing activity1304can be similar or identical to generating the ozone for a period of time based on detecting the weather event proximal to where the ozone is to be applied to the water as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, activity1304can be repeated one or more times. In many embodiments, activity1102can comprise activity1305of generating the ozone for a period of time based on detecting the non-use interval of the water. In some embodiments, performing activity1305can be similar or identical to generating the ozone for a period of time based on detecting the non-use interval of the water as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, activity1305can be repeated one or more times. In many embodiments, activity1102can comprise activity1306of generating the ozone for a period of time based on detecting the maintenance event at the water generating unit has been completed. In some embodiments, performing activity1306can be similar or identical to generating the ozone for a period of time based on detecting the maintenance event at the water generating unit has been completed as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, activity1306can be repeated one or more times. In many embodiments, activity1101can comprise an activity of generating the ozone for a period of time based on detecting present ozone and/or the concentration of present ozone proximal to where the ozone is to be applied to the water. In some embodiments, performing the activity of generating the ozone for a period of time based on detecting present ozone and/or the concentration of present ozone proximal to where the ozone is to be applied to the water can be similar or identical to generating the ozone for a period of time based on detecting present ozone and/or the concentration of present ozone proximal to where the ozone is to be applied to the water as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, the activity of generating the ozone for a period of time based on detecting present ozone and/or the concentration of present ozone proximal to where the ozone is to be applied to the water can be repeated one or more times. In many embodiments, activity1101can comprise an activity of generating the ozone for a period of time based on detecting micro-organisms and/or the concentration of micro-organisms proximal to where the ozone is to be applied to the water. In some embodiments, performing the activity of generating the ozone for a period of time based on detecting micro-organisms and/or the concentration of micro-organisms proximal to where the ozone is to be applied to the water can be similar or identical to generating the ozone for a period of time based on detecting micro-organisms and/or the concentration of micro-organisms proximal to where the ozone is to be applied to the water as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, the activity of generating the ozone for a period of time based on detecting micro-organisms and/or the concentration of micro-organisms proximal to where the ozone is to be applied to the water can be repeated one or more times. Turning now back toFIG.10, in many embodiments, method1000can comprise activity1002of applying the ozone to water. In some embodiments, performing activity1002can be similar or identical to applying the ozone to water as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, activity1002can be repeated one or more times. In many embodiments, method1000can comprise activity1003of measuring the ambient temperature proximal to where the ozone is to be applied to the water. In some embodiments, performing activity1003can be similar or identical to measuring an ambient temperature proximal to where the ozone is to be applied to the water as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, activity1003can be repeated one or more times. In many embodiments, method1000can comprise activity1004of detecting the weather event proximal to where the ozone is to be applied to the water. In some embodiments, performing activity1004can be similar or identical to detecting the weather event proximal to where the ozone is to be applied to the water as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, activity1004can be repeated one or more times. In many embodiments, method1000can comprise activity1005of detecting a non-use interval of the water. In some embodiments, performing activity1005can be similar or identical to detecting a non-use interval of the water as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In further embodiments, the non-use interval can be similar or identical to the non-use interval described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, activity1005can be repeated one or more times. In many embodiments, method1000can comprise activity1006of generating the water with a water generating unit. In some embodiments, performing activity1006can be similar or identical to generating the water with a water generating unit as described above with respect to system300(FIG.3) and/or water supply system301(FIG.3). In further embodiments, the water generating unit can be similar or identical to water generating unit306(FIG.3). In some embodiments, activity1006can be repeated one or more times. In many embodiments, method1000can comprise activity1007of detecting a maintenance event at the water generating unit has been completed. In some embodiments, performing activity1007can be similar or identical to detecting a maintenance event at the water generating unit has been completed as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In further embodiments, the maintenance event can be similar or identical to the maintenance event(s) described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, activity1007can be repeated one or more times. In many embodiments, method1000can comprise activity1008of applying the ozone to an interior surface of a condenser of the water generating unit. In some embodiments, performing activity1008can be similar or identical to applying the ozone to an interior surface of a condenser of the water generating unit as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In further embodiments, the condenser can be similar or identical to condenser309(FIG.3). In some embodiments, activity1008can be repeated one or more times. In many embodiments, method1000can comprise activity1009of applying the ozone to an interior surface of a desiccation device of the water generating unit. In some embodiments, performing activity1008can be similar or identical to applying the ozone to an interior surface of a desiccation device of the water generating unit as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In further embodiments, the desiccation device can be similar or identical to desiccation device308(FIG.3). In some embodiments, activity1009can be repeated one or more times. In many embodiments, method100can comprise an activity of detecting present ozone proximal to where the ozone is to be applied to the water. In some embodiments, performing the activity of detecting the present ozone proximal to where the ozone is to be applied to the water can be similar or identical to detecting the present ozone proximal to where the ozone is to be applied to the water as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, the activity of detecting present ozone proximal to where the ozone is to be applied to the water can be repeated one or more times. In many embodiments, method100can comprise an activity of measuring a concentration of present ozone proximal to where the ozone is to be applied to the water. In some embodiments, performing the activity of measuring the concentration of present ozone proximal to where the ozone is to be applied to the water can be similar or identical to measuring the concentration of present ozone proximal to where the ozone is to be applied to the water as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, the activity of measuring a concentration of present ozone proximal to where the ozone is to be applied to the water can be repeated one or more times. In many embodiments, method100can comprise an activity of detecting micro-organisms proximal to where the ozone is to be applied to the water. In some embodiments, performing the activity of detecting the micro-organisms proximal to where the ozone is to be applied to the water can be similar or identical to detecting the micro-organisms proximal to where the ozone is to be applied to the water as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, the activity of detecting micro-organisms proximal to where the ozone is to be applied to the water can be repeated one or more times. In many embodiments, method100can comprise an activity of measuring a concentration of micro-organisms proximal to where the ozone is to be applied to the water. In some embodiments, performing the activity of measuring the micro-organisms proximal to where the ozone is to be applied to the water can be similar or identical to measuring the concentration of micro-organisms proximal to where the ozone is to be applied to the water as described above with respect to system300(FIG.3) and/or ozone generator system302(FIG.3). In some embodiments, the activity of measuring a concentration of micro-organisms proximal to where the ozone is to be applied to the water can be repeated one or more times. Although the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes may be made without departing from the spirit or scope of the disclosure. Accordingly, the disclosure of embodiments is intended to be illustrative of the scope of the disclosure and is not intended to be limiting. It is intended that the scope of the disclosure shall be limited only to the extent required by the appended claims. For example, to one of ordinary skill in the art, it will be readily apparent that any element ofFIGS.1-13may be modified, and that the foregoing discussion of certain of these embodiments does not necessarily represent a complete description of all possible embodiments. For example, one or more of the activities of the methods described herein may include different activities and be performed by many different elements, in many different orders. As another example, the elements within system300(FIG.3) can be interchanged or otherwise modified. Generally, replacement of one or more claimed elements constitutes reconstruction and not repair. Additionally, benefits, other advantages, and solutions to problems have been described with regard to specific embodiments. The benefits, advantages, solutions to problems, and any element or elements that may cause any benefit, advantage, or solution to occur or become more pronounced, however, are not to be construed as critical, required, or essential features or elements of any or all of the claims, unless such benefits, advantages, solutions, or elements are stated in such claim. Moreover, embodiments and limitations disclosed herein are not dedicated to the public under the doctrine of dedication if the embodiments and/or limitations: (1) are not expressly claimed in the claims; and (2) are or are potentially equivalents of express elements and/or limitations in the claims under the doctrine of equivalents. | 98,133 |
11858836 | DETAILED DESCRIPTION OF THE EMBODIMENTS For clear understanding of the objectives, features and advantages of the present disclosure, detailed description of the present disclosure will be given below in conjunction with accompanying drawings and specific embodiments. It should be noted that the embodiments described herein are only meant to explain the present disclosure, and not to limit the scope of the present disclosure. Furthermore, the technical features related to the embodiments of the disclosure described below can be mutually combined if they are not found to be mutually exclusive. The disclosure is directed to iron-containing sludge generated by sludge or sewage treatment with an iron-containing conditioner (e.g., the advanced oxidation technology using Fenton reagent), and emphatically to an iron-containing sludge cake obtained by deep dewatering of sludge with the Fenton composite conditioner, in which the preparation process of the iron-containing sludge cake can be obtained by referring to, for example, the existing sludge dewatering composite conditioner and the application method thereof disclosed in the Chinese patent document CN102381828A to obtain a deeply dewatered sludge cake with a moisture content of 40% to 60% (the deeply dewatered sludge cake may also be dewatered to reduce the moisture content to 0 to 60%, for example, 10%). The deeply dewatered iron-containing sludge cake is pyrolyzed under an inert gas atmosphere, and the resulting residue is called iron-containing sludge pyrolysis residue. Pyrolysis gases and tar produced in the pyrolysis process can also be recycled as secondary fuel. The present disclosure relates to a sludge composite conditioner based on iron-containing sludge pyrolysis residue as well as a preparation method and use thereof, belonging to a method for recycling iron-containing sludge, in which a sludge deep dewatering conditioner for sludge conditioning can be obtained by a pyrolysis method, the preparation method of the iron-containing sludge pyrolysis residue comprising: Step S11: preparing a deeply dewatered sludge cake with a moisture content of 40% to 60% by using the Fenton or Fenton-like reagent and the skeleton builder (referring to the sludge conditioning method disclosed in Chinese Patent Application CN102381828A). In one embodiment, the used transition metal salt is a ferrous salt, the used free radical generator is hydrogen peroxide, and the used skeleton builder is red mud. Step S12: feeding the prepared deeply dewatered sludge cake into a pyrolysis furnace, and performing sludge pyrolysis under an inert atmosphere to obtain iron-containing sludge pyrolysis residue. In the step S12, the inert gas may be at least one of nitrogen gas and argon gas, and the flow rate of the inert gas may be 0.1 to 0.3 L/min; the pyrolysis temperature may be 600° C. to 1000° C., and the pyrolysis time may be 30 min to 90 min. In the step S12, in addition to the iron-containing sludge pyrolysis residue, pyrolysis gases and tar may be generated in the pyrolysis process of the sludge cake, and these pyrolysis gases and tar can also be recycled as secondary fuel. An application method of the prepared iron-containing sludge pyrolysis residue comprises the following steps: Step S21: adjusting a pH of the surplus sludge to be treated to 1 to 6.5 with an acid. The used acid may be one of sulfuric acid, hydrochloric acid and nitric acid (of course, other acids such as oxalic acid and citric acid may also be used to satisfy the pH). Step S22: adding the above pyrolysis residue to the sludge, the additive amount being 20% to 80% in sludge dry basis; and then performing a stirring operation. The stirring rate may be, for example, 120 to 200 rpm, and the stirring time may be, for example, 2 to 8 minutes. Step S23: adding an oxidant to the sludge, the additive amount being 3% to 10% in sludge dry basis; and then performing a stirring operation. The stirring rate may be, for example, 70 to 120 rpm, and the stirring time may be, for example, 15 to 50 minutes. In the preparation and application methods of the above-mentioned iron sludge pyrolysis residue, the iron-containing sludge is pyrolyzed to obtain residue with high iron content, and then the residue is used to replace the originally purchased ferrous salt in the conventional advanced oxidation process for sludge conditioning, which not only solves the problem of the treatment and disposal of a large amount of iron-containing sludge, but also combines sludge dewatering and sludge pyrolysis processes to form a sustainable development route of sludge dewatering, pyrolysis gas production and residue recycling. The following are specific embodiments: Embodiment 1 In the present embodiment, preparation and application methods of the iron-containing sludge pyrolysis residue are as follows. (1) 17 kg of sludge and 128.2 g of FeSO4.7H2O were respectively added to a sludge conditioning tank, and stirring was performed at a stirring rate of 150 rpm and a stirring time of 5 min; then, 104.9 mL of 30% hydrogen peroxide was added, and stirring was performed at a stirring rate of 100 rpm and a stirring time of 30 min to allow the oxidant to fully react with the sludge; finally, 166 g of red mud was added, and rapid stirring was performed for conditioning at a stirring rate of 150 rpm and a stirring time of 5 min. In the above red mud, the percentage of iron is 26%, the mass percentage of aluminum oxide is 18%, the mass percentage of titanium oxide is 6%, and the mass percentage of silica and other minerals is 50%. Finally, 17.4 kg of conditioning sludge was obtained. (2) The conditioning sludge was dewatered with a plate and frame filter press. 17.4 kg of conditioning sludge was firstly pumped into a 50 L sludge feed tank by a pump, and then the conditioning sludge in the sludge feed tank was pressed into a diaphragm plate frame by a pneumatic press to be dewatered. In order to squeeze the sludge, the pressure of the pneumatic press was increased to 0.8 MPa at a rate of 0.1 MPa/min and kept for 25 min; and then the pressure was increased to 1.2 MPa at a rate of 0.1 MPa/min and kept for 25 min. Finally, 1.08 kg of deeply dewatered sludge cake with a moisture content of 52% can be obtained, and the iron content of the sludge cake was tested to be 18.35% (the iron content is measured in sludge cake dry basis, and specifically, a part of sludge cake is dried and then measured). (3) The obtained sludge cake was dried, and placed in an oven at 105° C. for 24 h, thereby obtaining 518.4 g of absolute-dried sludge cake. (4) The absolute-dried sludge cake was pyrolyzed by using a horizontal tube pyrolysis furnace. Nitrogen was introduced at 0.3 L/min to discharge air in the system, 30 g of the absolute-dried sludge cake as pyrolysis material was placed the furnace, and the temperature was raised to 800° C. at a heating rate of 10° C./min and then kept for 90 min, thereby obtaining pyrolysis residue. (5) 200 g of sludge with a water content of 97% was placed in a beaker (the dry mass of the sludge is 6 g), and the pH of the sludge was adjusted to 2 with a 30% sulfuric acid solution; 1.3 g of the above residue was added to the sludge, and then stirring is performed at a stirring rate of 150 rpm and a stirring time of 5 min; 2 mL of 30% hydrogen peroxide was added, and then stirring was performed at a stirring rate of 100 rpm and a stirring time of 30 min, thereby obtaining residue conditioned sludge. The capillary sop time (CST) and the specific resistance to filtration (SRF) of the conditioned sludge in the present embodiment are shown in Table 1. Embodiment 2 In the present embodiment, preparation and application methods of the iron-containing sludge pyrolysis residue are as follows. (1) 17 kg of sludge and 58.57 g of FeCl2were respectively added to a sludge conditioning tank, and stirring was performed at a stirring rate of 150 rpm and a stirring time of 5 min; then, 104.9 mL of 30% hydrogen peroxide was added, and stirring was performed at a stirring rate of 100 rpm and a stirring time of 30 min to allow the oxidant to fully react with the sludge; finally, 15 g of quick lime was added, and rapid stirring was performed for conditioning at a stirring rate of 150 rpm and a stirring time of 5 min. Finally, 17.3 kg of conditioning sludge was obtained. (2) The conditioning sludge was dewatered with a plate and frame filter press. 17.3 kg of conditioning sludge was firstly pumped into a 50 L sludge feed tank by a pump, and then the conditioning sludge in the sludge feed tank was pressed into a diaphragm plate frame by a pneumatic press to be dewatered. In order to squeeze the sludge, the pressure of the pneumatic press was increased to 0.8 MPa at a rate of 0.1 MPa/min and kept for 25 min; and then the pressure was increased to 1.2 MPa at a rate of 0.1 MPa/min and kept for 25 min. Finally, 1.11 kg of deeply dewatered sludge cake with a moisture content of 55% can be obtained, and the iron content of the sludge cake was tested to be 11.35%. (3) The deeply dewatered sludge cake was pyrolyzed by using a horizontal tube pyrolysis furnace. Nitrogen was introduced at 0.1 L/min to discharge air in the system, 30 g of the sludge cake with a moisture content of 55% as pyrolysis material was placed in the furnace which has been heated to 900° C., and heat preservation was performed for 30 min to obtain pyrolysis residue. (4) 200 g of sludge with a water content of 97.3% was placed in a beaker (the dry mass of the sludge is 5.4 g), and the pH of the sludge was adjusted to 4 with a 30% sulfuric acid solution; 4.3 g of the above residue was added to the sludge, and then stirring is performed at a stirring rate of 150 rpm and a stirring time of 2 min; 0.54 mL of 30% hydrogen peroxide was added, and then stirring was performed at a stirring rate of 100 rpm and a stirring time of 50 min, thereby obtaining residue conditioned sludge. The capillary sop time (CST) and the specific resistance to filtration (SRF) of the conditioned sludge in the present embodiment are shown in Table 1. Embodiment 3 In the present embodiment, preparation and application methods of the iron-containing sludge pyrolysis residue are as follows. (1) 15.4 kg of sludge and 73.92 g of FeCl2were respectively added to a sludge conditioning tank, and stirring was performed at a stirring rate of 150 rpm and a stirring time of 5 min; then, 154.1 mL of 30% hydrogen peroxide was added, and stirring was performed at a stirring rate of 100 rpm and a stirring time of 30 min to allow the oxidant to fully react with the sludge. Finally, 15.4 kg of conditioning sludge was obtained. (2) The conditioning sludge was dewatered with a plate and frame filter press. 15.4 kg of conditioning sludge was firstly pumped into a 50 L sludge feed tank by a pump, and then the conditioning sludge in the sludge feed tank was pressed into a diaphragm plate frame by a pneumatic press to be dewatered. In order to squeeze the sludge, the pressure of the pneumatic press was increased to 0.8 MPa at a rate of 0.1 MPa/min and kept for 25 min; and then the pressure was increased to 1.2 MPa at a rate of 0.1 MPa/min and kept for 25 min. Finally, 1.03 kg of deeply dewatered sludge cake with a moisture content of 43% can be obtained, and the iron content of the sludge cake was tested to be 8.35%. (3) The obtained sludge cake was dried. The sludge cake was placed in a ventilated place for 24 h to obtain 763.46 g of sludge cake with a moisture content of 23.1%. (4) The dried sludge cake was pyrolyzed by using a horizontal tube pyrolysis furnace. Nitrogen was introduced at 0.12 L/min to discharge air in the system, 30 g of the sludge cake with a moisture content of 23.1% as pyrolysis material was placed in the furnace which has been heated to 600° C., and heat preservation was performed for 60 min to obtain pyrolysis residue. (5) 200 g of sludge with a water content of 95.2% was placed in a beaker (the dry mass of the sludge is 9.6 g), and the pH of the sludge was adjusted to 1 with a 30% sulfuric acid solution; 7 g of the above residue was added to the sludge, and then stirring is performed at a stirring rate of 150 rpm and a stirring time of 8 min; 2.4 mL of 30% hydrogen peroxide was added, and then stirring was performed at a stirring rate of 100 rpm and a stirring time of 40 min, thereby obtaining residue conditioned sludge. The capillary sop time (CST) and the specific resistance to filtration (SRF) of the conditioned sludge in the present embodiment are shown in Table 1. Embodiment 4 In the present embodiment, preparation and application methods of the iron-containing sludge pyrolysis residue are as follows. (1) 15.4 kg of sludge and 177.42 g of FeSO4.7H2O were respectively added to a sludge conditioning tank, and stirring was performed at a stirring rate of 150 rpm and a stirring time of 5 min; then, 144.8 mL of 30% hydrogen peroxide was added, and stirring was performed at a stirring rate of 100 rpm and a stirring time of 30 min to allow the oxidant to fully react with the sludge; finally, 256 g of red mud was added, and rapid stirring was performed for conditioning at a stirring rate of 150 rpm and a stirring time of 5 min. In the above red mud, the percentage of iron is 36%, the mass percentage of aluminum oxide is 18%, the mass percentage of titanium oxide is 6%, and the mass percentage of silica and other minerals is 40%. Finally, 15.8 kg of conditioning sludge was obtained. (2) The conditioning sludge was dewatered with a plate and frame filter press. 15.8 kg of conditioning sludge was firstly pumped into a 50 L sludge feed tank by a pump, and then the conditioning sludge in the sludge feed tank was pressed into a diaphragm plate frame by a pneumatic press to be dewatered. In order to squeeze the sludge, the pressure of the pneumatic press was increased to 0.8 MPa at a rate of 0.1 MPa/min and kept for 25 min; and then the pressure was increased to 1.2 MPa at a rate of 0.1 MPa/min and kept for 25 min. Finally, 1.05 kg of deeply dewatered sludge cake with a moisture content of 49% can be obtained, and the iron content of the sludge cake was tested to be 27.35%. (3) The obtained sludge cake was dried. The sludge cake was placed in a ventilated place for 12 h to obtain 800.45 g of sludge cake with a moisture content of 33.1%. (4) The dried sludge cake was pyrolyzed by using a horizontal tube pyrolysis furnace. Nitrogen was introduced at 0.3 L/min to discharge air in the system, 30 g of the sludge cake with a moisture content of 33.1% as pyrolysis material was placed in the furnace which has been heated to 1000° C., and heat preservation was performed for 90 min to obtain pyrolysis residue. (5) 200 g of sludge with a water content of 96.4% was placed in a beaker (the dry mass of the sludge is 7.2 g), and the pH of the sludge was adjusted to 6.5 with a 10% hydrochloric acid; 5.7 g of the above residue was added to the sludge, and then stirring is performed at a stirring rate of 200 rpm and a stirring time of 2 min; 2.1 mL of 30% hydrogen peroxide was added, and then stirring was performed at a stirring rate of 150 rpm and a stirring time of 15 min, thereby obtaining residue conditioned sludge. The capillary sop time (CST) and the specific resistance to filtration (SRF) of the conditioned sludge in the present embodiment are shown in Table 1. TABLE 1Moisturecontent ofConditionedPyrolysisPyrolysispyrolysisConditionedsludgetemperaturetimematerialsludgeSRFSludge conditioner(° C.)(min)(%)CST (s)(1013m/kg)Embodiment 1Fenton + red mud———36.40.306Embodiment 1Residue + oxidant80090028.350.253Embodiment 2Fenton + lime———35.70.311Embodiment 2Residue + oxidant900305560.10.564Embodiment 3Fenton———41.10.472Embodiment 3Residue + oxidant6006023.178.20.713Embodiment 4Fenton + red mud———29.20.266Embodiment 4Residue + oxidant10009033.144.10.502 It can be seen from Table 1 that conditioning effects (sludge dewatering performance) of the conditioning sludge pyrolysis residue in Embodiments 1-4 are equivalent to that of the methods in which ferrous salt is added, proving that the iron element in the sludge cake can be effectively activated by high temperature pyrolysis in a protective atmosphere and is subjected to advanced oxidation reaction with the oxidant to achieve good sludge conditioning. The method has simple operation and obvious effect, and at the same time allows the sludge treatment and disposal to form a sustainable development route of sludge dewatering, sludge pyrolysis and residue recycling. In addition to existing advanced oxidation technologies such as a Fenton oxidation method (i.e., using a Fenton reagent) and a Fenton-like oxidation method (i.e., using a Fenton-like reagent), the present disclosure is also applicable to iron-containing sludge obtained by other existing advanced oxidation technologies such as a method using persulfate-ferrous salt combination reagent, as long as an advanced oxidation conditioner containing iron is used in the advanced oxidation technology. In the present disclosure, an oxidant that combines with the iron-containing sludge pyrolysis residue to form a sludge composite conditioner may be at least one of peroxide, persulfide and ozone, and of course, two or more types of oxidants may be used at the same time. In the present disclosure, an existing pyrolysis furnace such as a horizontal tubular pyrolysis furnace or a vertical tubular pyrolysis furnace may be used in the sludge cake pyrolysis process. It should be readily understood to those skilled in the art that the above description is only preferred embodiments of the present disclosure, and does not limit the scope of the present disclosure. Any change, equivalent substitution and modification made without departing from the spirit and scope of the present disclosure should be included within the scope of the protection of the present disclosure. | 17,991 |
11858837 | DETAILED DESCRIPTION Aspects and embodiments disclosed herein are not limited to the details of construction and the arrangement of components set forth in the following description or illustrated in the drawings. Aspects and embodiments disclosed herein are capable of being practiced or of being carried out in various ways. Also, the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of “including,” “comprising,” “having,” “containing,” “involving,” and variations thereof herein is meant to encompass the items listed thereafter and equivalents thereof as well as additional items. Sequencing batch reactors (SBRs) are vessels used in some wastewater treatment systems. SBRs often are utilized for performing the breakdown of solids utilizing an activated sludge process. Wastewater treated in SBRs may include, for example, sewage or output from anaerobic digesters or mechanical biological treatment facilities. Wastewater is typically treated in batches in an SBR. In many implementations, oxygen is bubbled through a mixture of wastewater and activated sludge in an SBR to break down organic matter, often measured as biochemical oxygen demand (BOD) or chemical oxygen demand (COD), to produce a waste sludge and a treated effluent, referred to herein as solids-lean supernatant.SBRs typically operate in a series of treatment stages including:A. FillB. ReactC. SettleD. DecantE. Idle In the fill stage (SeeFIG.1A), an inlet to an SBR vessel10is opened and wastewater is introduced into the SBR vessel10and mixed with activated sludge15that is either present in the vessel or introduced with the wastewater and possibly with supernatant20remaining in the vessel10from a previous cycle to form a mixed liquor25. Mixing of the wastewater, activated sludge15, and residual supernatant20may be performed mechanically under anoxic, anaerobic, or aerobic conditions during and/or after the wastewater is introduced into the SBR vessel10. In various implementations, the volume and/or rate of introduction of wastewater into the SBR vessel10may not be known ahead of time. In the react stage (SeeFIG.1B), the mixed liquor25may be provided with oxygen by aerators at the surface of the mixed liquor, for example, floating surface aerators (not shown), or by bubbling of oxygen-containing gas, for example, air, through the mixed liquor25from an aeration system30. The oxygen is used by aerobic microbes to oxidize organic solids in the mixed liquor25. In some embodiments, the SBR is operated under anoxic and/or anaerobic conditions, and no oxygen is introduced to the mixed liquor25. During the settle stage (SeeFIG.1C) suspended solids in the mixed liquor25are allowed to settle by ceasing aeration or mechanical agitation of the mixed liquor. The suspended solids form a blanket of sludge15on the bottom of the SBR vessel10and a solids-lean supernatant20is formed above the sludge layer15. As the term is used herein, a solids-lean supernatant is supernatant having a suspended solids level at or below an upper limit for environmental discharge of the supernatant in a jurisdiction in which the SBR is located. Microorganisms in the settled sludge15may use up substantially all oxygen in the sludge15, providing for anaerobic processes, for example, denitrification to proceed in the settled sludge15. The solids-lean supernatant20is removed from the vessel during the decant stage (SeeFIG.1D), for example, by opening an outlet valve of the vessel10or by pumping. In some embodiments, supernatant is removed from the surface or proximate the surface of the supernatant in the SBR vessel10. The supernatant may be discharged to the environment or further treated, for example, to remove dissolved solids or chemical species if necessary to meet local regulations for environmental discharge. Settled sludge15may be removed from the vessel10as waste activated sludge (WAS) (SeeFIG.1E) during or after the settle or decant stage, for example, by opening an outlet valve of the vessel10or by pumping. The WAS may be disposed of or further treated. After the solids-lean supernatant20is removed from the SBR vessel, the SBR may enter an idle stage (SeeFIG.1F) awaiting introduction of a next batch of wastewater. The SBR vessel10may include residual supernatant20and sludge15while in the idle stage. The amount of time provided for the settle and decant stages in many existing SBR systems is typically fixed. Variations in process conditions, for example, liquid level in the SBR and type and amount of solids in the wastewater may result in either too much or too little supernatant and/or WAS being removed. If too much supernatant is removed, there is a risk that the level of supernatant in the SBR may be decreased to a point at which some suspended solids from the settled sludge may be removed with the supernatant. The decanted supernatant may thus exceed a maximum permitted suspended solids level and may require additional treatment or retreatment, resulting in an increase in treatment cost and time. Different municipalities may have different maximum allowable suspended solids levels for supernatant that is to be discharged into the environment for example, between 5 mg/L and 30 mg/L. If an amount of supernatant that is well below a volume that would result in a risk of decanting supernatant with an undesirably high suspended solids level is removed from the SBR vessel, the SBR would not be producing the amount of supernatant it was capable of, and would be running less efficiently than desired, reducing an amount of wastewater that could be treated or necessitating an increased number of SBRs in a wastewater treatment plant to accommodate a given wastewater flow. If too little WAS is removed the SBR vessel may accumulate an unnecessarily high level of solids, which may increase the time required to settle the solids and thus increase the SBR cycle time. If too much WAS is removed, an insufficient population of bacteria may remain in the SBR vessel to properly treat influent wastewater. Aspects and embodiments disclosed herein are generally directed to an automated process of controlling solids-lean supernatant removal in a system supplied with varying quantities of wastewater by continually monitoring the liquid level and level of settling or settled solids in the system and to apparatus configured to perform such a process. Aspects and embodiments of this method and apparatus may be utilized in SBRs in which varying operating water levels are often encountered to optimize settling, idle, and decant cycles. The time for which suspended solids may take to settle from wastewater in an SBR may vary based on process conditions, for example, a concentration of solids in the wastewater, ambient temperature or temperature of liquid in the SBR, volume of wastewater introduced into the SBR, type and/or quantity of bacteria in the SBR, etc. The amount of solids-lean supernatant produced in an SBR and the time used to produce the solids-lean supernatant may also vary based on factors such as, for example, a concentration of solids in the wastewater, ambient temperature or temperature of liquid in the SBR, volume of wastewater introduced into the SBR, type and/or quantity of bacteria in the SBR, etc. Aspects and embodiments disclosed herein provide for the decanting of solids-lean supernatant from a SBR or other treatment system once solids have settled out from the supernatant to a desired degree by monitoring or measuring the amount of sludge settled to the bottom of the SBR and/or rate of sludge settling, rather than blindly relying on a pre-set time for the solids to settle. Aspects and embodiments disclosed herein provide for the decanting of an amount of solids-lean supernatant consistent with the amount of solids-lean supernatant actually produced from a batch of wastewater by monitoring or measuring the total liquid level and sludge level in an SBR or other treatment system and calculating the amount of available solids-lean supernatant instead of simply decanting for a pre-set time period. Systems disclosed herein may thus operate more efficiently than prior art systems by decanting solids-lean supernatant at a proper time and in a proper amount and/or rate to recover a greater amount of solids-lean supernatant having a desired low solids content than might be achievable by relying on fixed settling and decanting times. Systems disclosed herein may also or alternatively operate with a reduced cycle time as compared to conventional SBRs by performing the sludge settling and solids-lean supernatant decant stages at least partially concurrently. In one embodiment, an automatic control system utilizes solids positioning sensors or switches to optimize solids-lean supernatant removal from a varying or fixed water level system. The solids positioning sensors or switches may be suspended solids sensors that are positioned at fixed locations within a wastewater treatment vessel, tank, or reactor. In another embodiment either single of multiple sensors or switches may be movable to various levels in a wastewater treatment vessel, tank, or reactor. The solids positioning sensors or switches may include one or more ultrasonic sludge level sensors. The ultrasonic sludge level sensors may be operated at a frequency or frequencies that provides a desired level of precision and/or sensitivity for determining the position of an interface between settling or settled sludge and supernatant in the wastewater treatment vessel, tank, or reactor. It has been observed that ultrasonic level sensors operating at high frequencies, for example, above 750 kHz may not be capable of providing a reliable measurement of the position of a sludge blanket having low levels of suspended solids, such as those that might be present as the sludge has just begun to settle in an SBR. Ultrasonic level sensors operating at lower frequencies, for example, between 5 KHz and 800 KHz have been observed to be more capable of providing a reliable measurement of the position of a sludge blanket having low levels of suspended solids than ultrasonic level sensors operating at higher frequencies. Accordingly, in some embodiments, solids positioning sensors or switches utilized in the systems and methods disclosed herein may include one or more ultrasonic sludge level sensors that operate at a frequency of between about 5 KHz and about 800 KHz, between about 50 kHz and about 800 kHz, between about 50 kHz and about 200 kHz, or between about 200 kHz and 455 KHz. In some embodiments, solids positioning sensors or switches utilized in the systems and methods disclosed herein may include one or more ultrasonic sludge level sensors that operate at frequencies that commercially available ultrasonic transducers operate at, for example, 50 kHz, 200 kHz, 455 kHz, or 800 kHz, or combinations thereof. In other embodiments, the solids positioning sensors or switches may include one or more CHIRP (Compressed High-Intensity Radar Pulse) sonar units. CHIRP sensors include a transducer that outputs a progressively increasing frequency in a specific range (for example, 28 kHz-60 kHz, 42 kHz-65 kHz, or 130 kHz-210 kHz) so a variety of frequencies are utilized to gain further resolution with regard to the depth and position of submerged objects as compared to ultrasonic level sensors operating at a single frequency. In some embodiments, ultrasonic level sensors which continuously move with the varying water level are utilized. In some embodiments, ultrasonic level sensors, radar level sensors, floating level sensors, and/or fixed level sensors or switches may be used alone or in combination to detect both the solids level and the water level in a wastewater treatment vessel, tank, or reactor. One or more liquid level sensors may be used in combination with a solids position detecting instrument or sensor so that the solids level and the position of the supernatant/solids interface in a wastewater treatment vessel, tank, or reactor can be determined. The sensors or switches may be connected either with a cable or may be wirelessly connected to a control system and can be moored or mounted within the wastewater treatment vessel, tank, or reactor so that they may float and ride with the varying water levels. When used in an SBR, the solids and liquid level or position sensors may profile the location of settling or settled solids and the interface between settling or settled solids and supernatant formed above the settling or settled solids. By knowing this information, it is possible to optimize the removal of solids-lean supernatant and/or the solids, for example, WAS from the wastewater treatment vessel, tank, or reactor. For example, a control system in communication with the liquid level and/or solids level sensors can trigger the start and stop of the solids-lean supernatant removal based on the relative level of liquid and settled solids in the wastewater treatment vessel, tank, or reactor. In another embodiment, a controller can control the rate of solids-lean supernatant removal based at least in part on, for example, a degree of sharpness of an interface between a sludge blanket and supernatant in the wastewater treatment vessel, tank, or reactor. In another embodiment, the sensors and control system can be used to trigger the start and stop of solids removal and can also control the rate at which the solids are removed. In some embodiments, a “buffer layer” above the interface between a sludge blanket and supernatant in a vessel may be defined and solids-lean supernatant is removed from the vessel only at depths above the buffer layer. The thickness of the buffer layer may be determined based on the degree of sharpness of the interface between the sludge blanket and the supernatant. If the interface between the sludge blanket and the supernatant is not very sharp, decanting supernatant from a region close to the interface might risk decanting supernatant with an undesirably high concentration of suspended solids and so the buffer layer, or minimum depth above the sludge blanket from which supernatant should be decanted, may be defined with a greater depth than if the interface between the sludge blanket and the supernatant was more sharp. If the interface between the sludge blanket and the supernatant is very sharp, supernatant may be decanted from a position close to the interface between the sludge blanket and the supernatant with little risk of decanting supernatant with an undesirably high concentration of suspended solids and so the buffer layer, or minimum depth above the sludge blanket from which supernatant should be decanted, may be defined with a lesser depth than if the interface between the sludge blanket and the supernatant was less sharp. In some embodiments, the control system may utilize data from the liquid level and/or solids level sensors to determine a degree of sharpness of an interface between a sludge blanket and supernatant in a wastewater treatment vessel and a desired minimum depth above the sludge layer or blanket from which supernatant should be decanted to avoid decanting supernatant with an undesirably high concentration of suspended solids. The control system may operate the wastewater treatment vessel or a decanting sub-system thereof to decant solids-lean supernatant from the vessel at a time and/or rate to maintain the level of supernatant in the vessel at or just above the desired minimum depth above the sludge layer or blanket during at least a portion or throughout substantially the entirety of the decant stage. The degree of sharpness of an interface between a sludge blanket and supernatant in a wastewater treatment vessel may vary due to various factors, for example, changes in the content of wastewater introduced into the vessel, age of sludge in the vessel, changes in environmental conditions, for example, temperature, and/or changes to the types or quantity of bacteria present in the vessel (which may vary based on sludge age and/or temperature). Accordingly, the desired minimum depth above the sludge layer or blanket in a vessel from which supernatant should be decanted to avoid decanting supernatant with an undesirably high concentration of suspended solids may vary over time, for example, with seasons of the year. In some embodiments, the control system of the wastewater treatment vessel may utilize data from the liquid level and/or solids level sensors to periodically or continuously recalculate a degree of sharpness of an interface between a sludge blanket and supernatant in the vessel and the desired minimum depth above the sludge layer or blanket from which supernatant should be decanted to avoid decanting supernatant with an undesirably high concentration of suspended solids to account for changes over time in the degree of sharpness of the interface between the sludge blanket and the supernatant. The controller may utilize the recalculated value of the desired minimum depth above the sludge layer or blanket from which supernatant should be decanted to avoid decanting supernatant with an undesirably high concentration of suspended solids to periodically or continuously adjust the time and/or rate of solids-lean supernatant decanting to maintain the level of supernatant in the vessel at or just above the recalculated desired minimum depth above the sludge layer or blanket during at least a portion or throughout substantially the entirety of the decant stage. In some embodiments, the system may be operated in batch mode with non-predetermined and varying quantities of wastewater introduced to the wastewater treatment vessel, tank, or reactor at unknown and varying flow rates. In some embodiments, a ballast material, for example, magnetite or other high density material may be added to the wastewater treatment vessel, tank, or reactor to enhance the settling rate of the solids. Aspects and embodiments disclosed herein are not limited to being used in an SBR and may be used in aerobic and/or anaerobic digesters to optimize thickening and waste cycles from these tanks. Aspects and embodiments disclosed herein are not limited to the type, number, location and combination of sensors or switches used. In some embodiments, a wastewater treatment system includes a wastewater treatment vessel, tank, or reactor equipped with a system to determine and/or continuously monitor an overall liquid level as well as a depth or level of a blanket of settling or settled sludge in the vessel, tank, or reactor. The terms “vessel,” “tank,” and “reactor” are used synonymously herein and should be understood to encompass SBRs. The system may be further configured to determine a change in concentration of suspended solids with depth in the vessel and to quantify a degree of sharpness of an interface between settled or settling sludge and a supernatant in the vessel. As the term is used herein, a degree of sharpness of a solids/liquid or solids/supernatant interface is defined by a change in suspended solids concentration with depth across the interface. As the terms are used herein low-solids supernatant, solids-lean supernatant, or simply supernatant is wastewater in a wastewater treatment vessel from which solids have been at least partially removed, for example, by settling. Typically, when wastewater including suspended solids is left in a wastewater treatment vessel under quiescent conditions solids having a specific gravity greater than water will settle to the bottom of the vessel over time resulting in a sludge “blanket” on the bottom of the vessel covered by a layer of low-solids supernatant, for example, low-solids water. The term “low-solids” is a relative term used herein to characterize supernatant as opposed to solids-rich sludge in a wastewater treatment vessel. A liquid and sludge level monitoring system may include one or more sensors. In some embodiments one type of sensor may be utilized to monitor or measure the overall liquid level in the vessel and another type of sensor may be utilized to monitor or measure a level or depth of a layer of sludge or an interface between sludge and supernatant in the vessel. The overall liquid level in the vessel typically will correspond with the upper surface of the supernatant in the vessel. In other embodiments, similar or the same types of sensors may monitor or measure the overall liquid level in the vessel and the level or depth of a layer of sludge or an interface between sludge and supernatant in the vessel. In further embodiments, the same sensor may monitor or measure the overall liquid level in the vessel and the level or depth of a layer of sludge or an interface between sludge and supernatant in the vessel. The level or depth sensors of the liquid and sludge level monitoring system may be in wired or wireless communication with a controller of the wastewater vessel and may communicate data including indications of measured liquid or sludge levels, depths, or suspended solids or sludge concentrations to the controller. The controller may be programmed to control various operating parameters of the vessel, for example, timing or rate of introduction of wastewater to the vessel, timing or rate of removal of supernatant or sludge from the vessel, timing or rate or aeration or mixing of the vessel, or any other operating parameters of interest based at least partially on data received from one or more of the sensors. In one embodiment, illustrated inFIG.2, a wastewater treatment vessel10includes an overall liquid level or supernatant level sensor35and a sludge level/suspended solids concentration sensor40. The sludge level/suspended solids concentration sensor40(hereinafter the “sludge sensor”) includes a plurality of sensor elements40afixed in place on a wall12of the vessel10. The sludge sensor40, or a controller with which the sludge sensor40communicates, may determine a location of a top50of a layer of sludge15(also referred to herein as the interface between the sludge layer15and the supernatant20) by comparing measurements of suspended solids concentration provided by the different sensor elements40a. The sludge sensor40may also be used to determine a degree of sharpness of the interface between the sludge layer15and the supernatant20by providing an indication of how the level of suspended solids changes from one sensor element40ato the next, and hence how the concentration of suspended solids changes with depth. The sensor elements40aof the sludge sensor40may include, for example, optical (e.g., infrared) or ultrasonic sensors. In one example, illustrated inFIG.3, the sensor elements40aof the sludge sensor40may include a signal transmitter42(e.g., an infrared light emitter or an ultrasonic transducer) and a signal receiver44(e.g., an infrared or ultrasound receiver) separated by a gap46from the signal transmitter42. Liquid in a vessel in which the sensor element40ais disposed fills the gap46between the signal transmitter42and signal receiver44. The sensor elements40amay provide output signals indicative of a degree of attenuation of the signal (the infrared light or ultrasound) from the signal emitter42that is received at the signal receiver44. The degree of attenuation of the signal may be correlated with suspended solids concentration or turbidity of the liquid in the vessel10. The difference in signal attenuation at the different sensor elements40aof the sludge sensor40ofFIG.2can be used to determine a profile of suspended solids or sludge concentration versus depth in the vessel10and thus may be used to determine a position and/or degree of sharpness of the sludge/supernatant interface50. The sensor elements40aof the sludge sensor40are not limited to being optical or ultrasonic sensors and may include any type of sensor capable of providing a signal indicative of a concentration of suspended solids or sludge at locations in the vessel10. More or fewer sensor elements40athan illustrated, for example, 64 or more sensor elements40amay be provided. The sensor elements40aof the sludge sensor40may be disposed on a single wall12of the vessel10as illustrated or on more than one wall. The sensor elements40amay include wipers (not shown inFIG.3) or other self-cleaning mechanisms to remove foulants from the signal transmitter42and/or signal receiver44as desired. The sensor elements40amay additionally or alternatively be utilized to sense a level of liquid in the vessel10. If a signal passing from a signal transmitter42to a signal receiver44in a first sensor element40aabove a second sensor element40ais not attenuated, or not significantly attenuated, while the signal passing from the signal transmitter42to the signal receiver44in the second sensor element40ais attenuated significantly more than that of the first sensor element40a, it can be concluded that the liquid surface is between the first and second sensor elements. The overall liquid level or supernatant level sensor35may also be fixed in place on a wall12of the vessel, which may be the same or a different wall than that to which the sludge sensor40is attached. The overall liquid level or supernatant level sensor35may alternatively be suspended by a pole, cable, scaffold, or other mechanism above the surface of liquid in the vessel10. The sensor35may be an ultrasonic sensor, a radar sensor, an optical sensor, or any other type of sensor capable of providing an indication of the height or level of the top surface45of the supernatant20or wastewater in the vessel10. In some embodiments, for example, the embodiment illustrated inFIG.2, the level sensor35may be disposed at a position above an expected upper level of liquid in the vessel10. Together, the sludge sensor40and level sensor35may be used to determine a supernatant depth D1, a sludge layer thickness or depth D2, and an overall liquid depth D3in the vessel10. In some embodiments, the supernatant depth D1and/or depth of the sludge/supernatant interface is determined by a controller by subtracting a sludge layer thickness D2determined from an output of the sludge sensor40from the liquid level D3determined from an output of level sensor35. In another embodiment, illustrated inFIG.4, the sludge sensor40includes an elongate element, for example, a rod, pole, or cable that is mounted in the vessel10at a position displaced from walls12of the vessel. Sensor elements40a, which may be similar in construction and operation to sensor elements40adiscussed with regard to the embodiment illustrated inFIG.2may be disposed at different positions along the length of the elongate element, and thus at different depths in the vessel10. In one particular example, the sludge sensor40may be similar to the Automated Sludge Blanket Level Detector available from Markland Specialty Engineering Ltd., having 64 photodetector sensor elements over a length of four feet (1.2 meters). The liquid level sensor35illustrated inFIG.4is a liquid pressure sensor. As the level of liquid in the vessel10increases, the liquid pressure at the bottom of the vessel10increases. The liquid level sensor35illustrated inFIG.4is configured to measure or monitor the liquid pressure at the bottom of the vessel10or proximate the bottom of the vessel10and provide data including an indication of the pressure to a controller that can determine the level of liquid (wastewater or sludge and supernatant) in the vessel based on the indication of the pressure. The liquid level sensor35is illustrated inFIG.4adjacent to a wall12of the vessel, but in different embodiments may be disposed in alternate locations. In the embodiment illustrated inFIG.5, the level sensor35is similar in construction and operation to the level sensor35illustrated inFIG.2. The sludge sensor40in the embodiment illustrated inFIG.5extends at least partially into the liquid in the vessel10. The sludge sensor40ofFIG.5may include, for example, an ultrasonic transceiver or separate transmitter and receiver. The speed of travel of ultrasound pulses emitted from the ultrasonic transceiver may be different in wastewater, low-solids supernatant20, and sludge15. The sludge sensor40ofFIG.5may measure a time between emission of an ultrasonic pulse and receipt of an echo of the ultrasonic pulse to determine the amount of sludge15in the vessel10and thus the height of the blanket of sludge15. In some embodiments, a controller may utilize knowledge of a positon of the sludge sensor40in a calculation of the height of the blanket of sludge15and/or depth of the sludge/supernatant interface calculated from data provided from the sludge sensor40. For example, if the sludge sensor40is positioned above X meters of liquid in the vessel10, and if it would be expected to take Y milliseconds for an ultrasound pulse emitted from the sludge sensor40to echo off the bottom of the vessel and return to the sludge sensor40if the vessel was filled with low-solids supernatant, the controller could compare an actual amount of time Z between pulse emission and echo detection to time Y in view of the expected speed of travel of the ultrasound pulse through low-solids supernatant and sludge to determine the height of the blanket of sludge15. In some embodiments, the sludge sensor40may be similar to the SONATAX™ sc Sludge Blanket Level Probe available from the Hach Company. The sludge sensor40ofFIG.5may include a wiper (not shown inFIG.5) or other self-cleaning mechanism to remove foulants from the its signal transmitter, receiver, or transceiver as desired. FIG.6illustrates an embodiment in which both the level sensor35and the sludge sensor40include floating elements that move vertically with the level of liquid in the vessel10. The level sensor35of the embodiment ofFIG.6is a float sensor including a float32mounted on a rod36. The rod36may be secured to a wall12of the vessel10or otherwise secured in place within the vessel10. The float32includes one or more magnets and the rod36includes one or more magnetic sensors, for example, reed switches, at known locations along its length. As the liquid level in the vessel10varies the float32moves up and down about the rod36. As the one or more magnets in the float32approach a magnetic sensor in the rod36, the magnetic sensor can provide a signal to a controller which can interpret the signal to determine the position of the float32and thus the level of liquid in the vessel10. The sludge sensor40ofFIG.6may include, for example, an ultrasonic transceiver or separate transmitter and receiver mounted on a float. The sludge sensor40ofFIG.6may float on the liquid in the vessel10and rise and fall with the overall liquid level in the vessel10. The sludge sensor40ofFIG.6may operate in a similar manner as the sludge sensor40ofFIG.5described above. In some embodiments, a controller may utilize data received from the level sensor35regarding the total level of liquid in the vessel10to refine a calculation of the height of the blanket of sludge15and/or depth of the sludge/supernatant interface calculated from data provided from the sludge sensor40. For example, if the data received from the level sensor35indicates that there is D3meters of liquid in the vessel10, and if it would be expected to take X milliseconds for an ultrasound pulse emitted from the sludge sensor40to echo off the bottom of the vessel and return to the sludge sensor40if the vessel was filled with low-solids supernatant, the controller could compare an actual amount of time Y between pulse emission and echo detection to time X in view of the expected speed of travel of the ultrasound pulse through low-solids supernatant and sludge to determine the height of the blanket of sludge15. The floating sludge sensor40ofFIG.6may be operable at a greater range of liquid levels than, for example, the sludge sensor40ofFIG.5which might be disposed outside of the liquid in the vessel if the liquid level fell too far. Further, a floating sludge sensor may be operable to measure more shallow layers of supernatant than a fixed sludge sensor. A floating sludge sensor may, for example, be used in a control system configured to remove or decant supernatant during the settling stage of an SBR cycle. The supernatant may be decanted while maintaining only a depth of supernatant, for example, about six inches (15.2 cm) sufficient to provide decanted solids-lean supernatant with a desired low solids concentration. The suspended solids level of the decanted solids-lean supernatant may be controlled or minimized by providing a sufficient supernatant depth above the supernatant/sludge interface to avoid decanting sludge or suspended solids from a mixing layer around the supernatant/sludge interface which may include an undesirably high amount of suspended solids. The sludge sensor40ofFIG.6may include a wiper (not shown inFIG.6) or other self-cleaning mechanism to remove foulants from the its signal transmitter, receiver, or transceiver as desired. In further embodiments, a sludge sensor including an ultrasonic transducer may be built into the float32of the level sensor35to produce a combination liquid level sensor/sludge depth sensor and separate sludge sensor40may be omitted. In another embodiment, illustrated inFIG.7, a sludge sensor40and/or level sensor35may include a submersible element45suspended by a cable in the liquid in the vessel10. A winch50may be utilized to drop the submersible element45to different depths within the vessel and may include a sensor to track the depth to which the submersible element45has been dropped. In one embodiment, the submersible element45may include a suspended solids concentration monitor having optical or ultrasonic signal transmitters and receivers, similar to the sensor element40aillustrated inFIG.3. In another embodiment, the submersible element45may additionally or alternatively include a liquid level sensor, for example a pressure sensor to provide an indication of a depth of the submersible element45below a surface of liquid in the vessel10. Additionally or alternatively, the submersible element45may have a density intermediate between that of the supernatant20and the sludge15in the vessel. The submersible element45may be lowered by the winch50into the liquid in the vessel until it comes to rest and floats on the surface of the layer of sludge15beneath the supernatant20, thereby providing an indication of a depth of the sludge/supernatant interface. The submersible element45and/or winch50may provide data indicative of the level of liquid in the vessel, the depth of the sludge/supernatant interface or height of the sludge layer, and/or a profile of suspended solids concentration versus depth to a controller of the vessel10. Data regarding the level of liquid in the vessel10and the depth of the sludge/supernatant interface or height of the sludge layer provided by any of the level sensors and sludge sensors disclosed herein may be utilized by a control system to control operation of the vessel10. For example, an indication of suspended solids concentration in wastewater introduced into the vessel provided by an embodiment of one of the sensors disclosed herein may be utilized by the control system to determine a desired amount or time of aeration or mixing or to estimate a desired solids settling time. An indication of a degree of sharpness of the sludge/supernatant interface provided by an embodiment of one of the sensors disclosed herein may be utilized by the control system to determine when to begin decanting solids-lean supernatant. Decanting of solids-lean supernatant may be initiated by the control system once the sludge/supernatant interface exhibits a desired degree of sharpness so that a solids-lean supernatant having a desirably low amount of suspended solids may be decanted. An indication of the degree of sharpness of the sludge/supernatant interface provided by an embodiment of one of the sensors disclosed herein may be utilized by the control system to determine how quickly to decant solids-lean supernatant from the vessel. The control system may initiate decanting of solids-lean supernatant while solids are still in the process of settling from the wastewater/supernatant. The control system may first decant the solids-lean supernatant slowly so solids-rich supernatant lower in the vessel is not decanted until the solids in the solids-rich supernatant settle out. The rate of solids-lean supernatant decanting may be increased by the control system as the sludge/supernatant interface becomes sharper as there will be more confidence that supernatant decanted from the vessel will not contain an undesirable concentration of solids. An indication of a depth of the sludge/supernatant interface provided by an embodiment of one of the sensors disclosed herein may be utilized by the control system to determine how much solids-lean supernatant may be decanted without risking decanting sludge along with the solids-lean supernatant. An indication of a depth of the sludge/supernatant interface provided by an embodiment of one of the sensors disclosed herein may be utilized by the control system to determine when and how much sludge to drain or waste from the vessel10to provide a desired amount of sludge (and microorganisms) in the vessel. An indication of the degree of sharpness of the sludge/supernatant interface provided by an embodiment of one of the sensors disclosed herein may be utilized by the control system to determine how quickly to drain or waste sludge from the vessel10. If the sludge/supernatant interface is not sharp, it may be desirable to drain the sludge from the vessel10at a relatively slow first rate so as not to introduce turbulence into the vessel that may remix the sludge and supernatant. If the sludge/supernatant interface is sharp it may be desirable to drain the sludge from the vessel10at a relatively higher second rate that is higher than the first rate so that the sludge is removed before it can remix with the supernatant. Various operating parameters of the wastewater treatment vessels or SBRs disclosed herein may be controlled or adjusted by an associated control system or controller based on various parameters measured by various sensors located in different portions of the vessels. The controller used for monitoring and controlling operation of the various elements of a vessel10or a wastewater treatment system including a vessel10may include a computerized control system. Various aspects of the controller may be implemented as specialized software executing in a general-purpose computer system100such as that shown inFIG.8. The computer system100may include a processor102connected to one or more memory devices104, such as a disk drive, solid state memory, or other device for storing data. Memory104is typically used for storing programs and data during operation of the computer system100. Components of computer system100may be coupled by an interconnection mechanism106, which may include one or more busses (e.g., between components that are integrated within a same machine) and/or a network (e.g., between components that reside on separate discrete machines). The interconnection mechanism106enables communications (e.g., data, instructions) to be exchanged between system components of system100. Computer system100also includes one or more input devices108, for example, a keyboard, mouse, trackball, microphone, touch screen, and one or more output devices110, for example, a printing device, display screen, and/or speaker. In addition, computer system100may contain one or more interfaces (not shown) that connect computer system100to a communication network in addition or as an alternative to the interconnection mechanism106. The output devices110may also comprise valves, pumps, or switches which may be utilized to introduce wastewater into a treatment vessel, mix or aerate the wastewater in the vessel, and/or remove supernatant or sludge from the vessel. The one or more input devices108may also include any of the liquid level or sludge sensors disclosed herein. The storage system112, shown in greater detail inFIG.9, typically includes a computer readable and writeable nonvolatile recording medium202in which signals are stored that define a program to be executed by the processor102or information to be processed by the program. The medium may include, for example, a disk or flash memory. Typically, in operation, the processor causes data to be read from the nonvolatile recording medium202into another memory204that allows for faster access to the information by the processor than does the medium202. This memory204is typically a volatile, random access memory such as a dynamic random access memory (DRAM) or static memory (SRAM). It may be located in storage system112, as shown, or in memory system104. The processor102generally manipulates the data within the integrated circuit memory204and then copies the data to the medium202after processing is completed. A variety of mechanisms are known for managing data movement between the medium202and the integrated circuit memory element204, and aspects and embodiments disclosed herein are not limited thereto. Aspects and embodiments disclosed herein are not limited to a particular memory system104or storage system112. The computer system may include specially-programmed, special-purpose hardware, for example, an application-specific integrated circuit (ASIC). Aspects and embodiments disclosed herein may be implemented in software, hardware or firmware, or any combination thereof. Further, such methods, acts, systems, system elements and components thereof may be implemented as part of the computer system described above or as an independent component. Although computer system100is shown by way of example as one type of computer system upon which various aspects and embodiments disclosed herein may be practiced, it should be appreciated that aspects and embodiments disclosed herein are not limited to being implemented on the computer system as shown inFIG.8. Various aspects and embodiments disclosed herein may be practiced on one or more computers having a different architecture or components that that shown inFIG.8. Computer system100may be a general-purpose computer system that is programmable using a high-level computer programming language. Computer system100may be also implemented using specially programmed, special purpose hardware. In computer system100, processor102is typically a commercially available processor such as the well-known Pentium™, Lore™, or Atom™ class processors available from the Intel Corporation. Many other processors are available, including programmable logic controllers. Such a processor usually executes an operating system which may be, for example, the Windows 7, Windows 8, or Windows 10 operating system available from the Microsoft Corporation, the MAC OS System X available from Apple Computer, the Solaris Operating System available from Sun Microsystems, or UNIX available from various sources. Many other operating systems may be used. The processor and operating system together define a computer platform for which application programs in high-level programming languages are written. It should be understood that the invention is not limited to a particular computer system platform, processor, operating system, or network. Also, it should be apparent to those skilled in the art that aspects and embodiments disclosed herein are not limited to a specific programming language or computer system. Further, it should be appreciated that other appropriate programming languages and other appropriate computer systems could also be used. One or more portions of the computer system may be distributed across one or more computer systems (not shown) coupled to a communications network. These computer systems also may be general-purpose computer systems. For example, various aspects of the invention may be distributed among one or more computer systems configured to provide a service (e.g., servers) to one or more client computers, or to perform an overall task as part of a distributed system. For example, various aspects and embodiments disclosed herein may be performed on a client-server system that includes components distributed among one or more server systems that perform various functions according to various aspects and embodiments disclosed herein. These components may be executable, intermediate (e.g., IL) or interpreted (e.g., Java) code which communicate over a communication network (e.g., the Internet) using a communication protocol (e.g., TCP/IP). In some embodiments one or more components of the computer system100may communicate with one or more other components over a wireless network, including, for example, a cellular telephone network. It should be appreciated that the aspects and embodiments disclosed herein are not limited to executing on any particular system or group of systems. Also, it should be appreciated that the aspects and embodiments disclosed herein are not limited to any particular distributed architecture, network, or communication protocol. Various aspects and embodiments disclosed herein are may be programmed using an object-oriented programming language, such as SmallTalk, Java, C++, Ada, or C# (C-Sharp). Other object-oriented programming languages may also be used. Alternatively, functional, scripting, and/or logical programming languages may be used, for example ladder logic. Various aspects and embodiments disclosed herein are may be implemented in a non-programmed environment (e.g., documents created in HTML, XML or other format that, when viewed in a window of a browser program, render aspects of a graphical-user interface (GUI) or perform other functions). Various aspects and embodiments disclosed herein may be implemented as programmed or non-programmed elements, or any combination thereof. Example 1: Measurement System Performance To illustrate the variability in liquid level and sludge levels between cycles in an SBR, liquid level and sludge level sensors were installed in an SBR in a wastewater treatment facility and measurements of the liquid levels and sludge levels were taken over a period of two days. The liquid level sensor was a SITRANS LU™ ultrasonic level sensor model number 7ML522-2AA18 from Siemens AG. The liquid level sensor was disposed 17 feet, 3 inches (5.26 meters) from above the bottom of the SBR vessel, well above the upper level of liquid reached in the vessel during testing, which was about 11 feet (3.35 meters). The sludge level sensor was a SONATAX™ sc Sludge Blanket Level Probe from the Hach Company. The sludge level sensor was mounted on floats and the ultrasonic transceiver of the sludge level sensor extended between 3 and 8 inches (between 7.6 cm and 20.3 cm) below the surface of the liquid in the SBR. Measurements were taken using the liquid level sensor and sludge sensor during normal operation of the SBR with a 2.5 hour timed fill stage, a one hour timed react stage, a one hour timed settle stage, and a 25 minute timed decant/idle stage. As can be seen inFIG.10, over the period of two days, the liquid and sludge levels in the SBR varied from cycle to cycle and were not pre-determined. The liquid level varied at the end of each fill cycle (the peaks in the water depth curve) between about 9.3 feet and about 10.5 feet. The sludge level at the end of each fill cycle varied from about eight feet to just over nine feet. At the end of each decant cycle the liquid level dropped to about 8.5 feet, with some variation between cycles, and the sludge level dropped to between about 5.5 feet and about 5.8 feet. Example 2: Measurement Accuracy The accuracy of the SITRANS LU™ ultrasonic level sensor and of the SONATAX™ sc Sludge Blanket Level Probe for measuring liquid level and sludge level, respectively, was examined by comparing the readings from these sensors to manually made physical measurements of the liquid and sludge levels during the settle and decant stages of one cycle of the same SBR used in Example 1.FIG.11illustrates a comparison between the sensor readings and the physical measurements of liquid level and sludge depth. As can be seen from this data, aside from some discrepancies in the sludge blanket depth at the beginning of the settle stage and the end of the decant stage, the sensor measurements closely matched the physically observed liquid and sludge levels. Without being bound to a particular theory it is believed that these discrepancies were due to the SONATAX™ sc Sludge Blanket Level Probe utilizing an operating frequency that rendered it unable to accurately determine the level of the low solids concentration sludge blanket at the beginning of the settle stage, and at the end of the decant stage when mixing of the liquid in the SBR began. This data illustrates that the sensors utilized may be used to accurately measure liquid level and sludge depth throughout at least a majority of an operating cycle in an SBR. Example 3: Prophetic Amount of Cycle Time Savings A control system of an SBR may be configured to begin decanting solids-lean supernatant during the settle stage of an SBR once the sludge/supernatant interface has dropped to a depth, for example, between about six inches (15.24 cm) and about three feet (91.4 cm) below the surface of the liquid in the SBR. This depth may be selected based on the degree of sharpness of the supernatant/sludge interface so that solids-lean supernatant having a desired low solids content, for example, a suspended solids content below that required for environmental discharge of the supernatant by regulations in a region in which the wastewater treatment system including the SBR is located. The solids-lean supernatant may be decanted from the surface or proximate the surface of the liquid in the SBR vessel via an outlet valve or pump. The degree of sharpness of the supernatant/sludge interface may vary based on, for example, the type of wastewater and amount and type of suspended solids, ambient temperature or temperature within the SBR, and other factors. When the sludge and/or liquid level sensors identifies that the desired depth of supernatant having the desired low solids content has formed, the control system of the SBR initiates decanting of the solids-lean supernatant. The flow rate of decanted solids-lean supernatant is controlled to maintain the desired depth of supernatant with the desired low solids content throughout the decant process. FIG.12represents liquid and sludge levels in one prophetic example of this process. InFIG.12the dashed line represents the overall liquid level in a conventionally operated SBR during an operating cycle. The SBR is filled, aerated, and the sludge is then allowed to settle. After settle time elapses the SBR decants the prescribed volume of solids-lean supernatant in preparation for the next cycle. The line labelled “Sludge Level” inFIG.12represents the depth of the sludge/supernatant interface. The solid line labelled “Liquid Level (Prophetic)” represents a potentially revised liquid level profile achievable while monitoring the sludge depth and decanting solids-lean supernatant to maintain a fixed supernatant depth in the SBR. By knowing where the sludge/supernatant interface is during the settle cycle some, or all, of the decant cycle may be performed concurrent with the settle cycle. In one particular prophetic example, an SBR is normally operated with a 2.5 hour timed fill stage, a one hour timed react stage, a one hour timed settle stage, and a 25 minute timed decant/idle stage. The sludge settles to form solids-lean supernatant with sufficiently low solids content to meet regulatory guidelines for environmental discharge at a linear rate of about two inches/min (5.1 cm/minute). The time to achieve six inches of supernatant during the settling cycle would thus be about 3 minutes. If the system was modified to operate in accordance with one or more of the embodiments disclosed herein, the decant stage could then begin 3 minutes into the settle stage and the rate of solids-lean supernatant removal would be adjusted to maintain the six inches of supernatant with the sufficiently low solids content above the sludge/supernatant interface. The decant stage would end at substantially the same time as the settle stage. The SBR cycle time would thus be reduced from four hours and 55 minutes to 4.5 hours, an 8.5% reduction. More wastewater flow may thus be treated in the same SBR footprint or the SBR footprint may be reduced by 8.5% and achieve the same wastewater treatment flow. For example, the number of SBR cycles could be increased from about 10 every two days to about 11 every two days, an increase of about 180 cycles per year. This reduction in cycle time would be greater for systems in which sludge settled faster, for example, in systems where magnetite was added to the sludge to enhance settling, and lesser in systems where sludge settling proceeded at a lower rate or where a greater depth of supernatant was desired to be maintained above the sludge/supernatant interface during decanting, for example, to meet stricter guidelines for solids content of solids-lean supernatant to be discharged to the environment. Example 4: Prophetic Increase in Supernatant Recovery The amount of solids-lean supernatant that is decanted during each cycle of an SBR is typically set at a fixed value. The fixed value is typically set so that during decanting the level of supernatant does not drop to a level close enough to the highest expected depth of the sludge/supernatant interface such that the decanted solids-lean supernatant does not include more suspended solids than allowed per local regulatory guidelines. Due to the variability in the depth of the sludge/supernatant interface below the surface of liquid in a typical SBR after a typical timed settle stage, the sludge/supernatant interface between the supernatant and settled sludge may be below the highest expected depth during many cycles. Decanting the fixed value of solids-lean supernatant in cycles in which the sludge/supernatant interface between the supernatant and settled sludge is below the highest expected depth may result in solids-lean supernatant that would meet regulatory guidelines for discharge remaining in the SBR after the decant stage, and the SBR may thus be operating below its optimal solids-lean supernatant production and wastewater treatment capacity and efficiency. By monitoring the depth of the sludge/supernatant interface, an amount of solids-lean supernatant that is decanted may be varied based on the observed depth of the sludge/supernatant interface, resulting in a greater amount of solids-lean supernatant that meets regulatory guidelines being decanted and increasing the solids-lean supernatant production and wastewater treatment capacity and efficiency of the SBR. In one particular prophetic example, the sludge/supernatant interface depth after sludge settling in an SBR with an average liquid fill volume of 1,000 ft3(28.3 m3) and average liquid fill height of 10 feet (with insignificant cycle-to-cycle fill height variation for this example) has a mean depth D of five feet (1.5 meters) with a standard deviation δ of one foot (0.3 meters). For solids-lean supernatant having a solids content meeting regulatory guidelines to be decanted with a confidence level of 99.9%, a set volume of solids-lean supernatant is decanted such that decanting stops when the supernatant level reaches one foot above D+3δ, or nine feet. If the level of the sludge/supernatant interface was monitored, on average, the solids-lean supernatant could be decanted until the supernatant level reached one foot above D, or six feet, while still meeting regulatory requirements for solids content. This would result in an average of an additional 300 ft3(8.5 m3) of solids-lean supernatant being decanted for each cycle. If each cycle lasted an average of 6 hours, this would result in an increased solids-lean supernatant production capacity and wastewater treatment capacity of about 438,000 ft3(12,402 m3) per year for the SBR. The phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. As used herein, the term “plurality” refers to two or more items or components. The terms “comprising,” “including,” “carrying,” “having,” “containing,” and “involving,” whether in the written description or the claims and the like, are open-ended terms, i.e., to mean “including but not limited to.” Thus, the use of such terms is meant to encompass the items listed thereafter, and equivalents thereof, as well as additional items. Only the transitional phrases “consisting of” and “consisting essentially of,” are closed or semi-closed transitional phrases, respectively, with respect to the claims. Use of ordinal terms such as “first,” “second,” “third,” and the like in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are performed, but are used merely as labels to distinguish one claim element having a certain name from another element having a same name (but for use of the ordinal term) to distinguish the claim elements. Having thus described several aspects of at least one embodiment, it is to be appreciated various alterations, modifications, and improvements will readily occur to those skilled in the art. For example, it should be appreciated that any of the level sensors and sludge sensors disclosed herein may be included in a wastewater treatment vessel or SBR with any other of the level sensors and sludge sensors disclosed herein. Any feature described in any embodiment may be included in or substituted for any feature of any other embodiment. In further embodiments, existing wastewater treatment systems or vessels may be retrofitted to include features of the wastewater vessels disclosed herein. Such alterations, modifications, and improvements are intended to be part of this disclosure, and are intended to be within the scope of the invention. Accordingly, the foregoing description and drawings are by way of example only. | 58,462 |
11858838 | The meanings of the reference signs in the above figures are as follows: 1A reactor tank body;2water inlet device;3water outlet device;4water inlet inner channel;5water inlet weir;6water inlet outer channel;7vertical water inlet branch pipe,8vertical bell mouth,9water outlet main pipe,10water outlet channel,11water outlet weir,12outer baffle plate,13inner baffle plate,14pipes along four directions. DETAILED DESCRIPTION OF THE INVENTION The sewage uniform treatment device and the method of using the same of the present disclosure will be described in detail below with reference toFIGS.1-4. A sewage uniform distribution treatment device for an aerobic granular sludge system, the sewage uniform distribution treatment device comprises a reactor tank body1, a water inlet device2and a water outlet device3, wherein, the water inlet device and the water outlet device are both arranged in the reactor tank body1, and the elevation of the water inlet device2is higher than the elevation of the water outlet device; and the water inlet device comprises a water inlet inner channel4, a water inlet weir5, a water inlet outer channel6, a vertical water inlet branch pipe7and vertical bell mouths8, the water inlet weir5is located at the top of the water inlet inner channel4and is connected with the water inlet inner channel4, the vertical water inlet branch pipe7is vertically arranged in the reactor tank body, and the upper and lower ends of the vertical water inlet branch pipe are respectively connected with the water inlet outer channel6and the vertical bell mouths8; the water inlet device is communicated with the bottom of the reactor tank body through the vertical bell mouths; the water outlet device3comprises a water outlet main pipe9, a water outlet channel10, a water outlet weir11, an outer baffle plate12and an inner baffle plate13; the water outlet channel10is connected with the water outlet main pipe9, the water outlet weir11is located at the top of the water outlet channel10and is connected with the water outlet channel10; the outer baffle plate12is a vertical baffle plate, and the vertical baffle plate is connected with the reactor tank body1; the inner baffle plate13is located at the bottom of the water outlet channel10and is connected with the water outlet channel10; the inner baffle plate13is provided at a certain included angle with the water outlet channel, and the value of the included angle is 30-60 degrees; the water outlet device3is communicated with the reactor tank body1through the water outlet channel10. The water inlet inner channel4is designed according to partially-filled flow, with a roughness coefficient of 0.0013, a degree of fullness ranging from 0.5-0.8, preferably 0.6, and a slope ranging from 0.002-0.005, preferably 0.003. The water inlet weir is a right triangular weir, the water inlet weir5is located at the top of the water inlet inner channel4and is connected with the water inlet inner channel4, and a load to check a single water inlet weir5is 2.5 L/(m·s), and theoretical calculation formulas are: flow of a single triangular weir q0=totalflowQnumberoftriangularweirsn; loss of water head on weir of a single triangular weir h0=flowofasingletriangularweirq02.521.4; load to check a single water inlet weir q1=0.5*totalflowQnumberoftriangularweirsn*lossofwaterheadonweirofasingletriangularweirh0. The bottom of the water inlet outer channel6is connected with the vertical water inlet branch pipe7, the water inlet inner channel4, the water inlet outer channel6and the vertical water inlet branch pipe7are located on the same axis of symmetry, and the bottom part of the vertical water inlet branch pipe7is divided into pipes14along four directions which form angles of 27°, 153°, 207° and 333° with the horizontal direction, and the vertical bell mouths8are distributed at said angles and can be uniformly distributed at the bottom of the reactor tank body1. The opening angle of the vertical bell mouth8is 60°-120°, preferably 90°, the vertical bell mouths8are arranged in a ring at equal intervals in the reactor tank body1relative to the central axis of the vertical water inlet branch pipe7. The height of the water outlet channel10is 100-300 mm lower than the height of the water inlet inner channel4and has no slope, the bottom of the water outlet channel10is connected with the inner baffle plate13, and the angle between the inner baffle plate13and the horizontal direction is 30°-60°, preferably 45°. The water outlet weir is a right triangular weir11, the water outlet weir11is located at the top of the water outlet channel10and is connected with the water outlet channel10, a load to check a single water outlet weir11is 1.47 L/(m·s), and theoretical calculation formulas are: flow of a single triangular weir q0=totalflowQnumberoftriangularweirsn; loss of water head on weir of a single triangular weir h0=flowofasingletriangularweirq02.521.4; load to check a single water inlet weir q1=0.5*totalflowQnumberoftriangularweirsn*lossofwaterheadonweirofasingletriangularweirh0. A method of use of the sewage uniform distribution treatment device for an aerobic granular sludge system according to the present disclosure comprises the following steps: 1) uniformly distributing the sewage selectively by the water inlet device: the sewage collected by the water inlet inner channel fells into the water inlet outer channel through the water inlet weir, and primary separation and distribution of the sewage are achieved; 2) the sewage in the water inlet outer channel flows to the vertical water inlet pipe automatically, and finally flows into the reactor tank body through the vertical bell mouths which are uniformly distributed at the bottom of the reactor tank body, so that secondary separation and distribution of sewage are realized; 3) because of the elevation difference between the water inlet device and the water outlet device, the sewage in the reactor tank body enters the water outlet channel through the water outlet weir, and the sewage in the water outlet channel flows out of the reactor tank body through the water outlet pipe, so that continuous and stable operation of the water distribution system is guaranteed. The beneficial effects of the sewage uniform distribution treatment device for an aerobic granular sludge system of the present disclosure are as follows: (1) The sewage is selectively diverted by the water inlet device and distributed uniformly in the reactor tank body, the water inlet weir is provided in the water inlet device, so that the sewage will be redistributed after falling through the water inlet weir, and the kinetic energy of the sewage in the water inlet inner channel is lowered. (2) A relatively stable area is created by the blocking effect of the inner baffle plate and the outer baffle plate, the sewage can settle down freely, which is advantageous to the separation of sewage and sludge and reduction of the concentration of suspended matters in the outlet water. (3) The water inlet device and water outlet device are utilized to achieve the effect of the inlet water withstanding the outlet water, the sludge and sewage organic matters are in complete contact in a gradient manner, creating a satiety-hungry environment, which is beneficial to denitrification and anaerobic phosphorus release and to achieve granulation of the sludge. (4) The process is simple, the processing capacity is large, and the efficiency is high, which plays an important role in achieving the granulation of the pilot and demonstration projects of existing granular sludge processes. The above description of the embodiments is to facilitate those skilled in the art to understand and apply the present disclosure. Those skilled in the art can obviously make various modifications to these embodiments easily, and apply the general principles described here to other embodiments without creative work. Therefore, the present disclosure is not limited to the embodiments herein. Based on the disclosure of the present disclosure, those skilled in the art should make improvements and modifications without departing from the scope of the present disclosure within the protection scope of the present disclosure. | 8,368 |
11858839 | DETAILED DESCRIPTION Management of the nitrogen cycle has been identified by the National Academy of Engineers of the United States as one of the fourteen Grand Challenges of Engineering in the 21st Century. The nitrogen cycle has been disrupted over the last century by human intervention with the synthesis of reactive nitrogen species for fertilizer production and the combustion of fossil fuels. Nitrogen plays an essential role in the production of food for humanity as it is usually the limiting nutrient for crop productivity. It is hypothesized that the existing or future population of the world could not be sustained without producing ammonia from synthetic fertilizers. The methods currently used to meet worldwide food challenges, however, have led to excess nitrogen in the planetary environment which has generated daunting impacts around the world. Excess nitrogen in the environment may play a role in disruption of ecosystems by the eutrophication of waters like the Gulf of Mexico or Chesapeake Bay, exacerbation of global warming by production of potent greenhouse gases, acidification of lakes and soils, and contribution to the disruption of the ozone layer. Promotion of smog in densely populated areas and contamination of drinking water caused by excess environmental nitrogen may have a direct impact on human health. The combined impacts of nitrogen cycle disruption for the United States are an estimated 210 billion a year. It is hypothesized that agriculture is responsible of over 50% of all reactive nitrogen inputs to the US. Non-point sources of ammonia pollution, such as those associated with agriculture, are prevalent in the US. Due to the gaseous nature of ammonia and its abundance in animal manures, a large volume of ammonia is released to the atmosphere or leached out to surface and/or groundwater during manure processing and land application of manure. Recovery of ammonia to produce fertilizers may reduce input to the atmosphere and offset demands for synthetic nitrogen production. Ammonia typically acts as a base when dissolved in water. Certain concentrations of ammonia may raise pH of the liquid to a value effective to release free ammonia into to the atmosphere. Free ammonia is often released during storage and land application of liquid manure Ammonia emissions from manure are a concern for the environment and well-being of humans Additionally, ammonia emissions from manure are a concern for the health and well-being of farm animals, as ammonia gas is pungent and toxic. To control or reduce ammonia emissions from liquid substances pH may be controlled to maintain ammonia in a dissolved form. Conventional methods may require the addition of an acid to control pH and stabilize ammonia. However, such methods of pH control for liquid manure applications are challenging due to the high concentration of ammonia and the expense and unintended effects of adding an acid to the liquid. Additionally, even though ammonia concentration in animal manure is high enough to produce free ammonia emissions, manure as a fertilizer is considered a dilute product. Transportation and application of the dilute product contribute to the high costs associated with animal manure fertilizer. The cost-effective area for application of the manure fertilizer is small, generally limited to a few miles from the farm. As a result, animal manure is usually employed as a fertilizer to saturate local soils. Thus, it is often desirable to remove water from the liquid manure and produce a concentrated stable nutrient rich liquid product. Concentration may be performed with technologies such as reverse osmosis, forward osmosis, evaporation, among others. When concentrating manure using reverse osmosis, nanofiltration, or evaporation, ammonia may be lost due to the volatile nature of free ammonia. Acidification of the liquid to transform free ammonia into ammonium ion may reduce losses. Without acidification, the relatively high pH associated with the increased concentration of ammonia in solution may induce precipitation of ions such as phosphate, calcium, magnesium, and sulfate, forming incrustations (such as, for example, struvite, calcite, brushite, vivianite, gypsum and others) that foul membranes, pipes, valves, and pumps. Furthermore, membrane fouling of ultrafiltration, nanofiltration, electrodialysis, and reverse osmosis membranes may also occur as a result of the high concentration of easily degradable organic matter that induces biofouling. The above problems are more prevalent in liquid wastes that have a high concentration of total nitrogen, measured as Total Kjeldahl Nitrogen (TKN). Examples of high TKN liquid wastes include liquids and slurries such as animal manure, e.g., urine and solids, liquid slaughterhouse waste, leachate from decomposing organic materials, waste activated sludge or primary sludge, or digestates of such liquids, such as when such liquids have been treated by anaerobic digestion, optionally in an acid step of anaerobic digestion. Briefly, in the anaerobic digestion process or in the acid step of anaerobic digestion, the organic nitrogen is mostly converted into ammonia. Digestate liquids include waste activated sludge, waste primary sludge, digestates of animal manure, digestates of food waste, or general digestates of organic slurries or solid or slurry organic materials. The manure high nitrogenous liquid wastes disclosed herein may be formed by passing raw animal manure, e.g., urine and solids, through a solid-liquid separator, such as a filter, centrifuge, hydrocyclone, decanter, or other separator to produce a first stream enriched in solids and a mostly liquid second stream. The mostly liquid stream may form the high nitrogenous liquid waste. The digestate high nitrogenous liquid waste disclosed herein may be raw digestate or digestate that has been further processed for separation of solids, as previously described. Such high nitrogenous liquid wastes may be stabilized and concentrated by the methods and systems disclosed herein. The methods and systems disclosed herein are practical and cost effective, reduce environmental impact, improve animal health by alleviating diseases and conditions associated with uncontrolled ammonia emissions, and recover a valuable resource producing a fertilizer that can be safely stored and accurately applied. In accordance with one or more embodiments, the nitrogenous compounds, including urea, uric acid, proteins, and ammonia, can be recovered from a stabilized liquid and converted into usable fertilizers for reuse in the agricultural production of food. The recovery and reuse of nitrogen may reduce ammonia emissions to the environment and contributes to a more sustainable food supply chain. Systems and methods disclosed herein may be employed to produce a fertilizer liquid that has a selected proportion of anions and cations in solution for agricultural use. In some embodiments, the oxidation of ammonia for acid production may be chemical in nature while in other embodiments the oxidation of nitrogenous compounds to produce scrubbing acid may be biological. The methods disclosed herein involve partial oxidation of nitrogenous compounds, such as ammonia, to form oxy-anions of nitrogen, such as nitrite or nitrate. In particular, the methods allow the conversion of a fraction of nitrogenous compounds to oxy-anions of nitrogen. The conversion may be effective to reduce pH of the liquid, stabilizing the ammonia and reducing ammonia emissions from free ammonia. In certain embodiments, the methods disclosed herein may effectively reduce pH of the liquid without addition of an external acid. The oxy-anions of nitrogen may be generated by an oxidation reaction of ammonia in solution with an oxidizing agent, such as oxygen, peroxide, or ozone. The rate of oxidation may be controlled to a desirable extent. The oxidation of ammonia to produce oxy-anions reduces the pH of the solution. Effective control of pH may be required to achieve a rate of oxidation useful in practice. In certain embodiments, an external base may be used to control pH of the solution. The extent of ammonia oxidation to produce oxy-anions of nitrogen such as nitrite or nitrate can be controlled by controlling a rate of addition of the nitrogenous liquid or the oxidant. Additionally, adding more or less base to keep pH of the solution at a desirable level may further control the oxidation reaction. In certain instances, the oxidation reaction may be inhibited by a high concentration of dissolved ions in solution. Dilution water may be combined with the liquid to reduce inhibition of oxidation. In such embodiments when dilution water is used, the liquid product may be concentrated by removing water to produce a concentrated liquid product. The graph ofFIG.1Ashows pH control of the nitrogenous liquid with potassium base as an example. The percentage of the ammonia captured that is oxidized may be controlled by adding different amounts of a base, such as the potassium base. As shown inFIG.1A, when there is no addition of base, the oxidation of ammonia is controlled to about 50%. By adding the base, increasing amounts of ammonia up to 100% may be oxidized and converted to oxy-anions of nitrogen. The following chemical reactions, which take place in one or more of the embodiments disclosed herein, illustrate the combination of an oxidant, ammonia, and water to produce ammonium salts in solution. Some of the reactions are physical and involve material transfer, while others are chemical in nature, like water ionization. In at least some embodiments, some reactions may be mediated by naturally present microorganisms in the liquid. In some embodiments the reactions of nitrogenous liquids with water and the oxidant may take place in one chamber. In other embodiments, the reactions may take place in separate chambers. NH3(gas)+H2O (liquid)↔NH3(aqueous)+H2O (1) NH3(aqueous)+2H2O (liquid)↔NH4++OH−(2) NH3(aqueous)+O2(aqueous)→NO2−+H+(3) NH3(aqueous)+3/2O2(aqueous)→NO3−+H+(4) NH3(aqueous)+⅔O3(aqueous)→NO2−+H+(5) NH3(aqueous)+O3(aqueous)→NO3−+H+(6) KOH+H2O→K++OH−+H2O (7) Equation (1) illustrates the release of free ammonia from solution into the atmosphere as ammonia gas. This reaction is the normal fate of ammonia in high nitrogenous liquid waste which is responsible for loses of ammonia from the liquid and impacts of ammonia on the environment. Equation (2) shows the acid-base reaction of free ammonia dissolved in liquid to form ammonium cation. The extent of the ionization between ammonia and ammonium-cation may generally depend on the pH of the solution Ammonia in solution reacts with an oxidant for example, ozone or oxygen, as shown in equations (3) through (6) to form oxy-anions of nitrogen depending on the pH of the solution and other chemical species in the background chemical matrix. Under such a reaction, the net effect is that a cation (ammonium ion) is consumed and an anion (nitrite or nitrate) is produced with a loss of two proton equivalents. The reaction may lower the pH if no base is added. Thus, pH may be controlled by limiting the extent of the ammonia oxidation and using the ammonia in the nitrogenous liquid waste as the base. The pH may further be controlled by adding an external base. In some embodiments, a base may be added. Equation (7) illustrates the effect of the addition of an exemplary base, potassium. Other bases may be used depending on the desired composition of the final product. The reactions may produce a solution that contains ammonium ions, nitrogen oxy-anions, cations which originate from the added base, and background cations and anions. A concentrated solution of nitrogen may be recovered as a byproduct in some embodiments. For example, a 1,000 to 170,000 mg/L concentrated solution of nitrogen may be recovered, with a fraction of ammonia oxidation selected, for example, from 30% to 100%. The ratio of ammonium to oxy-anions may be controlled by controlling pH and/or the addition of the external base. The reactions generally induce oxidation of other reduced compounds present in the high nitrogenous liquid. Examples of such compounds include reduced sulfur compounds, organic acids and other organic compounds, reduced iron and manganese. The compounds generally include substances measured as part of the biochemical oxygen demand test, BOD. The oxidation reactions may further serve to stabilize the waste to a form suitable for storage, for example, emitting low odor. In accordance with an aspect, there is provided a method of recovering nutrients from a high nitrogenous waste. The method may comprise collecting the high nitrogenous waste. The high nitrogenous waste may be an organic waste. For example, the high nitrogenous waste may comprise at least one of animal manure or animal litter. The animal manure or animal litter may comprise, for example, urine and/or solids. The high nitrogenous waste may comprise sewage sludge. The high nitrogenous waste may comprise food waste. The high nitrogenous waste may comprise dairy products. In exemplary embodiments, the high nitrogenous waste may comprise animal manure, for example, urine and/or solids, for example, swine manure, poultry manure, cow manure, or other livestock manure. In some embodiments, the high nitrogenous waste may comprise organic matter, an organic matter wastewater, and/or partially treated organic matter. For instance, the high nitrogenous waste may comprise enzymatically hydrolyzed organic waste, organic waste digestate, e.g., digestate from the acid digestion step of organic matter. The high nitrogenous waste may comprise digestates, condensates, and/or leachates of organic matter or an organic matter wastewater. In certain embodiments, the high nitrogenous waste may be a liquid waste having dissolved organic matter. The dissolved organic matter may be an aqueous solution associated with any source of organic matter, such as, animal manure, animal litter, sewage sludge, food waste, dairy products, organic matter wastewater, and/or a partially treated organic matter, as previously described. In certain exemplary embodiments, the liquid waste having dissolved organic matter is effluent from a high rate anaerobic digester. In certain exemplary embodiments, the liquid waste having dissolved organic matter is not associated with a drying process of organic matter. In some embodiments, the high nitrogenous waste may comprise an ammonia wastewater. The ammonia wastewater may comprise ammonia condensate formed by condensing ammonia from a gas into a liquid, ammonia distillate, aqua ammonia, and/or ammonia stillage. The ammonia distillate may comprise digestates, condensates, and/or leachates of ammonia distillate. In certain exemplary embodiments, the nitrogenous waste may comprise an ammonia distillate. The ammonia distillate may comprise an aqueous solution separated from a nitrogenous liquid source by distillation. In certain embodiments, the nitrogenous liquid source is an ammonia or ammonium containing liquid. In certain embodiments, the nitrogenous liquid source is an organic matter containing liquid. The nitrogenous compounds, for example ammonia and other nitrogen-containing species, may be recovered from the nitrogenous waste to produce an organic product or a bioproduct suitable for organic farming. In some embodiments, the nitrogenous compounds are recovered to produce fertilizer. The fertilizer may be a liquid fertilizer comprising nitrogenous compounds. In some embodiments the fertilizer may comprise ammonium crystals or nitrate crystals. In embodiments, for example, where the nitrogenous waste is produced from organic material, fertilizer produced by such methods as described herein may be organic fertilizer, for example, for use on organic farms. Methods and systems disclosed herein may produce an organic product, for example, a certified product suitable for organic farming. Certification may be dependent on the quality of the starting material. In some embodiments, the starting material (i.e. nitrogenous waste, oxidant, and optional base) is compliant with organic certification, and produces a certified organic product. Specifically, such fertilizer products produced by the disclosed methods may not require artificially added materials. Fertilizer products produced by the disclosed methods may comply with requirements outlined by the Organic Materials Review Institute (OMRI). In some embodiments, methods and systems disclosed herein may produce a fertilizer product comprising at least 16% nitrogen by mass. The high nitrogenous waste may be characterized by a high concentration of nitrogenous species, e.g., total nitrogen. In certain embodiments, the high nitrogenous waste may comprise high concentrations of total nitrogen, measured as Total Kjeldahl Nitrogen (TKN). The high nitrogenous waste may comprise about 1,000-12,000 mg/L N, for example, 1,000-3,000 mg/L; 3,000-5,000 mg/L; 5,000-10,000 mg/L; or 10,000-12,000 mg/L N. In certain embodiments, the high nitrogenous waste may comprise about 100,000-300,000 mg/L N, for example, 200,000-300,000 mg/L N. The high nitrogenous waste may be substantially liquid. In some embodiments, the high nitrogenous waste may have less than 10% solids, for example, 1%-10% solids, 1%-8% solids, 1%-6% solids, 1%-4% solids, or 1%-2% solids. Exemplary liquid nitrogenous wastes include flushing pit wastes, e.g., animal manure flushing pit wastes, sewage sludge, organic matter wastewaters, and partially treated organic matter, such as organic waste digestates, condensates, and/or leachates. In exemplary embodiments, the animal manure flushing pit waste may comprise swine manure. In certain embodiments, the liquid nitrogenous waste may be a liquid waste having dissolved organic matter. The high nitrogenous waste may have more than 6% solids, for example, 6%-10% solids, 10%-15% solids, 15%-20% solids, 20%-25% solids, 25%-30% solids, or 30%-35% solids. Exemplary high solids nitrogenous wastes include animal manure and animal litter. In exemplary embodiments, the animal manure and animal litter waste may comprise poultry manure. In some embodiments, the methods may comprise separating the high nitrogenous waste to produce a solids waste and a liquid waste. The liquid waste may comprise less than about 1% solids or about 1%-2% solids. For example, the liquid waste may comprise less than about 1%, about 1%, about 1.5%, or about 2% solids. In certain embodiments, for example, for high nitrogenous wastes having less than about 1% or about 1%-2% solids, the high nitrogenous waste may be referred to as a liquid waste. The solids waste may have about 15%-35% solids, for example 20%-30% solids. The methods may comprise composting or digesting the solids waste. The methods may comprise directing the solids waste to a composter or digester. During composting, aerobic microorganisms break down organic matter into compost. During anaerobic digestion, anaerobic microorganisms convert biologically degradable material in the solids primarily into water and biogas. In particular, anaerobic microorganisms facilitate decomposition of macromolecular organic matter in the solids into simpler compounds and biogas by methane fermentation. Such biogas is primarily carbon dioxide and methane but may include other constituents depending on the composition of the wastewater. In some embodiments, the methods may comprise removing phosphorus from the high nitrogenous waste and/or the liquid waste. Phosphorus may be removed by a biological phosphorus removal process. The methods may comprise directing the high nitrogenous waste and/or the liquid waste to a phosphorus removal process. The methods may comprise removing phosphorus from the high nitrogenous waste and/or the liquid waste to reduce toxicity of the liquid for any oxidation catalyzing microorganisms. In embodiments in which the high nitrogenous waste comprises harmful compounds, the methods may comprise removing at least some of the harmful compounds to maintain viability of the microorganisms. The methods may comprise oxidizing the liquid waste to produce oxy-anions of nitrogen. In particular, the methods may comprise contacting the liquid waste with an oxidant, for example, by introducing the liquid waste and an oxidant into a reactor. The partially oxidized liquid waste may be referred to as an intermediate nitrogenous liquid. Thus, the intermediate nitrogenous liquid may comprise the liquid waste and oxy-anions of nitrogen. The oxy-anions of nitrogen may include, for example, at least one of nitrite and nitrate. The oxidant may be introduced to oxidize a predetermined amount of the nitrogenous compounds to nitrogen ions. The oxidant may comprise oxygen, ozone, a peroxide, such as hydrogen peroxide, or a halogen. In some embodiments, introducing an oxidant comprises contacting the liquid waste with air. Aqueous ammonia may partially oxidize to produce nitrate and nitrite according to equations (3) through (6) above. Oxidation to nitrogen ions will generally lower the pH of the solution by exchanging a weak acid for a strong acid. Controlling oxidation conditions may also provide for a more stable product, for example, by inhibiting the formation of odorous and corrosive compounds in the final product. Controlling dissolved solid concentrations and oxidation reactions may provide for operation in pH ranges that favor operational and capital costs of investment. The oxidation reactions may be inhibited by a high concentration of dissolved ions in solution. In certain embodiments, dilution water may be added to reduce inhibition. For example, makeup water may be added to replace liquid lost in the process and/or to dilute the liquid waste to avoid inhibition effects on the rate of oxidation. The dilution water may be recirculated from a downstream process to reduce environmental impact of the process. When dilution water is added, the product may later be concentrated using several alternative means of removing water from the solution to produce a concentrated liquid fertilizer. As disclosed herein, oxidation may comprise partial oxidation and need not be a complete conversion of ammonia to ionic species. For example, oxidation may be controlled to oxidize between about 5%-80% of the nitrogenous compounds, for example, by controlling supply of the oxidant to the liquid solution. Oxidation may be controlled to between about 5%-40%, 5%-30%, 5%-20%, 5%-15%, 5%-10%, 10%-15%, 10%-20%, 10%-30%, 10%-40%, 10%-50%, 10%-80%, 50%-60%, 50%-70%, or 50%-80%. Oxidation may be controlled to less than 5%, less than 10%, less than 15%, less than 20%, less than 25% conversion, less than 30% conversion, less than 35% conversion, less than 40% conversion, less than 45% conversion, less than 50% conversion, less than 55% conversion, less than 60% conversion, less than 65% conversion, less than 70% conversion, less than 75% conversion, or less than 80% conversion. The extent of conversion may be controlled as required by design of the final fertilizer product. In some embodiments, a fraction of the liquid waste is oxidized. Thus, the methods may comprise controlling a rate of oxidation of the liquid waste. In certain embodiments, the rate of oxidation may be controlled by controlling pH of the liquid. The methods may comprise maintaining the intermediate nitrogenous liquid at a predetermined pH to control a concentration of the oxy-anions of nitrogen and produce a stabilized nitrogenous liquid. The methods may comprise selecting the predetermined pH. The predetermined pH may be selected to correspond with a desired rate of oxidation. For example, the predetermined pH may be selected to control composition of the liquid product and produce a liquid product having a desired composition. The predetermined pH may be between about 3 and about 9, for example, between about 4.0 and about 8.5, for example, between about 5.5 and about 8.5. In exemplary embodiments, a predetermined pH between about 4.5 and about 8.5 may correspond with 5% to about 80% oxidation of nitrogenous compounds in the liquid waste. In some embodiments, the methods may comprise measuring pH of the intermediate nitrogenous liquid. The methods may comprise adjusting pH of the intermediate nitrogenous liquid responsive to the measurement. In some embodiments, methods disclosed herein may comprise maintaining a pH of the intermediate nitrogenous liquid above 3, above 4, above 5, above 6, above 7, or above 8. Methods may comprise maintaining a pH of the intermediate nitrogenous liquid below 9, below 8, below 7, below 6, below 5, or below 3. In some embodiments, the predetermined pH is about 3, about 4, about 4.5, about 4.7, about 5, about 5.5, about 5.7, about 6, about 6.7, about 7, about 7.3, about 7.5, about 8, about 8.5, or about 9. In some embodiments, fluctuations in pH may arise responsive to varying properties of the liquid waste. In practice, maintaining a pH of the liquid may comprise controlling pH to a value within tolerance from the predetermined pH value. Tolerance may be ±1% of the predetermined pH, ±2% of the predetermined pH, ±5% of the predetermined pH, or ±10% of the predetermined pH value. In other embodiments, maintaining pH of the liquid may comprise controlling pH to the predetermined pH value. The predetermined pH and/or desired rate of oxidation may be selected to control composition of the liquid product. The liquid product may comprise ammonia and oxy-anions of nitrogen. The predetermined pH may generally correlate with the desired conversion of nitrogenous compounds to oxy-anions, i.e. with the desired concentration of oxy-anions of nitrogen in the nitrogenous liquid. The composition of the liquid product may comprise 20%-100% oxidation of ammonia to oxy-anions of nitrogen. For example, the composition of the liquid product may be selected to have less than 50% oxidized ammonia. The composition of the liquid product may be selected to have 50%-100% oxidized ammonia. Generally, a greater pH (closer to 9) may correspond with a lesser rate of oxidation (closer to 20% oxidation). A lesser pH (closer to 5) may correspond with a greater rate of oxidation (closer to 100%). In some embodiments, maintaining the intermediate nitrogenous liquid at the predetermined pH and/or adjusting pH of the intermediate nitrogenous liquid comprises at least one of controlling a rate of introduction of the oxidant and controlling a rate of introduction of the liquid waste into the reactor. For example, flow rate of the of the oxidant may be controlled. Flow rate of the liquid waste may be controlled. Generally, a greater flow rate of the oxidant and/or a lesser flow rate of the liquid waste may correspond with a lesser pH and greater rate of oxidation (closer to 100% oxidation). A lesser flow rate of the oxidant and/or a greater flow rate of the liquid waste may correspond with a greater pH and a lesser rate of oxidation (closer to 20%). In some embodiments, the method may comprise introducing a base into the liquid waste or intermediate nitrogenous liquid. Thus, the method may further comprise introducing a base into the reactor. Maintaining the intermediate nitrogenous liquid at the predetermined pH comprises introducing a predetermined amount of a base into the reactor. The base may be a weak or strong base, as required to control oxidation or pH of the process solutions. The base may be a salt of a base, for example, as shown in equation (7), above. Generally, oxidation of the nitrogenous compounds to oxy-anions of nitrogen may be controlled up to 50% conversion without externally adding a base. As shown inFIGS.1A-1C, potassium base, such as potassium hydroxide, may be added to control pH of the intermediate nitrogenous liquid. The percentage of the ammonia oxidized from the nitrogenous waste may be controlled by adding different amounts of the potassium base. When there is no addition of potassium base, the oxidation of ammonia is controlled to 50%. By adding the potassium base, increasing amounts of ammonia may be oxidized up to 100% and converted to oxy-anions of nitrogen. The amount of base added may be selected to correlate with a desired percent conversion of ammonia to oxy-anions, as shown inFIG.1C. For example, in some embodiments, base addition as 2% potassium oxide (K2O) may convert 56% of the ammonia, as 4% K2O may convert 63% of the ammonia, as 7% K2O may convert 71% of the ammonia, as 11% K2O may convert 83% of the ammonia, and as 17% K2O may convert 100% of the ammonia. Thus, the methods may comprise oxidizing between about 50% and about 100% of the nitrogenous compounds by addition of varying amounts of a base. In some embodiments the base may comprise potassium, for example potassium hydroxide or potassium dioxide. The base may comprise any one or more of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, and barium. The base may comprise or be associated with a weak base element, for example, ammonia, carbon, nitrogen, oxygen, fluoride, phosphorus, sulfur, chloride, bromide, and iodine. In some embodiments, the base may be prepared by introducing a salt into water to produce a salt solution. Ions in the salt solution may be electrically separated, for example in an electrodialysis process, to produce a cation stream and an anion stream. The cation stream may be employed as the base, such that the cation stream may be introduced into the liquid waste or intermediate nitrogenous liquid as needed. The anion stream may be employed in a separate process to produce a treated gas and nitrogenous liquid from a nitrogenous gas, as conventionally practiced. The specific salt may be selected to control composition of the final fertilizer product. The oxidation may be catalyzed by microorganisms. In some embodiments, methods may comprise dosing the nitrogenous waste or liquid waste with a biological catalyst. In accordance with certain embodiments, a naturally occurring microbial culture may be employed to enhance the oxidation of nitrogenous compounds. Process liquids may be dosed with biological catalyst, for example a microbial or enzymatic organism. The microbial or enzymatic organism may comprise bacteria and/or archaea. The microbial or enzymatic organism may generally be a nitrifying organism. Catalysis may be accomplished by retaining the biological organisms catalyzing the oxidation in the reaction tank where the oxidant, e.g., oxygen, is supplied. The pH may be controlled between about 4 and 8.5, for example, between about 4.5 and 8.1, depending on the viability of the biological organisms, to allow growth, proliferation, and catalysis of the biological organisms. For instance, it has been found that certain nitrifying microorganisms are capable of growth, proliferation, and catalysis at pH levels as low as 4.0. In certain embodiments, the microorganisms may grow in suspension within the reactor. In some embodiments, the microorganisms may grow attached to surfaces forming a biofilm. In some embodiments, the microorganisms may grow in a combination of suspended growth and biofilm growth. The biofilm may be static in the reactor or moving. The oxidation reaction may be performed in one or several reactors. For instance, microorganisms may be positioned in a first reactor from a plurality of oxidation reactors in series. Microorganisms may be positioned in a second or subsequent reactor from a plurality of oxidation reactors in series. In certain exemplary embodiments, for example, when oxidation is performed in more than one reactor, excess suspended solids may be rich in phosphorus, creating a segregation of nitrogen and phosphorous streams. Once the organisms grow and are established in the system, they may be separated out of the final liquid and/or solid product. In accordance with certain embodiments, the separated biological organisms may be returned to the reaction tank to enhance the culture, further speeding the oxidation reaction. Thus, in some embodiments, methods may comprise separating solids from a stabilized liquid or liquid product. The solids may contain the biological organisms and/or crystalized or precipitated components of the product. The concentration of the final ions in solution may be controlled by employing dilution of process liquids with water. In some embodiments, process liquids may be diluted to preserve viability of the microorganisms. For instance, dilution water may be directed to the reactor to avoid toxicity of the microorganisms. An effective amount of dilution water may be directed to reduce concentration of the toxic creating substance. In some embodiments, process liquids may be diluted or evaporated to induce formation of crystals. In some embodiments, methods disclosed herein comprise controlling a concentration of total dissolved solids (TDS) in the intermediate nitrogenous liquid. For example, the methods may comprise maintaining a concentration of TDS in the intermediate nitrogenous liquid below about a threshold concentration to avoid the formation of crystals. For example, the concentration of TDS may be maintained below about 35%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, or 50% (m/v). In some embodiments, methods comprise maintaining a concentration of TDS above the threshold concentration to induce formation of crystals. For example, methods may comprise maintaining a concentration of TDS above about 46%, 47%, 48%, 49%, 50%, or 55% (m/v). The threshold concentration will generally be dependent on the composition of the nitrogenous waste or liquid waste. The oxidant, base, and/or any additional component added may dictate the threshold concentration to avoid formation of crystals. In some embodiments, for example, wherein the nitrogenous waste comprises sulfur species, the threshold concentration may be 46% (m/v). Exemplary methods disclosed herein may comprise maintaining a concentration of TDS between about 1 g/L and about 500 g/L, for example between about 1 g/L and about 50 g/L. Thus, the methods may comprise measuring TDS of the intermediate nitrogenous liquid. The methods may comprise concentrating or diluting the liquid waste or intermediate nitrogenous liquid responsive to the TDS measurement. In some embodiments, the method comprises collecting the liquid product, the crystals, or both. The crystals may further be processed as a final product. For example, the crystals may be processed as a solid fertilizer. The solid product may comprise at least 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, or 25% nitrogen by mass. In some embodiments, the solid product may comprise less than 1% phosphate and potassium. The solid product may be substantially free of phosphate and potassium. For example, the solid product may comprise less than 0.1%, 0.01%, 0.01% or 0.001% phosphate and potassium. The methods disclosed herein may comprise maintaining a temperature of the liquid waste or intermediate nitrogenous liquid between about 4° C. and about 80° C., for example, between about 10° C. and about 80° C. The methods may comprise measuring temperature of the liquid waste or intermediate nitrogenous liquid. The methods may comprise heating or cooling the liquid responsive to the temperature measurement. The temperature of the process may be controlled to below about 80° C., below about 70° C., below about 60° C., below about 50° C., below about 40° C., below about 30° C., below about 20° C., below about 15° C. In some embodiments, methods may comprise maintaining a temperature of the liquid waste or intermediate nitrogenous liquid at about 4° C., 5° C., 10° C., 15° C., 20° C., 25° C., 30° C., 35° C., 40° C., 45° C., 50° C., 55° C., 60° C., 65° C., 70° C., 75° C., or 80° C., or any range in between. In embodiments in which the oxidation is catalyzed by microorganisms, the methods may comprise controlling temperature of the liquid waste or intermediate nitrogenous liquid to a temperature effective to maintain viability of the microorganisms. In some embodiments, conductivity of one or more process liquids may be measured. Upon reaching a threshold conductivity, one or more of the process liquids may be diluted to maintain the conductivity within a working range. The value of the threshold conductivity may generally vary with certain parameters. For example, the threshold conductivity may be a factor of the quality of the nitrogenous waste or the composition of the added base, oxidant, and/or salt. The threshold conductivity may be between about 200 μS and about 2000 μS, between about 2000 μS and about 20000 μS, between about 20 thousand μS and about 200 thousand μS, or between about 200 thousand μS and about 1.2 million μS. The methods disclosed herein may comprise controlling the rate of oxidation of the nitrogenous compounds in the liquid waste to produce a stabilized nitrogenous liquid. The stabilized nitrogenous liquid may be controlled to a predetermined pH range and have a selected fraction of oxidized nitrogenous compounds. The methods may further comprise concentrating the stabilized nitrogenous liquid to produce a concentrated liquid product and a dilute water. Thus, the stabilized nitrogenous liquid may further be processed as a final product. The method may comprise collecting a liquid product comprising at least a fraction of the stabilized nitrogenous liquid, remaining nitrogenous compounds (for example, nitrogenous compounds that have not been oxidized), and the oxy-anions of nitrogen. The liquid product may be processed as a liquid fertilizer, as described in more detail below. The methods may comprise concentrating the stabilized nitrogenous liquid by removing excess water. Concentrating the stabilized nitrogenous liquid to produce the liquid product may comprise directing the stabilized nitrogenous liquid to a membrane based dissolved solids concentrator and/or an electrochemical separation device. The dissolved solids concentrator may be an evaporation process. The dissolved solids concentrator may be a reverse osmosis process. In some embodiments, the electrochemical separation device may be an electrodialysis process. The electrochemical separation device may be a capacitive deionization process. Other concentration processes may be employed. In certain embodiments, the methods may comprise concentrating the liquid product to further remove excess water. For instance, the methods may comprise concentrating the stabilized nitrogenous liquid by a first concentration process to produce a liquid product and concentrating the liquid product by a second concentration process to produce a further concentrated liquid product. The first and second concentration processes may be the same unit operation or different unit operations, as described above. In exemplary embodiments, the methods may comprise concentrating the stabilized nitrogenous liquid by a reverse osmosis process to produce a liquid product and concentrating the liquid product by evaporation to produce a further concentrated liquid product. In some embodiments, the methods may comprise separating suspended solids from the stabilized nitrogenous liquid. Suspended solids may be separated prior to concentrating the stabilized nitrogenous liquid. For instance, the method may comprise directing the stabilized nitrogenous liquid to a solids-liquid separation unit. The method may comprise separating solids from the stabilized nitrogenous liquid to produce a liquid stream being free of solid materials that interfere with the dissolved solids concentrator. The separated solids may be collected or recirculated within the system. For instance, the method may comprise directing the excess solids to the reactor where the high nitrogenous liquid is processed. The solids-liquid separation may comprise one or more of sedimentation, microfiltration, or ultrafiltration. In certain embodiments, the water removed from the liquid effluent stream may be recirculated back as dilution water to minimize the use of external dilution water. For example, in embodiments where the liquid product is concentrated, the method may comprise returning at least a fraction of the excess water removed from the product to the nitrogenous liquid. The excess water may be returned to control a concentration of components in the liquid waste, for example, oxidant, base, or TDS. The excess water may be returned to control pH of the intermediate nitrogenous liquid, as needed. In some embodiments, the stabilized nitrogenous liquid or liquid product comprises at least 4% nitrogen by mass. The stabilized liquid or liquid product may comprise at least 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, or 20% nitrogen by mass. The quality of the liquid product may be controlled by maintaining a pH between about 3 and about 9, for example maintaining a pH between about 5.5 and 8.5. The pH may generally alter the composition of the solution, by pushing the reaction of equation (2) forwards or backwards or by driving the reactions of equations (2) through (6). Additionally, the quality of the liquid product may be controlled by controlling addition of an oxidant (ORP of the solution), for example, to maintain balance of nitrogenous compounds and oxy-anions of nitrogen in the solution. In some embodiments, the liquid product may comprise less than 1% phosphate and potassium. The liquid product may be substantially free of phosphate and potassium. For example, the liquid product may comprise less than 0.1%, 0.01%, 0.01% or 0.001% phosphate and potassium. The methods disclosed herein may produce a concentrated liquid product that is 2×-10× concentrated for nitrogenous compounds as compared to the high nitrogenous waste. Thus, the concentrated liquid product may have 50%-10% the volume of the high nitrogenous waste. In certain embodiments, the concentrated liquid product may have less than 20% the volume of the high nitrogenous waste. In certain embodiments, the concentrated liquid product may have less than 10% the volume of the high nitrogenous waste. The concentrated liquid product may be easier to handle, store, and transport than the high nitrogenous waste. The concentrated nitrogenous compounds in the liquid product may be in the form of ammonia and oxy-anions of nitrogen. The concentrated liquid product may further be processed as a final product. The method may comprise collecting the concentrated liquid product comprising at least a fraction of the nitrogenous liquid, remaining nitrogenous compounds (for example, nitrogenous compounds that have not been oxidized), and the oxy-anions of nitrogen. The concentrated liquid product may be processed as a liquid fertilizer. In some embodiments, the methods may comprise combining the liquid product with a salt to produce a fertilizer. The salt and/or concentration of the salt added may be selected to control composition of the fertilizer product. Thus, a fertilizer product having an effective amount of nitrogenous compounds and desired composition may be produced by collecting and processing high nitrogenous waste. Concentrating the stabilized nitrogenous liquid to produce the liquid product may also produce a dilute water. The dilute water may have less than 10% w/v nitrogenous compounds of the liquid waste. For example, the dilute water may have less than 5% w/v nitrogenous compounds of the liquid waste. The methods disclosed herein may comprise directing the dilute water to an on-site water demand. In some embodiments, the on-site water demand may be a component of the system for recovery of nitrogenous compounds. For example, dilute water may be directed to the reactor to control composition of the intermediate liquid product. In some embodiments, dilute water may be directed upstream from the reactor. An amount of dilute water effective to inhibit formation of crystals (as previously described) may be directed to the liquid waste or intermediate liquid waste. In some embodiments, the on-site water demand may be separate from the system for recovery of nitrogenous compounds. Exemplary on-site water demands include manure flushing, irrigation, or other agricultural and farm uses, such as cleaning. Exemplary on-site water demands include industrial uses. Dilute water may be directed to an on-site heating or cooling system. Dilute water may be directed to an on-site wastewater treatment system. In accordance with another aspect, there is provided a system for recovering nutrients from a high nitrogenous waste. The system may comprise a reactor fluidly connected to a source of a liquid waste and a source of an oxidant. The reactor may be configured to combine the liquid waste and oxidant to produce an intermediate liquid waste having oxy-anions of nitrogen, as previously described. The reactor may be a tank reactor. The reactor may be aerated. The reactor may be stirred. In some embodiments, the reactor may be a bioreactor. The bioreactor may comprise microorganisms for catalyzing the oxidation reaction. The bioreactor may be constructed and arranged to contact the biological microorganisms with the liquid waste or intermediate nitrogenous waste to enhance oxidation. The bioreactor may be configured to contain suspended microorganisms. The bioreactor may comprise a substrate attaching a biofilm of the microorganisms. The substrate may be suspended in the bioreactor. The substrate may be agitated in the bioreactor. The system may comprise a plurality of reactors. The plurality of reactors may be positioned in series. The plurality of reactors may be positioned in parallel. In certain embodiments, a subset of the plurality of reactors may be arranged in series, with multiple subsets arranged in parallel, forming an array of reactors. In certain embodiments, a first reactor in a series may be a bioreactor. In certain embodiments, a second or subsequent reactor in a series may be a bioreactor. The source of the liquid waste may be configured to provide a liquid waste to the reactor. The source of the liquid waste may be associated with an organic waste, for example, animal manure or animal litter (comprising, e.g., urine and/or solids), sewage sludge, food waste, or dairy products. The source of the liquid waste may comprise enzymatically hydrolyzed organic waste, organic waste digestate, for example, digestate from the acid digestion step of organic matter, or digestates, condensates, and/or leachates of organic matter or an organic matter wastewater. In certain embodiments, the source of the liquid waste may be a liquid waste having dissolved organic matter. The source of the liquid waste may be associated with an ammonia wastewater, for example, ammonia condensate formed by condensing ammonia from a gas into a liquid, aqua ammonia, ammonia distillate, and/or ammonia stillage. The ammonia distillate may comprise, for example, digestates, condensates, and/or leachates of ammonia distillate. In some embodiments, the system may comprise a liquid waste holding tank, a manure flushing pit, a septic tank, a composter, an organic waste or wastewater treatment unit, or an ammonia wastewater treatment unit. The system may comprise a source of an oxidant. The source of the oxidant may be configured to provide an oxidant to the reactor. The source of the oxidant may be a source of air, oxygen, ozone, a peroxide, or a halogen, for example, a liquid tank, gas tank, or an air blower. In some embodiments, the source of the oxidant comprises an aeration vent. The source of the oxidant may comprise one or more oxidant pre-treatment units configured to remove contaminants from the oxidant. In some embodiments, the oxidant is fluidly connectable to the reaction subsystem, for example, through one or more oxidant pre-treatment units. In some embodiments, the oxidant may be a gas, for example, oxygen gas, ozone gas, or air. The reactor may comprise a gas-liquid contactor. The gas-liquid contactor may introduce the oxidant gas into the liquid waste by dispersing the gas with a fine mist of solution or by flowing the gas though a volume of solution. The gas-liquid contactor may be a differential gas-liquid contactor or a stagewise gas-liquid contactor. The reactor may comprise one or more of a gas sparger, a gas-liquid column (for example, a falling-film column, a packed column, a bubble column, or a plate column), a spray tower, an agitated vessel, a scrubber, a rotating disc contactor, a Venturi tube, a dispersion tube, or any other vessel configured to contact a gas and a liquid. In some embodiments, the oxidant may be a liquid, for example, liquid oxygen, a peroxide, or a halogen in liquid form. In exemplary embodiments, the oxidant may be liquid oxygen. In other exemplary embodiments, the oxidant may be hydrogen peroxide. Other liquid oxidants may be employed. The source of the oxidant may be a liquid tank or reservoir. The system may comprise a pH control subsystem configured to maintain a predetermined pH within the reactor. The pH control subsystem may comprise a pH meter configured to measure pH of a solution within the system, for example, of the liquid waste, the intermediate liquid waste, and/or the stabilized liquid waste. One or more setting may be adjusted manually or automatically upon measuring the pH. The pH control subsystem may comprise a control module electrically connected to the pH meter. The control module may be configured to adjust pH within the subsystem, for example, manually or automatically, responsive to a measurement obtained by the pH meter. The pH may be adjusted as required by addition of a pH adjuster, adjusting flow rate of the liquid waste, adjusting flow rate of oxidant (for example, increasing or decreasing aeration), or by dilution or evaporation of a solution within the system. In particular, pH may be adjusted by adjusting a concentration of oxy-anions in the intermediate nitrogenous liquid or the stabilized nitrogenous liquid. The control module may be configured to adjust pH to a value as previously described herein. For example, in some embodiments, the control module may be configured to maintain a pH between about 3 and about 9, maintain a pH between about 5 and about 7, maintain a pH between about 6 and about 8.5, or maintain a pH between about 6.7 and about 8.1. In some embodiments, a pH may be maintained between 4-5, 4-6, 4-7, 4-8, 4-9, 5-6, 5-7, 5-8, 5-9, 6-7, 6-8, 6-9, 7-8, 7-9, or 8-9. The control module may be configured to maintain a pH correlated to a desired concentration of nitrogen oxy-anions in solution, for example, as shown inFIGS.1A-1C. In some embodiments, the pH may be selected such that at least 50% of the nitrogenous compounds are oxidized. The pH may be selected such that at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 99%, or 100% of the nitrogenous compounds are oxidized to oxy-anions of nitrogen. The selection of pH will generally depend on the desired composition of the final product. In some embodiments, the pH control subsystem may comprise at least one flow controller configured to control flow rate of the liquid waste and/or the source of the oxidant. The flow controller may be operatively connected to the control module. The control module may be configured to instruct the flow controller to increase or decrease flow rate of the liquid waste and/or the source of the oxidant into the reactor responsive to the pH measured by the pH meter. For example, the control module may be configured to instruct the flow controller to increase or decrease flow rate of the liquid waste and/or or the source of the oxidant to control pH within the reactor to the preselected pH value. The flow controller may comprise a pump. The flow controller may comprise a valve. The flow controller may comprise a flow meter. In some embodiments, the pH control subsystem may comprise a source of a pH adjuster. The source of the pH adjuster may be fluidly connected to the reactor. In general, the pH adjuster may be a base. In certain embodiments, the pH adjuster may be an acid. The system may comprise a source of a base. The source of the base may be configured to provide a base to the reactor. The source of the base may comprise an acid base production subsystem, such that the source of the base may receive a salt of a base and water, and discharge a cation stream and an anion stream. The acid base production subsystem may be constructed and arranged to introduce salt into the water and electrically separate ions in the salt solution to produce the basic stream (cation stream) and an acidic stream (anion stream). In some embodiments, the acid base production subsystem comprises an ion exchange separation device or an electrically driven membrane separation device, for example, an electrodialysis unit. The acid base subsystem may have a salt inlet, a water inlet, a cation stream outlet, and an anion stream outlet. The acid base production subsystem may be fluidly connectable to the reactor, such that the cation stream may be conveyed to the reactor as the pH adjuster. The source of the base may further comprise one or more base pre-treatment units configured to remove contaminants from any one or more of the base, the salt, the water, the anion stream, or the cation stream. In some embodiments, the base is fluidly connectable to the reactor, for example, through one or more base pre-treatment units. The salt or the water may be fluidly connectable to the acid base production subsystem through one or more base pre-treatment units. The anion stream may be fluidly connectable to the second reaction subsystem through one or more base pre-treatment units. The system may comprise a dissolved solids concentrator configured to produce a concentrated liquid product and a dilute water from the stabilized nitrogenous liquid waste. The dissolved solids concentrator may be fluidly connected downstream from the reactor. The dissolved solids concentrator may employ one or more of reverse osmosis (RO), ion exchange, electrodialysis (ED), capacitive deionization, evaporation, or other similar process to separate dissolved solids from a liquid product. The dissolved solids concentrator may comprise a product outlet and a dilute liquid outlet. The product may be further processed for use, for example, by further concentration and/or by post-treatment as fertilizer. In certain embodiments the system may comprise a plurality of dissolved solids concentrators fluidly connected downstream from the reactor in series. For instance, the system may comprise a first dissolved solids concentrator having an inlet fluidly connected to the reactor and a second dissolved solids concentrator having an inlet fluidly connected to the first dissolved solids concentrator. In exemplary embodiments, the system may comprise a reverse osmosis unit and an evaporator fluidly connected downstream from the reactor in series. The concentrated liquid product may be directed to a fertilizer production unit. In some embodiments, the system may comprise the fertilizer production unit. In some embodiments, the concentrated liquid product may be transported to an off-site fertilizer production unit. The fertilizer production unit may comprise a mixing chamber. The fertilizer production unit may be fluidly connected to a source of a salt. The salt may be selected to control composition of the final product. The dilute water may be recirculated in the system. For instance, a dilute water outlet of the dissolved solids concentrator may be fluidly connected to the reactor or a unit operation upstream from the reactor. In some embodiments, the system may comprise a recirculation line extending between the dissolved solids concentrator and an inlet of the reactor. The recirculation line may be constructed and arranged to reintroduce dilute liquid from the dissolved solids concentrator to the reactor. The recirculation line may provide further control of the concentration of the TDS throughout the process. Liquid from the reactor may be conveyed to the dissolved solids concentrator, for example, to an evaporator or reverse osmosis unit, to adjust the solids concentration within the dissolved solids concentrator. Where the liquid is conveyed to an evaporator, the concentrated liquid may then be conveyed to a solids-liquid separation unit to remove excess solids from the liquid fraction. The liquid fraction may be used as a product or returned to the reactor. In this embodiment, the system could produce a dilute liquid product or a concentrated product by controlling the operating conditions. The dilute water may be fluidly connected to an on-site water demand. In some embodiments, the on-site water demand may be a component of the system. For example, dilute water may be directed through the recirculation line. In some embodiments, the on-site water demand may be separate from the system. Exemplary on-site water demands include manure flushing, irrigation, or other agricultural and farm uses, such as cleaning. Exemplary on-site water demands include industrial uses. Dilute water may be directed to an on-site heating or cooling system. Dilute water may be directed to an on-site wastewater treatment system. In certain embodiments, the system may comprise a solids-liquid separator fluidly connected to a source of a high nitrogenous waste. The solids-liquid separator may be configured to separate solids from the high nitrogenous waste and produce the liquid waste, which is directed to the reactor for oxidation, as previously described. The solids may be directed to a solids treatment unit. The solids-liquid separator may be a course suspended solids separator. In certain exemplary embodiments, the solids-liquid separator may be a centrifuge or hydrocyclone. In some embodiments, the solids-liquid separator may be a sedimentation unit. In some embodiments, the solids-liquid separator may be a filter, for example, a coarse filter. In particular embodiments, the coarse filter may be a filter in the ground where manure is collected. The solids-liquid separator may employ one or more of centrifugation, sedimentation (for example, comprising a clarifier or thickener), filtration (for example, by size, charge, or density) (for example, nanofiltration, microfiltration, ultrafiltration, or another membrane filtration), evaporation, or other similar process to separate suspended solids from the liquid waste. The solids outlet of the solids-liquid separator may be connectable to a solids treatment unit. In some embodiments, the system may comprise the solids treatment unit. In other embodiments, the solids may be transported to an off-site solids treatment unit. The solids treatment unit may comprise, for example, a composter and/or an anaerobic digester. The composter may comprise a tank or reactor comprising aerobic microorganisms. The anaerobic digester may comprise a tank or reactor comprising anaerobic microorganisms. A source of nutrients to facilitate digestion may be fluidly connected to the composter and/or anaerobic digester. In some embodiments, the system may comprise a pre-treatment unit positioned upstream from the reactor. The pre-treatment unit may be configured to remove contaminants harmful to reactor microorganisms upstream from the reactor. In some embodiments, the pre-treatment unit has an inlet fluidly connected to the source of the high nitrogenous waste and an outlet fluidly connected to the reactor or a solids-liquid separation unit upstream from the reactor. In some embodiments, the pre-treatment unit has an inlet fluidly connected to a liquid waste outlet of a solids-liquid separation unit and an outlet fluidly connected to the reactor. One exemplary pre-treatment unit comprises a phosphorus removal unit. The phosphorus removal unit may be configured to remove phosphorus from the high nitrogenous waste and/or the liquid waste. The phosphorus removal unit may be a biological phosphorus removal unit, comprising a tank or reactor comprising phosphorus accumulating organisms (PAOs). In some embodiments, a plurality of reactors may be arranged to induce biological phosphorus removal. Other pre-treatment units may be employed for removal of phosphorus or other contaminants. In certain embodiments, the system may comprise a second solids-liquid separator fluidly connected to an outlet of the reactor and an inlet of the dissolved solids concentrator. The second solids-liquid separator may be configured to separate solids from the stabilized nitrogenous liquid and produce a liquid, which is directed to the dissolved solids concentrator. The second solids-liquid separator may be a fine solids separator. In certain exemplary embodiments, the second solids-liquid separator may be a sedimentation unit, a microfiltration unit, or an ultrafiltration unit. In some embodiments, the second solids-liquid separator employs filtration (for example by size, charge, or density) to separate a liquid fraction from solids. In some embodiments, the second solids-liquid separator employs sedimentation (for example, comprising a clarifier or thickener) to separate a liquid fraction from solids. The second solids-liquid separator may comprise a solids outlet and a liquid product outlet. The liquid product may comprise nitrogenous liquid fertilizer. The liquid product may be further processed for use, for example, as a fertilizer. The solids outlet of the second solids-liquid separator may be fluidly connected to the reactor. The system may comprise a solids recirculation line extending from the solids outlet of the second solids-liquid separator and the reactor. Some of the solid fraction may be returned to the reactor, while some of the solid fraction may be removed from the system as waste. In some embodiments, for example, in embodiments in which the system employs biological organisms to catalyze oxidation reactions, the solids retained may comprise biological flocs of organisms. The biological flocs may be returned to the reaction subsystem to further catalyze oxidation reactions. In some embodiments, the solids may comprise crystals of ammonium salts, or other precipitates, such as calcium sulfate or iron oxides, formed from elements present in the water and the absorbed gases. The nature of the solids separated will generally depend on the design and operational conditions of the system and method. The composition of the solid and/or liquid product may be controlled by adding salts to the process liquids. In some embodiments, the system may comprise a source of a salt. The source of the salt may be fluidly connectable to the reactor. The source of the salt may comprise a mixing chamber. For example, the source of the salt may comprise a mixing chamber constructed and arranged to combine the salt with water or with nitrogenous liquid. The source of the salt may be positioned upstream or downstream from the reactor. In some embodiments, the source of the salt may be configured to introduce the salt into the liquid upstream of the reactor. The source of the salt may comprise one or more salt pre-treatment units configured to remove contaminants from the salt. In some embodiments, the salt is fluidly connectable to the reactor, for example, through one or more salt pre-treatment units. The system may comprise a temperature control subsystem configured to maintain a predetermined temperature within the reactor. The temperature control subsystem may comprise a temperature sensor. The temperature sensor may be configured to measure temperature of one or more solution within the system. For example, the temperature sensor may be configured to measure temperature of the intermediate nitrogenous liquid within the reactor, of the high nitrogenous waste, of the liquid waste, or of the oxidant. One or more setting may be adjusted manually or automatically upon measuring the temperature. The temperature control system may comprise a control module electrically connected to the temperature sensor. The control module may be configured to maintain a predetermined temperature range, as previously described herein, within the reactor. In some embodiments, the control module may be configured to adjust a temperature within the reactor, for example, manually or automatically, responsive to a measurement obtained by the temperature sensor. In some embodiments, the predetermined temperature range is between about 4° C. and about 80° C., for example, between about 10° C. and about 80° C. The temperature control subsystem may comprise a heat exchanger. The system may employ active or passive heat transfer to control the temperature. In some embodiments, the temperature control subsystem comprises a chiller or cooling tower. In some embodiments, the temperature control subsystem comprises a cooling and heating unit. The system may further be configured to provide heat to the source of the high nitrogenous waste. The system may be configured to provide heat to the source of the oxidant. The system may comprise a heat exchanger constructed and arranged to transfer heat between components of the system. The heat exchanger may employ mechanisms to diffuse heat within the system, for example, to conserve heat energy. In some embodiments, the heat exchanger is employed to adjust a temperature within the reactor to a working temperature, as previously described herein. In some embodiments, the heat exchanger may be configured to adjust the temperature within the reactor to between about 4° C. and about 80° C., for example, between about 10° C. and about 80° C. The system may comprise an oxidation control subsystem. The oxidation control subsystem may be configured to maintain a predetermined oxidation reduction potential (ORP) within the reactor. In some embodiments, the oxidation control system may comprise ORP sensor configured to measure ORP of a solution within the reactor. One or more setting may be adjusted manually or automatically upon measuring the ORP. The system may further comprise a control module electrically connected to the ORP sensor. The control module may be configured to adjust the ORP within the reactor, for example, manually or automatically, responsive to a measurement obtained by the ORP sensor. The control module may be configured to provide more or less oxidant to the reactor, to adjust the ORP therein. The control module may be configured to increase or decrease flow rate of the liquid waste into the reactor, to adjust the ORP therein. In some embodiments, the predetermined ORP is between about +400 mV and about +900 mV. The predetermined ORP may be between about +200 mV and about +1200 mV, between about +400 mV and about +1000 mV, between about +500 mV and about +700 mV, between about +400 mV and about +600 mV, between about +500 mV and about +800 mV, or between about +600 mV and about +900 mV. The predetermined ORP may be about +400 mV, about +500 mV, about +600 mV, about +700 mV, about +800 mV, or about +900 mV. The predetermined ORP may be less than about +900 mV, less than about +800 mV, less than about +700 mV, less than about +600 mV, less than about +500 mV or less than about 400 mV. In some embodiments, the predetermined ORP may be more than about +400 mV, more than about +500 mV, more than about +600 mV, more than about +700 mV, more than about +800 mV, or more than about +900 mV. In some embodiments, the system may comprise a conductivity meter. The conductivity meter may be configured to measure conductivity of a solution within the reactor. One or more settings may be adjusted manually or automatically upon measuring the conductivity. The system may comprise a control module electrically connected to the conductivity meter. The control module may be configured to adjust the conductivity of the solution within the reactor, for example manually or automatically, responsive to a measurement obtained by the conductivity meter. In some embodiments, the control module may adjust conductivity by adjusting one or more of pH, temperature, concentration of ions (for example, by adding a salt), flow rate of the liquid waste, flow rate of the oxidant, or flow rate of the base into the reactor. In accordance with certain embodiments, the control module may be configured to maintain a predetermined concentration of TDS in the solution within the reactor. For instance, the control module may be configured to maintain a concentration of TDS below a threshold concentration to avoid formation of crystals. The control module may be configured to maintain a concentration of TDS in the solution within the reactor above a threshold concentration to induce formation of crystals. The threshold concentration may be selected based on the composition of the solution, which in turn may generally depend on composition of the waste, selection of the oxidant, and any base and/or salt added. In certain embodiments, composition of the final product may be controlled or designed for a particular use by selecting the base and/or salt. In some embodiments, the control module may adjust a concentration of TDS within the reaction subsystem by adjusting one or more of pH, temperature, concentration of ions (for example, by adding a salt), flow rate of the liquid waste, flow rate of the oxidant, or flow rate of the base into the reactor. The system may comprise one or more control module. The control module may be a computer or mobile device. The control module may comprise a touch pad or other operating interface. For example, the control module may be operated through a keyboard, touch screen, track pad, and/or mouse. The control module may be configured to run software on an operating system known to one of ordinary skill in the art. The control module may be electrically connected to a power source. The control module may be digitally connected to the one or more components. The control module may be connected to the one or more components through a wireless connection. For example, the control module may be connected through wireless local area networking (WLAN) or short-wavelength ultra-high frequency (UHF) radio waves. The control module may further be operably connected to any additional pump or valve within the system, for example, to enable the control module to direct fluids or additives as needed. The control module may be coupled to a memory storing device or cloud-based memory storage. Multiple control modules may be programmed to work together to operate the system. For example, a control module may be programmed to work with an external computing device. In some embodiments, the control module and computing device may be integrated. In other embodiments, one or more of the processes disclosed herein may be manually or semi-automatically executed. FIG.2presents one exemplary embodiment of the system. A schematic of an exemplary system for the recovery of nitrogenous compounds in the form of a liquid product is shown inFIG.2. A liquid containing nitrogenous compounds114may be introduced into a reactor100and put in contact with an oxidant104. Optionally, a base102may be introduced into the reactor100. A pH control subsystem174is configured to maintain a predetermined pH of the liquid within reactor100. Stabilized nitrogenous liquid122may be transferred to a dissolved solids concentrator120to remove dilution water124and produce a concentrated product126. Excess solids108may be conveyed out of the system. Dilution water124may be directed to an on-site demand. FIG.3illustrates another embodiment. In the exemplary embodiment ofFIG.3a solids-liquid separator134may be positioned upstream from the reactor100before liquid containing nitrogenous compounds114is introduced into reactor100. This configuration may be employed, for example, when the nitrogenous waste123has a greater concentration of solids. Nitrogenous waste123may be directed to the solids-liquid separator134to produce the liquid containing nitrogenous compounds114which is conveyed to the reactor100. The stream containing separated solids136may be directed to a solids treatment unit138. FIG.4illustrates another embodiment. In the exemplary embodiment ofFIG.4a solids-liquid separator130may be coupled to the reactor100before the stabilized nitrogenous liquid122is conveyed to the dissolved solids concentrator120. This configuration may be employed, for example, when the oxidation reaction is catalyzed by microorganisms. The liquid product121after reaction may be conveyed to the solids-liquid separator120. The stream containing separated solids132may be returned to reactor100. Excess solids109may be removed from the reactor100. FIG.5illustrates another embodiment. In the exemplary embodiment ofFIG.5, dilution water128is directed to the reactor100. Temperature of the reactor100may be controlled. In some embodiments, heat106may be added or removed from one or more components of the system. Heat106may be added or removed from the system using a heat exchanger or by evaporating or condensing water in the system to control temperature. FIG.6illustrates another embodiment. In the exemplary embodiment ofFIG.6, dilution water124is directed from dissolved solids concentrator120to reactor100. FIG.7illustrates one embodiment of the reactor100. In the exemplary embodiment ofFIG.7a tank containing the intermediate nitrogenous liquid with submerged gas spargers is used. Fine bubbles of the oxidant, e.g., air, are created by the gas spargers, inducing oxidation of the nitrogenous liquid, for example, according to Equations (1) to (7) above. FIG.8illustrates another embodiment of the system. In the exemplary embodiment ofFIG.8the concentrated liquid product126after the dissolved solids concentrator120may be combined with a salt152in a mixing chamber150. The salt may be selected to control composition of final product154. In certain embodiments, no base is added to the reaction chamber100and, instead, the salt of the base152may be added in the mixing chamber150, as required, to control composition of the final product154. FIG.9illustrates another embodiment. In the exemplary embodiment ofFIG.9, the process employs an acid base production chamber160. The cation stream from the acid base production may be introduced into the reactor100as the base102. The anion stream may be used as an acid162for on-site or off-site purposes. This arrangement may employ the use of a salt152and water128for capturing nitrogenous compounds as needed, to produce the desired final product. The systems disclosed herein may comprise a plurality of channels extending between separate components of the system for delivering gases and solutions between the components of the system. The systems may comprise one or more pumps, blowers, or fans to drive gases and solutions within the system. The systems may further comprise one or more tanks for holding gases or solutions, for example, product tanks for holding liquid product and/or product comprising solids. FIG.10illustrates one exemplary embodiment for a method of recovering nitrogenous compounds from a nitrogenous waste. The exemplary embodiment ofFIG.10illustrates a method where organic waste from a swine flushing pit is separated to produce a liquid waste and solids. The liquid waste is directed to an oxidation reactor. In the exemplary embodiment ofFIG.10, an oxidant (for example, oxygen) is combined with the liquid waste. A stabilized nitrogenous liquid containing oxy-anions of nitrogen is produced by the oxidation. The stabilized nitrogenous liquid is concentrated by ultrafiltration-reverse osmosis to remove a dilute water and produce a concentrated liquid product. A laboratory trial of the method ofFIG.10is described in more detail below. FIG.11illustrates another embodiment of a system. The exemplary embodiment ofFIG.11includes source of nitrogenous waste112, pre-treatment unit136, solids-liquid separator134, reactor100, second solids liquid separator130, and dissolved solids concentrator120. In the exemplary embodiment ofFIG.11, a nitrogenous waste112is directed to pre-treatment unit136to remove contaminants. The pre-treatment unit may be a phosphorus removal unit, such as a biological phosphorus removal unit, or any other contaminant removal. InFIG.11, pre-treatment unit136is positioned upstream from solids-liquid separator134. However, pre-treatment unit136may be positioned downstream from solids-liquid separator134. The waste is directed to solids-liquid separator134to produce solids and a liquid waste. The liquid waste is directed to reactor100. A source of an oxidant104and a source of a base102are fluidly connected to the reactor100. The liquid waste, oxidant, and base may be combined in the reactor100. A source of a salt117may fluidly connected to the reactor100, depending on the desired composition of the final product. Optionally, dilution water128may be fluidly connected to the reactor100. In certain embodiments, dilution water128may be directed from dissolved solids concentrator120(shown inFIG.6). A pH control unit174may provide pH control to the system. The pH control unit174may be operatively connected to liquid waste flow controller143and/or oxidant flow controller145. The pH control unit174may be operatively connected to source of the base102. A temperature control unit190may provide temperature control to the system. Temperature control unit190may be operatively connected to heat exchanger106. An oxidation control unit176may provide oxidation control to the system. Ion concentration control unit178may provide ion concentration control to the system. A sensor or meter182(for example, temperature sensor, pH meter, ORP sensor, and/or conductivity meter) may be configured to take measurements within reactor100. A control module170may be electrically connected to the sensor or meter182, for example via one or more wires (not shown) or wirelessly. Control module170may be operatively connected to any one or more of pH control unit174, temperature control unit190, oxidation control unit176, and ion concentration control unit178. Stabilized nitrogenous liquid may be removed from the reactor100and concentrated, for example in dissolved solids concentrator120, to produce a concentrated liquid product and dilute water. The concentrated product may be stored in tank142. The concentrated product may be stored, used, or processed for further use. The dilute water may be stored in tank146. The dilute water may be stored, used, or processed for further use. Excess solids removed by solids-liquid separator134may be stored in tank144. The excess solids may be stored, used, or processed for further use. Excess solids removed from second solids-liquid separator130may be returned to the reactor100. EXAMPLES The function and advantages of these and other embodiments can be better understood from the following examples. These examples are intended to be illustrative in nature and are not considered to be limiting the scope of the invention. Example 1 System for Recovery of Nitrogenous Compounds Operation of an exemplary system for recovery of nitrogenous compounds was estimated using laboratory results.FIG.10illustrates the estimated performance of a system processing the manure of 5,000 pigs from a manure flushing pit, corresponding to an estimated nitrogenous waste volume of about 1,300 ft3/day. The estimated flow rates and nitrogen, phosphorous, and potassium content of the process streams are shown in Table 1. TABLE 1Process StreamsSlurryLiquidProductWaterFlowrate (ft3/day)1,3001,100751,025N (lb/kgal)12.57.51030.53P (lb/kgal)4.71.4190.10K (lb/kgal)9.78.91230.63 As shown in the exemplary embodiment ofFIG.10, the nitrogenous waste slurry is conveyed to a decanter for separation of the solids and liquids. The liquid waste is estimated to be 1,100 ft3/day. The liquid waste is conveyed to an aerated tank for biological oxidation of the organic and nitrogenous material under controlled pH conditions. After biological oxidation, the stabilized nitrogenous liquid having an approximate ratio of 50% ammonia and 50% nitrate is directed to an ultrafiltration-reverse osmosis unit for concentration. Water removed from the stabilized nitrogenous liquid (permeate from the reverse osmosis) is estimated to be about 1,025 ft3/day. The water can be directed to an on-site demand, such as for use in the farm. The concentrated liquid product is estimated to be about 75 ft3/day. The concentrated liquid product may be stored on-site for further use. Accordingly, the system for recovery of nutrients from a high nitrogenous waste produces a concentrated liquid product effective for reuse in agricultural applications. Example 2 pH Control System An exemplary pH control system was operated according to the methods disclosed herein. The results are shown in the graph ofFIG.12. The results correspond to operation of an exemplary pump delivering the high nitrogenous liquid waste to a bioreactor for oxidation of nitrogenous compounds to nitrate. A pH sensor measured pH of the liquid within the bioreactor. In the exemplary embodiment, pH was controlled to about 7.3 by controlling flow rate of the high nitrogenous liquid waste into the reactor. Aeration was maintained substantially constant. The graph ofFIG.12shows pH of the bioreactor as a function of amount of time that the high nitrogenous waste pump was on. Pump operation is a proxy for the rate of high nitrogenous liquid waste introduced to the reactor, as the pump was maintained at a constant setting. As shown in the data ofFIG.12, pH may be controlled to a selected target pH (here approximately 7.3) by controlling a rate of introduction of the liquid waste into the reactor. Thus, oxidation of the high nitrogenous liquid waste (by controlling the rate of delivery of the liquid waste) may control pH and composition of the liquid without addition of an external agent, such as an acid. The phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. As used herein, the term “plurality” refers to two or more items or components. The terms “comprising,” “including,” “carrying,” “having,” “containing,” and “involving,” whether in the written description or the claims and the like, are open-ended terms, i.e., to mean “including but not limited to.” Thus, the use of such terms is meant to encompass the items listed thereafter, and equivalents thereof, as well as additional items. Only the transitional phrases “consisting of” and “consisting essentially of,” are closed or semi-closed transitional phrases, respectively, with respect to the claims. Use of ordinal terms such as “first,” “second,” “third,” and the like in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are performed, but are used merely as labels to distinguish one claim element having a certain name from another element having a same name (but for use of the ordinal term) to distinguish the claim elements. Having thus described several aspects of at least one embodiment, it is to be appreciated various alterations, modifications, and improvements will readily occur to those skilled in the art. Any feature described in any embodiment may be included in or substituted for any feature of any other embodiment. Such alterations, modifications, and improvements are intended to be part of this disclosure and are intended to be within the scope of the invention. Accordingly, the foregoing description and drawings are by way of example only. Those skilled in the art should appreciate that the parameters and configurations described herein are exemplary and that actual parameters and/or configurations will depend on the specific application in which the disclosed methods and materials are used. Those skilled in the art should also recognize or be able to ascertain, using no more than routine experimentation, equivalents to the specific embodiments disclosed. | 84,323 |
11858840 | DETAILED DESCRIPTION OF THE INVENTION FIG.1shows a preferred embodiment of the apparatus of the present invention designated generally by the numeral10. Wastewater treatment system10can include a first phase to replace ferric salts and to verify treatment efficacy. A second phase verifies yields on protein/fat. InFIG.1, wastewater flow11from an animal processing plant can be for example about one thousand gallons per minute (1,000 gpm). The raw biological oxygen demand (B.O.D.) of this wastewater stream11can be between about 1800-2000 milligrams per liter (mg/l). The first stage treatment can include a first flocculation unit or floc tube16. A second stage treatment can include a second floc tube20as part of a second chemical injection site. As part of the first stage of the method of the present invention, acid12(e.g., sulfuric acid, hydrochloric acid) is added to acidify wastewater stream11, bringing pH to between 4.8 and 5.2, preferably about 5.0. A density modifier13is then added to wastewater stream11, between 10 and 1000 milligrams per liter (mg/l), preferably between about eighty to two hundred forty (80-240) milligrams per liter. The density modifier13can be lanthanum, lanthanum salt, a lanthanum water mix, cerium, praseodymium salt or a combination of one or more of those. Arrows34,35,36,37schematically illustrate flow of chemicals from vessels12,13,14,15to first flocculation unit16via flow lines22,23,24,25. Each flow line22,23,24,25can be equipped with a pump (30,31,32,33inFIG.1) to assist in transmission of material in vessels12,13,14,15to flocculation unit16. A cationic polymer 14 can then be added to wastewater stream11between and 50 mg/l, preferably about 8 mg/l. An anionic polymer 15 is added preferably between about 5 and 50 mg/l and preferably about 8 mg/l. After the chemical treatment in first flocculation unit16, the wastewater stream discharges from flocculation unit16to first dissolved air floatation unit17via flow line47. In dissolved air floatation unit17, protein floats to the top of the dissolved air flotation unit17where it can be skimmed off into a sludge hopper or other suitable vessel. This treated wastewater stream exits first dissolved air flotation unit17via line48with a pH of between about 4.8 and 5.2, preferably about 5.0. This treated waste stream has a B.O.D. of between about 500-1000 mg/l. The treated wastewater discharged from first dissolved air floatation unit17is pumped/transmitted via line48to a holding tank or reactor vessel18(e.g., 300,000 gallons). Treated wastewater is retained in holding tank/reactor18for 1 to 12 hours. In reactor vessel18, a lanthanum promoted redox reaction occurs that produces alkalinity. The reactor18effluent is pumped/transmitted via flow line46(arrow19) to a second phase chemical treatment which can include use of a second flocculation unit20. The flow rate to the second flocculation unit20and second dissolved air flotation vessel21can be between 1,000 and 1,500 gallons per minute, such as about 1200 gallons per minute. In line chemical injection at second flocculation unit or floc tube20further reduces the B.O.D. of the wastewater stream to less than 240 mg/l. Chemical injection of sulfuric acid12, rare earth/lanthanum mix13, cationic polymer 14 and anionic polymer 15 are via flow lines26,27,28,29as shown inFIG.1. Each flow line26,27,28,29can be supplied with a pump (38,39,40,41inFIG.1). Arrows42,43,44,45schematically show flow from vessels12,13,14,15via flow lines26,27,28,29to second flocculation unit20. Flow line/arrow22designates flow of the wastewater stream from second flocculation unit20to second dissolved air floatation unit21. Protein floats to the top of the second dissolved air floatation unit21separating from the wastewater and is skimmed off the top of the dissolved air floatation unit into a sludge hopper or selected vessel. Recovered skimmed material is now suitable for disposal or further processing such as separating the fat and protein. After the chemical treatment with the selected rare earth density modifier of second flocculation unit20and second dissolved air floatation unit21treatment, the wastewater stream is suitable for discharge via flow line49into, for example, a municipal water stream and is well within required regulatory parameters for safety (e.g., BOD equals 500-1,000 mg per liter). FIG.2shows an extraction process of the apparatus and method of the present invention. Dissolved air floatation “float” from the processing plant (dissolved air flotation units) is preferably dried in a vacuum rotary dryer (and then preferably baked in an oven, if necessary) until the solid content is approximately 85%. The process of separating the protein meal from the fat is as follows: The dried dissolved air floatation “float” is placed into an extraction vessel50, which preferably has a heat resistant liner bag, until the bag is approximately 90% full. The vessel50is preferably closed using a quick-closure lid60. Extraction vessel50can have a volume of 2,100 L, a temperature of 60° C., and a pressure of 70 bar, and can hold 550 gallons. At this time, a heated solvent from solvent storage tank56and via heater53is pumped with solvent pump54and compressor59into the extraction vessel50(for example, acetone, ethyl, laurate, hexane, and/or CO2) at a ratio of 10% solvent to 90% dissolved air floatation “float”. Solvent storage tank56can have a volume of 3,000 L and ambient temperature, and can hold 800 gallons. Solvent heater53can be 5 KW. Solvent pump54can be 10 KW. Compressor59can be 40 KW. The CO2is then pumped from a CO2storage55into the extraction vessel50until the desired pressure is attained. For example, for a 2100 liter (≈550 gallons) vessel, and a temperature of 60° C. (140° F.), the CO2is pumped via pump58into the extraction vessel50until a pressure of 70 Bar (1000 psi). CO2storage55can have a volume of 2,000 L, a temperature of 20° C., and a pressure of 60 bar, and can hold 500 gallons. The cycle is repeated at least one more time, or multiple times. When the desired number of cycles have been completed, the extraction vessel50is pressurized using the CO2, and the new separated fat is “pressed” out of the extraction vessel50through a bottom valve61. The compound of fat, acetone and some CO2now flows through piping68to a CO2evaporator57(150 kilowatt for example) where the CO2gas is sent to a CO2condenser52(150 KW) and then returned in liquid form into the CO2storage tank55. Evaporator57can be 150 KW. Condenser can be 150 KW. Meanwhile, the fat/acetone (solvent) compound enters a separator51at a temperature of, for example 30° C. (70° F.) and a pressure of 1000 psi. Alternatively, the fat/acetone compound could be processed through a distiller (for example, 100 liter) at a temperature of 150° C. (302° F.) and a pressure of 1 Bar (14 psi). The acetone is separated in the liquid/gaseous form, and leaves the separator51(or distiller) and enters into the solvent storage tank56for the next cycle. Separator51can have a volume of 100 L, a temperature of 30° C., and a pressure of 70 bar. The dried protein meal bag is removed from the extraction vessel50, the fat is removed from the separator51(distiller) and the next cycle begins. FIG.3shows a method of mixing lanthanum and water. Lanthanum is a commercially available solid crystal material. The lanthanum is placed in a hopper67. Auger or conveyor device62transports the lanthanum into a mixing tank63. Mixing tank63can be about 8′ diameter and about 7′ in height, and can hold about 2,000 gallons. Lanthanum is dissolved with water in mixing tank63with rotating paddles64. Paddles64can be driven by motor drive69and drive shaft70. The mixture of lanthanum and water is then pumped via piping65to holding tank66. Holding tank/vessel66can be 12′ diameter and 8′ in height, and can hold about 7,500 gallons. Holding tank/vessel66can be provided with discharge pipe71. The following is a list of parts and materials suitable for use in the present invention: PARTS LIST:PART NUMBERDESCRIPTION10treatment system11wastewater stream/influent pipe12acid/vessel13density modifier/vessel14cationic polymer/vessel15anionic polymer/vessel16flocculation unit/floc tube17first dissolved air flotation unit18reactor/vessel19arrow - reactor discharge20flocculation unit/floc tube21second dissolved air flotation unit22flow line/arrow23flow line/arrow24flow line/arrow25flow line/arrow26flow line/arrow27flow line/arrow28flow line/arrow29flow line/arrow30pump31pump32pump33pump34pump35pump36pump37pump38pump39pump40pump41pump42arrow43arrow44arrow45arrow46flow line47flow line48flow line49flow line50extraction vessel51separator52CO2condenser53solvent heater54solvent pump55CO2storage56solvent storage57CO2evaporator58CO2pump59compressor60quick closure lid61valve62auger/conveyor device63mixing tank64paddles65piping66holding tank67hopper68piping69motor drive70drive shaft71pipe All measurements disclosed herein are at standard temperature and pressure, at sea level on Earth, unless indicated otherwise. All materials used or intended to be used in a human being are biocompatible, unless indicated otherwise. The foregoing embodiments are presented by way of example only; the scope of the present invention is to be limited only by the following claims. | 9,332 |
11858841 | DETAILED DESCRIPTION OF THE BEST MODE A raw water stream1will be drawn into a treatment facility, typically by pumping stream1from a lake, river, stream, or reservoir. Raw water in stream1could come from a ground water well. However, ground water typically includes many fewer contaminants than surface water. Thus, many of the steps disclosed herein will be most applicable to surface water treatment. That being said, the utility of the steps disclosed herein will depend upon the contaminants in stream1, not its source. Stream1will be passed through one or more screens2. The object of screens2is to remove debris and other solids from stream1. The primary targets of screens2will be things like fish, plants, litter, and most large objects that may be present in surface waters. Screens2may also include some finer filtration as well. However, in most embodiments screening is primarily directed toward larger objects. Next, a pre-oxidant3(sometimes referred to herein as a secondary oxidant) may be added to stream1. Pre-oxidants3include chemicals such as chlorine, chlorine dioxide, ozone, and potassium permanganate. These chemicals can oxidize organic carbon, though that is a secondary purpose of adding them at this stage of treatment. At this stage, they are being added to stream1predominantly to control bacterial growth. In the preferred embodiment, about 0.1 to about 0.5 mg/L of a halogen pre-oxidant3is added to stream1. (As used herein, the term “about” means plus or minus 10 percent, unless otherwise indicated.) At this point, it is observed that any addition to stream1should be NSF approved. Chemicals used to treat drinking water throughout North America are required to comply with NSF/ANSI 60. The list of chemicals and additives approved under this standard may vary with time. Suitable pre-oxidants3and other additives discussed below will likewise vary. A coagulant5is added to stream1. The preferred coagulant comprises about 10 to 20 percent polydadmac or other cationic polymer and about 30 to 60 percent aluminum chlorohydrate or sodium aluminate. Suitable commercial coagulants include the Floquat® line available from SNF and the Magnafloc® line available from BASF. Coagulant5will typically be added to stream1at concentrations of between about 3 mg/L and 15 mg/L. Ideally, coagulant5will be added as far upstream from clarifier6as practical in order to allow dispersal of coagulant5across stream1prior to entry into clarifier6. Also, early addition of coagulant5will allow coagulation to commence prior to entry of stream1into clarifier6(discussed below). Coagulant5may also help activated carbon4(discussed below) stay suspended in stream1if coagulant5is introduced to stream1prior to activated carbon4. The foregoing notwithstanding, activated carbon4may be added before coagulant5, when convenient. As indicated above, activated carbon4is also added to stream1. Activated carbon4is a carbon source that has been processed to have numerous small pores. Carbon may be activated via chemical activation or steam activation. Steam is the predominant method. In steam activation, the carbon source is heated in an inert atmosphere. This drives off moisture and volatile components. Temperatures typically stay below about 1300 degrees F. Removal of water and volatile materials will create pores throughout the carbon source. Superheated steam is then added to the carbon material. Typical temperatures range from about 1600 to about 2000 degrees F. The steam will react with the carbon across the entire surface, including the pores. The steam will convert the surface carbons to carbon monoxide, carbon dioxide, and methane—all gases. As the carbon is gasified, the pores are enlarged substantially. Pore size can be controlled by changing the conditions of steam activation—i.e., varying the temperature, pressure, and/or length of exposure. As a general rule, larger pore sizes are desired for removal of smaller particles. Activated carbon4is then ground to the desired size. Granular material having a diameter of about 1-3 mm is a typical size upon completion of the activation process, with further grinding as desired. In the preferred embodiment, activated carbon4is powdered, meaning it has a diameter of less than about 325 mesh (90 percent or more has a diameter of less than about 44 micrometers). Activated carbon4preferably has a pore diameter of about 2.2178 nanometers (nm) as measured on the Barret Joyner Halenda adsorption method. While the pore size will vary, in the preferred embodiment, at least about fifty percent of the pores will be of the desired size or larger. The preferred carbon source for the activated carbon4is lignite. Lignite is a form of coal, often referred to as brown coal. It is formed over geologic time scales by the compaction of peat by overlying sediment. Compared to bituminous coal or anthracite, lignite has a much higher moisture content. Lignite will typically be about 30 to 60 percent moisture and sometimes as high as 70 percent moisture. In comparison, bituminous coal and anthracite will both have less than 15 percent moisture. The higher moisture content in lignite is expected to result in more and larger pores in activated carbon4when the moisture is driven off, as compared to other, dryer forms of coal. Lignite also has a lower carbon content than bituminous coal or anthracite. The fixed carbon content—that is, the carbon left after removal of volatiles—is typically only about 25 to 35 percent for lignite, whereas fixed carbon will be in the 45 to 85 percent range for bituminous coal and above 85 percent for anthracite. Chlorine is another difference between lignite on one hand and bituminous coal and anthracite on the other. Bituminous coal and anthracite have much higher chlorine contents, typically about 340 parts per million (ppm). Chlorine will usually only be about 120 ppm in lignite. Having a chlorine content of less than about 150 ppm is an advantage of using lignite as the carbon source. Activated carbon4, preferably formed from lignite, is added to stream1. Typically, this is done shortly before stream1enters clarifier6. However, there is an obstacle to the addition of activated carbon4to stream1. The powdered carbon must be incorporated into stream1, and activated carbon is essentially insoluble in water. Adding the powdered activated carbon to a flowing stream will result in the bulk of the carbon clumping uselessly on the stream sides and bottom. Powdered activated carbon also tends to make a mess when attempts are made to introduce it directly to stream1. Powdered activated carbon is a substantial source of dust and tends to get dispersed onto everything when added dry. Powdered activated carbon can be suspended in water. Relatively high concentrations can be obtained, but only by maintaining high speed agitation. Typically, bulk fluid velocities of about 40 to 60 ft/min are required. If high speed agitation ceases, the carbon will fall out of suspension and form a cake on the bottom of the carrier. Returning such prior art carbon to suspension is very difficult without direct mechanical agitation of the cake. Thus, carbon in the cake is, for all practical purposes, effectively lost. For large volume suspensions, keeping the carbon from falling out of suspension is quite difficult if the suspension must be transported at all. This poses practical obstacles to getting significant amounts of carbon into suspension in stream1. To get any substantial amount of carbon into stream1, mixing must be done on site, and excess volumes of carbon must be used to account for the carbon that will fall out of suspension after it is introduced to stream1. The present invention increases the amount of activated carbon that may be suspended in a water stream. A high carbon content slurry11is prepared. Relatively low volumes of high concentration slurry11may be pumped into stream1and allowed to disperse to achieve the desired concentration in stream1. Concentrations of about 250 gm/L (20% by weight) have been achieved in slurries comprising an aqueous suspension of activated carbon4in water. The initial step in forming high concentration slurry11is to prepare an aqueous polymer solution12. The preferred polymers are non-ionic, low molecular weight polyacrylamide polymers. Typical molecular weights are between about 8,000,000 and 12,000,000. Suitable polymers include WWC-911H and WWC-906H available from Water Science Technology, located in Bessemer. Alabama, and Superfloc N-300 (7000 LMW) available from Kemira, a global chemical supplier with offices in Houston, Texas. Polymer solution12is made by mixing from about 0.5 percent to about 3.0 percent by weight, and preferably about 1.0 percent by weight polymer into water. The finished solution12will be neutral to somewhat acidic (pH of between about 4 and about 7). The preferred polymers should be compatible with the other treatment steps being used on stream1. The preferred polymer should not adversely react with any coagulant used in stream1. Similarly, the preferred polymer should not adversely effect the clarifier dynamics. Of course, the polymer selected should be NSF approved. The amount of polyacyrlamide present in potable water should be minimized. NSF regulations limit the amount of polyacrylamide that may be added to potable water as a filtration aid. In the present application, polyacrylamide is not being added as a filtration aid. Rather, polyacrylamide is being used to form a suspension agent for activated carbon4. While higher concentrations of polyacrylamide would increase the amount of carbon4that may be suspended in slurry11, it would also limit the amount of polymer solution12that could be added to stream1. In the preferred embodiment, slurry11will contain the largest amount of carbon4that can be suspended using the smallest amount of polymer. The preferred polymers are provided in a dry, granular form and should preferably be combined with water using venturi eduction. Water flows through an eduction mixer and the venturi effect creates a vacuum which draws the powdered polymer into the mixing vessel with the water at the desired concentration. When the required concentration is obtained, a high velocity or high shear mixer is used to thoroughly incorporate the polymer into the water. Best results are obtained if polymer solution12is allowed to stand for about 24 hours or longer after mixing. The polymer granules are packed tangles of long molecules. As each molecule absorbs water, it will uncoil. When an ionic polymer is used, the polymers will contain a variety of charged functional groups. As the molecules unwind, the charged functional groups become separated which will tend to repulse the components of adjacent polymers. When present, these repulsive forces will help the polymers separate from the granule. Regardless of the ionic or non-ionic nature of the polymers, the separation process is relatively slow. As each polymer is wetted, it will behave as a highly viscous gel. This will both inhibit the ability of water to reach interior polymers and restrict the movement of each wetted exterior polymer away from the granule. The mixers referenced above will create turbulence within solution12. This will tend to pull polymers away from the granule surface and keep the polymers in suspension. Once separated, the polymers will continue to hydrate and unwind. Preferably, this agitation will continue for about 24 hours prior to use of the finished solution12. Upon completion, polymer solution12will serve as a suspension agent13for activated carbon4. Once suspension agent13is ready, activated carbon4may be mixed with plain water, usually taken from the tap, a well, or other conventional source. The desired amount of water is added to a mixing tank. Typical blend sizes will be about 5000 to 5500 gallons. Powdered activated carbon4is added to the water. The activated carbon particle size is quite small in the preferred embodiment: ˜325 mesh (˜45 μm). In part because of the small particle size, care must be taken to avoid dust generation and clumping. An induction mixer can help avoid both. The preferred mixing system is a TDS (transport and dispersing system) induction mixer, such as the Conti-TDS, available from the Ystral company of Ballrechten-Dottingen, Germany. An induction mixer will pull powdered activated carbon4from a storage container, mix it with water, and inject the wetted carbon into the center of the mixing tank. This ensures that carbon4is both thoroughly wetted and evenly dispersed throughout the fluid in the mixing tank. In the preferred embodiment, approximately 10,425 pounds of activated carbon4will be added to 5000 gallons of water to achieve the desired concentration of 20 percent by weight. Once carbon4is thoroughly mixed, suspension agent13is added to the mixture. Agitation on the order of about 40 to 60 feet per minute (bulk fluid velocity) is maintained with an immersed rotation mixer. This ensures that the carbon will remain suspended while suspension agent13is introduced. Suspension agent13should be added slowly. Ideally, about 1.25 gallons (about 10 pounds or 4.7 kg) of suspension agent13is added per minute. For a 5000 gallon mixture, this is an addition rate of about 0.025 percent by volume per minute. Adding suspension agent13more quickly can cause clumping. It may be added more slowly, but agitation should be continuous regardless of the addition rate so activated carbon4will remain dispersed while suspension agent13is being incorporated. Salt is preferably added to the mixture after suspension agent13has been fully incorporated. The salt will help maintain the stability of the suspension. NaCl is the preferred salt. The preferred salt concentration is about 1.0 percent by weight. Once aqueous activated carbon slurry11has been formed, it will keep for several weeks, if the product is agitated regularly and preferably continuously. However, much lower agitation rates are required to keep the carbon in suspension in slurry11. Bulk fluid velocity rates on the order of about 6 to 12 feet per minute are sufficient to keep the carbon in suspension. Preferably, the immersed rotation mixer—essentially a plurality of blades on a rotating shaft—will continue to agitate slurry11continuously until slurry11is ready for introduction into stream1. If agitation of slurry11is suspended for ten minutes, at least about 80 percent of carbon4will still be in suspension. This can be contrasted with powdered carbon suspended in untreated water. If agitation is suspended for 10 minutes, at least 80 percent of the carbon—and in most cases 100 percent of the carbon—will have fallen out of suspension. A bigger advantage of slurry11occurs if agitation is suspended for hours or days—long enough for substantially all of carbon4to fall out of suspension. A major advantage of the present invention over the prior art is that most of carbon4may be easily returned to suspension in slurry11merely by resuming agitation. The polyacrylamide polymers increase the viscosity of slurry11. This will help suspend much of carbon4in the aqueous media so that the slurry behaves like a colloidal suspension—albeit a relatively unstable one—if agitation is interrupted. Settling of the carbon particles is impeded by the viscosity of the media. When carbon4does fall out of suspension in slurry11, the formation of cake on the bottom of whatever container slurry11is in will be impeded. Particles that reach the bottom of the container will not have left the suspension entirely. These carbon particles will still be surrounded by the viscous aqueous media of slurry11, including the dissolved polymers. The viscous media will inhibit the ability of the carbon to clump together. As a result, the carbon that has fallen out of suspension will remain loosely piled on the bottom of the container. This allows slurry11to be formed off-site and transported to the injection site for stream1via container, even if the container lacks agitation. While some carbon4will fall out of suspension, most carbon4may be returned to suspension simply by stirring slurry11. No physical manipulation of the carbon4that has settled out, beyond stirring slurry11, is required to return most carbon4to suspension. Even after weeks with no agitation, substantially all of carbon4may be returned to suspension by subjecting slurry11to mild to moderate agitation. Bulk fluid velocities on the order of about 6 to 12 ft/min (mild agitation) are believed to be sufficient to restore carbon4to suspension. However, most common commercial agitators can provide agitation on the order of about 18 to 36 ft/min (moderate agitation). Agitation at these rates are more than sufficient to restore settled carbon in slurry11to suspension. Significantly, restoration of suspension does not require mechanical raking of carbon that has fallen out of suspension. It will be appreciated that the ability to restore carbon4to suspension after a substantial interruption in the agitation of slurry11will facilitate the transport of slurry11. Slurry11may be formed in one location and shipped substantial distances for application. As long as slurry11may be agitated upon arrival, slurry11can be pumped into stream1or other application. Large volumes of slurry11may be transported via tanker truck and then pumped out upon the application of agitation to the tanker. The use of a smooth, substantially corner free tanker with sloping sides and a sloping bottom can help restore carbon4to suspension. Likewise, the use of hydraulics to impart a slope to a conventional tanker can facilitate the transfer of any carbon4that may have settled into an area of the tanker shielded from agitation (i.e., corners and areas distal from the point of discharge). In the preferred embodiment, carbon slurry11will be about 20 percent by weight (250 gm/L) activated carbon4. When it is desired to introduce activated carbon4into stream1for treatment, activated carbon4may be added by pumping carbon slurry11directly into stream1. By way of example, if an activated carbon concentration of 15 mg/L is desired in a water stream with a flow rate of 5500 liters per minute, only about ⅓ of a liter of 250 gm/L carbon slurry need be pumped into the stream per minute to achieve the desired concentration. Much higher carbon concentrations may be obtained in stream1than would be possible by mixing powdered activated carbon4directly into stream1, and the method of introduction is much more convenient. Because activated carbon4is in aqueous slurry11, it may be introduced with a conventional pump, such as a peristaltic metering pump or a diaphragm metering pump suitable for high viscosity fluids. If powdered activated carbon4were added directly, some type of solids handling system would be required, such as an induction pump. Such an attempt would be further complicated when the stream being treated is flowing, making re-circulation difficult. After being pumped into stream1, aqueous slurry will simply dissipate into the flowing waters of stream1. No other introduction steps are required to incorporate the activated carbon4within slurry11into stream1. As alluded to above, subsequent to the addition of activated carbon4, coagulant5, and any pre-oxidants3, stream1is directed into a clarifier6. Preferably, stream1will enter clarifier6shortly after the addition of slurry11. Clarifier6will preferably be an up-flow clarifier. In an up-flow clarifier, water will enter clarifier6in an inverted cone14(point at top). Inverted cone14is contained in a larger tank15. Tank15will usually have walls19that diverge from gravitational bottom to top. This will result in tank15having an interior space20between walls19and cone14whose cross sectional volume increases from bottom to top. That is, the volume of a slice taken of interior space20will be larger than the volume of a similar slice taken below the first slice. Water entering clarifier6must flow down through the open bottom16of cone14to enter tank15. An outflow line18is located in tank15well above open bottom16. This requires water in stream1flowing through clarifier6to flow down through cone14and then up through tank15to pass through clarifier6. Stream1will decelerate after it moves through open bottom16. Once stream1has exited cone14, it will move upward through interior space20. As noted above, the volume of interior space20will increase from bottom to top. Thus, as stream1moves through interior space20, it will move through a channel of increasing volume, which will cause stream1to slow. As stream1slows, coagulant5and other materials suspended in stream1will fall out of suspension. As coagulant5falls out of suspension, it will form a bed17in the quiescent portion of tank15. The relatively fast and upwardly flowing water at the bottom of tank15will suspend bed17above the bottom of tank15. As coagulant5remains relatively stationary within bed17, coagulant5will flocculate. This is the formation of sponge-like clumps or “flocs” that make up bed17. The flocs will physically enmesh activated carbon4. As stream1flows through bed17, activated carbon4will capture organic material and other material from stream1. The flocs will also independently capture bacteria, algae, and other contaminants in stream1. A plurality of mixing blades21are preferably positioned on a rotating shaft within cone14. These are intended to help bring contaminants in stream1into contact with coagulant5. However, blades21will also help bring carbon particles4into contact with coagulant5. The area within cone14agitated by blades21is the mixing zone22. One or more sludge agitators23will preferably be provided below open end16of cone14. These agitators will prevent sludge from building up below open end16and obstructing outflow from cone14. Activated carbon4will have its primary contact time with stream1in bed17, and, to a lesser degree, in mixing zone22. Contact time will depend upon the fluid mechanics of clarifier6. However, contact time between the activated carbon4suspended in bed17and stream1flowing through bed17will typically range from hours to days. Carbon4will commonly remain in bed17long enough that contact time is not the limiting factor in the ability of activated carbon4to adsorb contaminants from stream1. The carbon particles are likely to become saturated with contaminants before they exit clarifier6, as described below. Rather, the more limiting factor is likely to be the rate at which stream1flows through clarifier6in general, and bed17in particular, as well as the concentration of activated carbon4within bed17. Eventually, under the quiescent conditions of tank15, the flocs will agglomerate, sticking to one another and capturing more material, until they become heavy enough to fall out of suspension via gravity. Alternatively, a portion of bed17may be removed via controlled blow down. Either way, coagulant5will settle out into the sludge at the bottom of clarifier6. The sludge will be physically removed and either discarded or transferred for further treatment. Stream1will flow out of tank15via an outflow line18located in the upper portion of tank15. When stream1exits tank15, it should have passed through bed17, but coagulant5and other non-dissolved contents of bed17should preferably not be able to exit tank15via outflow line18. This is accomplished by controlling the thickness of bed17, via forced blowdown or otherwise, before the top of bed17reaches outflow line18. Thus, stream1will flow out of clarifier6with little or no coagulant5or activated carbon4still in stream1. The contaminants captured by coagulant5and activated carbon4will, likewise, have been removed from stream1. Once an equilibrium is established, the amount of carbon4added should preferably equal the amount removed per unit time. Otherwise, carbon4will increase the mass of bed17. Such an increase could be managed by increasing the frequency at which bed17is drawn down. However, the preferred approach is to match the quantity of carbon4in with the amount out. Once in stream1, activated carbon4will capture dissolved and suspended organic carbon. To the extent that pre-oxidants3have formed any chlorination by-products, such as HAA's or THM, activated carbon4will also capture them. Contaminants, such as bacteria, hydrocarbons, pharmaceuticals, and algae will be captured as well. Furthermore, to the extent bacteria or algae may have released Geosmin, MIB, or other contaminants that adversely effect taste and smell, the activated carbon will also absorb these contaminants. In short, activated carbon4will effect an overall reduction in contaminants present in stream1. This will primarily occur in bed17and mixing zone22. Summarizing the process to this point briefly, screen2will remove most large solids from stream1. Coagulant5will be added to stream1, typically shortly after screening though coagulant5may be added later when more convenient. A slurry11is used to add activated carbon4to stream1. Stream1will flow into clarifier6. Coagulant5will form bed17within clarifier6. As stream1flows through bed17, bed17will capture and suspend activated carbon4, which will adsorb from stream1many of the contaminants present, including dissolved organic carbon and chlorination by-products that may have been formed by pre-oxidation chemicals, if any. Coagulant5will also capture contaminants independently. Coagulant5will settle out of stream1in clarifier6, allowing activated carbon4and the contaminants captured by activated carbon4and/or coagulant5to be removed from stream1. After exiting clarifier6, stream1will usually still contain some organic carbon and other contaminants that require treatment. Commonly, this treatment will entail the addition of a primary oxidizing agent10, such as chlorine. However, because of the capture of organic carbon by activated carbon4, fewer primary oxidizing agents10will be required than would otherwise have been needed. This will result in a reduction in the formation of chlorination by-products such as HAA's and THM. The number of agents with a potential adverse effect on odor and flavor, such as Geosmin and MIB producing bacteria, will also have been reduced. The number of pharmaceuticals and hydrocarbons remaining in stream1will have been reduced as well. By reducing the number of these contaminants present, the need for their subsequent treatment will be minimized, or in some cases eliminated. There are also regulations in many jurisdictions limiting the amount of chlorine that may be added to potable water. Reducing the organic carbon in stream1will reduce the need for chlorine to oxidize organic carbon, thereby helping ensure compliance with the regulatory limits on chlorine. Using lignite as the carbon source in activated carbon4instead of bituminous coal or anthracite is advantageous, in part, because of the lower chlorine content of lignite. As discussed above, the use of chlorine to oxidize organic carbon in stream1can produce undesirable chlorination by-products. Minimizing ancillary sources of chlorine, as well as minimizing chlorine intentionally added to stream1as an oxidation or pre-oxidation agent, will help limit the formation of chlorination by-products. Accordingly, forms of coal with lower chlorine content are advantageous relative to higher chlorine carbon sources. After oxidation, stream1will be filtered again. Typically, this involves flowing stream1through layers of anthracite, sand, and gravel—a mixed bed filter7. From there, stream1will flow to a storage facility8, such as an above ground tank, to be held until ready for use. Most treatment systems will include a clear well9downstream from filter7. Stream1will be diverted to clear well9as it comes out of filter7. When clear well9is full, clear well9will be closed and stream1will be directed to storage facility8. When filter7becomes clogged to the point that flow through filter7is impeded, inflow to filter7will be stopped. Once the water in filter7has passed through to storage facility8, water in clear well9will be allowed to back flow into filter7. Flowing water through filter7in the opposite direction from ordinary flow will clean filter7. Once filter7is cleaned, inflow into filter7will resume, clear well9will be refilled, and outflow from filter7will be returned to storage facility8. Example 1 A water treatment plant with parallel water streams was identified. This plant had two separate incoming streams with substantially identical characteristics. This allowed one to be tested and the other to be used as a control. Each stream was screened for solids. “Before” samples were taken from each stream post-screening. An activated carbon slurry was then added to the test stream. The activated carbon slurry had a carbon concentration of 250 gm/liter. The activated carbon slurry was added at a rate sufficient to create a carbon concentration of 10 mg per liter in the stream. This was slightly more than about ⅓ of a liter of slurry added per minute to a stream flowing at about 9,100 liters per minute. Over five days, approximately 265 Kg carbon were added to the stream. The slurry was formed as described above. In addition to water and activated carbon, the slurry included about 1.0 percent by weight Superfloc™ N-300 (7000 LMW) low molecular weight polyacrylamide non-ionic polymer and about 1.0 percent by weight NaCl. The carbon in the activated slurry was 100% lignite based activated carbon. Prior to formation of the slurry, the activated carbon was a 325 mesh powder, meaning that at least 90 percent of the carbon powder had a diameter of 44 microns or smaller. It had an average pore diameter of about 2.2178 nm. In each stream, the halogen residual was measured continuously. Halogen residual is a measure of free available chlorine (FAC). Essentially, there should be enough chlorine to oxidize the organic carbon in each stream. Organic carbon present in the stream will consume chlorine, causing FAC to fall. If the FAC falls below the plant target, more chlorine (or other halogen, where approved), must be added. The halogen residual was maintained above 2.25 mg/L in each stream; however, to maintain FAC above the target, more chlorine was required to be added to the stream without activated carbon4than was needed in the stream with activated carbon4. These results are shown inFIG.3. Jar “after” samples were taken from each stream on five consecutive days. The after samples were taken from the sand filter effluent. THM was measured in each sample. The results are provided inFIG.2. As can be seen, THM content was uniformly lower in the sample in which activated carbon was added. It is not clear whether the difference is attributable to THM being captured by the activated carbon or to less THM being produced because of the removal of organic carbon by the activated carbon or to some combination thereof. However, it is clear that the addition of activated carbon to the stream both reduced the total amount of oxidizing agent required to treat the stream and the amount of THM present in the treated stream. These and other improvements to the treatment of water will be apparent to those of skill in the art from the foregoing disclosure and drawings and are intended to be encompassed by the scope and spirit of the following claims. | 31,477 |
11858842 | DETAILED DESCRIPTION As used herein throughout this disclosure and in the claims, the singular forms “a,” “an,” and “the” include the plural forms unless the context clearly dictates otherwise. Additionally, the term “includes” means “comprises.” Further, the term “coupled” does not exclude the presence of intermediate elements between the coupled items. Also, the terms “modify” and “adjust” are used interchangeably to mean “alter.” The systems, apparatus, and methods described herein should not be construed as limiting in any way. Instead, the present disclosure is directed toward all novel and non-obvious features and aspects of the various disclosed embodiments, alone and in various combinations and sub-combinations with one another. The disclosed systems, methods, and apparatus are not limited to any specific aspect or feature or combinations thereof, nor do the disclosed systems, methods, and apparatus require that any one or more specific advantages be present or problems be solved. Any theories of operation are to facilitate explanation, but the disclosed systems, methods, and apparatus are not limited to such theories of operation. Although the operations of some of the disclosed methods are described in a particular, sequential order for convenient presentation, it should be understood that this manner of description encompasses rearrangement, unless a particular ordering is required by specific language set forth below. For example, operations described sequentially may in some cases be rearranged or performed concurrently. Moreover, for the sake of simplicity, the attached figures may not show the various ways in which the disclosed systems, methods, and apparatus can be used in conjunction with other systems, methods, and apparatus. Additionally, the description sometimes uses terms like “produce” and “provide” to describe the disclosed methods. These terms are high-level abstractions of the actual operations that are performed. The actual operations that correspond to these terms will vary depending on the particular implementation and are readily discernible by one of ordinary skill in the art. In some examples, values, procedures, or apparatus are referred to as “lowest”, “best”, “minimum,” or the like. It will be appreciated that such descriptions are intended to indicate that a selection among many used functional alternatives can be made, and such selections need not be better, smaller, or otherwise preferable to other selections. Examples are described with reference to directions indicated as “above,” “below,” “upper,” “lower,” and the like. These terms are used for convenient description, but do not imply any particular spatial orientation. Definitions Definitions of words and terms as used herein:1. The term “beam characteristics” refers to one or more of the following terms used to describe an optical beam. In general, the beam characteristics of most interest depend on the specifics of the application or optical system.2. The term “beam diameter” is defined as the distance across the center of the beam along an axis for which the irradiance (intensity) equals 1/e2of the maximum irradiance. While examples disclosed herein generally use beams that propagate in azimuthally symmetric modes, elliptical or other beam shapes can be used, and beam diameter can be different along different axes. Circular beams are characterized by a single beam diameter. Other beam shapes can have different beam diameters along different axes.3. The term “spot size” is the radial distance (radius) from the center point of maximum irradiance to the 1/e2point.4. The term “beam divergence distribution” is the power vs the full cone angle. This quantity is sometimes called the “angular distribution” or “NA distribution.”5. The term “beam parameter product” (BPP) of a laser beam is defined as the product of the beam radius (measured at the beam waist) and the beam divergence half-angle (measured in the far field). The units of BPP are typically mm-mrad.6. A “confinement fiber” is defined to be a fiber that possesses one or more confinement regions, wherein a confinement region comprises a higher-index region (core region) surrounded by a lower-index region (cladding region). The RIP of a confinement fiber may include one or more higher-index regions (core regions) surrounded by lower-index regions (cladding regions), wherein light is guided in the higher-index regions. Each confinement region and each cladding region can have any RIP, including but not limited to step-index and graded-index. The confinement regions may or may not be concentric and may be a variety of shapes such as circular, annular, polygonal, arcuate, elliptical, or irregular, or the like or any combination thereof. The confinement regions in a particular confinement fiber may all have the same shape or may be different shapes. Moreover, confinement regions may be co-axial or may have offset axes with respect to one another. Confinement regions may be of uniform thickness about a central axis in the longitudinal direction, or the thicknesses may vary about the central axis in the longitudinal direction.7. The term “intensity distribution” refers to optical intensity as a function of position along a line (1D profile) or on a plane (2D profile). The line or plane is usually taken perpendicular to the propagation direction of the light. It is a quantitative property.8. “Luminance” is a photometric measure of the luminous intensity per unit area of light travelling in a given direction.9. “M2factor” (also called “beam quality factor” or “beam propagation factor”) is a dimensionless parameter for quantifying the beam quality of laser beams, with M2=1 being a diffraction-limited beam, and larger M2 values corresponding to lower beam quality. M2is equal to the BPP divided by λ/π, where λ is the wavelength of the beam in microns (if BPP is expressed in units of mm-mrad).10. The term “numerical aperture” or “NA” of an optical system is a dimensionless number that characterizes the range of angles over which the system can accept or emit light.11. The term “optical intensity” is not an official (SI) unit, but is used to denote incident power per unit area on a surface or passing through a plane.12. The term “power density” refers to optical power per unit area, although this is also referred to as “optical intensity.”13. The term “radial beam position” refers to the position of a beam in a fiber measured with respect to the center of the fiber core in a direction perpendicular to the fiber axis.14. “Radiance” is the radiation emitted per unit solid angle in a given direction by a unit area of an optical source (e.g., a laser). Radiance may be altered by changing the beam intensity distribution and/or beam divergence profile or distribution. The ability to vary the radiance profile of a laser beam implies the ability to vary the BPP.15. The term “refractive-index profile” or “RIP” refers to the refractive index as a function of position along a line (1D) or in a plane (2D) perpendicular to the fiber axis. Many fibers are azimuthally symmetric, in which case the 1D RIP is identical for any azimuthal angle.16. A “step-index fiber” has a RIP that is flat (refractive index independent of position) within the fiber core.17. A “graded-index fiber” has a RIP in which the refractive index decreases with increasing radial position (i.e., with increasing distance from the center of the fiber core).18. A “parabolic-index fiber” is a specific case of a graded-index fiber in which the refractive index decreases quadratically with increasing distance from the center of the fiber core.19. “Free space propagation” and “unguided propagation” are used to refer to optical beams that propagate without being constrained to one or more waveguides (such as optical fibers) over optical distances that are typically 5, 10, 20, 100 times or more than a beam Rayleigh range. Such propagation can be in optical media such as glass, fused silica, semiconductors, air, crystalline materials, or vacuum.20. “Collimated beams” are generally produced by situating a lens or other focusing element such as a curved mirror, a Fresnel lens, or a holographic optical element such that an apparent distance from a location at which a beam has, would have, or appears to have a planar wavefront (such as at a focus of a Gaussian beam or at an output of an optical fiber) that is less than 10%, 5%, 2%, 1%, 0.5%, 0.1% of a focal length f from a focal point of a focal length f. Fiber for Varying Beam Characteristics Disclosed herein are methods, systems, and apparatus configured to provide a fiber operable to provide a laser beam having variable beam characteristics (VBC) that may reduce cost, complexity, optical loss, or other drawbacks of the conventional methods described above. This VBC fiber is configured to vary a wide variety of optical beam characteristics. Such beam characteristics can be controlled using the VBC fiber thus allowing users to tune various beam characteristics to suit the particular requirements of an extensive variety of laser processing applications. For example, a VBC fiber may be used to tune: beam diameter, beam divergence distribution, BPP, intensity distribution, M2factor, NA, optical intensity, power density, radial beam position, radiance, spot size, or the like, or any combination thereof. In general, the disclosed technology entails coupling a laser beam into a fiber in which the characteristics of the laser beam in the fiber can be adjusted by perturbing the laser beam and/or perturbing a first length of fiber by any of a variety of methods (e.g., bending the fiber or introducing one or more other perturbations) and fully or partially maintaining adjusted beam characteristics in a second length of fiber. The second length of fiber is specially configured to maintain and/or further modify the adjusted beam characteristics. In some cases, the second length of fiber preserves the adjusted beam characteristics through delivery of the laser beam to its ultimate use (e.g., materials processing). The first and second lengths of fiber may comprise the same or different fibers. The disclosed technology is compatible with fiber lasers and fiber-coupled lasers. Fiber-coupled lasers typically deliver an output via a delivery fiber having a step-index refractive index profile (RIP), i.e., a flat or constant refractive index within the fiber core. In reality, the RIP of the delivery fiber may not be perfectly flat, depending on the design of the fiber. Important parameters are the fiber core diameter (dcore) and NA. The core diameter is typically in the range of 10-1000 micron (although other values are possible), and the NA is typically in the range of 0.06-0.22 (although other values are possible). A delivery fiber from the laser may be routed directly to the process head or work piece, or it may be routed to a fiber-to-fiber coupler (FFC) or fiber-to-fiber switch (FFS), which couples the light from the delivery fiber into a process fiber that transmits the beam to the process head or the work piece. Most materials processing tools, especially those at high power (>1 kW), employ multimode (MM) fiber, but some employ single-mode (SM) fiber, which is at the lower end of the dcoreand NA ranges. The beam characteristics from a SM fiber are uniquely determined by the fiber parameters. The beam characteristics from a MM fiber, however, can vary (unit-to-unit and/or as a function of laser power and time), depending on the beam characteristics from the laser source(s) coupled into the fiber, the launching or splicing conditions into the fiber, the fiber RIP, and the static and dynamic geometry of the fiber (bending, coiling, motion, micro-bending, etc.). For both SM and MM delivery fibers, the beam characteristics may not be optimum for a given materials processing task, and it is unlikely to be optimum for a range of tasks, motivating the desire to be able to systematically vary the beam characteristics in order to customize or optimize them for a particular processing task. In one example, the VBC fiber may have a first length and a second length and may be configured to be interposed as an in-fiber device between the delivery fiber and the process head to provide the desired adjustability of the beam characteristics. To enable adjustment of the beam, a perturbation device and/or assembly is disposed in close proximity to and/or coupled with the VBC fiber and is responsible for perturbing the beam in a first length such that the beam's characteristics are altered in the first length of fiber, and the altered characteristics are preserved or further altered as the beam propagates in the second length of fiber. The perturbed beam is launched into a second length of the VBC fiber configured to conserve adjusted beam characteristics. The first and second lengths of fiber may be the same or different fibers and/or the second length of fiber may comprise a confinement fiber. The beam characteristics that are conserved by the second length of VBC fiber may include any of: beam diameter, beam divergence distribution, BPP, intensity distribution, luminance, M2factor, NA, optical intensity, power density, radial beam position, radiance, spot size, or the like, or any combination thereof. In some disclosed embodiments, a fiber is referred to a being urged to conform to a surface. Unless otherwise indicated, such a fiber need not contact such a surface nor acquire a curvature corresponding to the surface. FIG.1illustrates an example VBC fiber100for providing a laser beam having variable beam characteristics without requiring the use of free-space optics to change the beam characteristics. VBC fiber100comprises a first length of fiber104and a second length of fiber108. First length of fiber104and second length of fiber108may be the same or different fibers and may have the same or different RIPs. The first length of fiber104and the second length of fiber108may be joined together by a splice. First length of fiber104and second length of fiber108may be coupled in other ways, may be spaced apart, or may be connected via an interposing component such as another length of fiber, free-space optics, glue, index-matching material, or the like or any combination thereof. A perturbation device110is disposed proximal to and/or envelops perturbation region106. Perturbation device110may be a device, assembly, in-fiber structure, and/or other feature. Perturbation device110at least perturbs optical beam102in first length of fiber104or second length of fiber108or a combination thereof in order to adjust one or more beam characteristics of optical beam102. Adjustment of beam102responsive to perturbation by perturbation device110may occur in first length of fiber104or second length of fiber108or a combination thereof. Perturbation region106may extend over various widths and may or may not extend into a portion of second length of fiber108. As beam102propagates in VBC fiber100, perturbation device110may physically act on VBC fiber100to perturb the fiber and adjust the characteristics of beam102. Alternatively, perturbation device110may act directly on beam102to alter its beam characteristics. Subsequent to being adjusted, perturbed beam112has different beam characteristics than beam102, which will be fully or partially conserved in second length of fiber108. In another example, perturbation device110need not be disposed near a splice. Moreover, a splice may not be needed at all, for example VBC fiber100may be a single fiber, first length of fiber and second length of fiber could be spaced apart, or secured with a small gap (air-spaced or filled with an optical material, such as optical cement or an index-matching material). Perturbed beam112is launched into second length of fiber108, where perturbed beam112characteristics are largely maintained or continue to evolve as perturbed beam112propagates yielding the adjusted beam characteristics at the output of second length of fiber108. In one example, the new beam characteristics may include an adjusted intensity distribution. In an example, an altered beam intensity distribution will be conserved in various structurally bounded confinement regions of second length of fiber108. Thus, the beam intensity distribution may be tuned to a desired beam intensity distribution optimized for a particular laser processing task. In general, the intensity distribution of perturbed beam112will evolve as it propagates in the second length of fiber108to fill the confinement region(s) into which perturbed beam112is launched responsive to conditions in first length of fiber104and perturbation caused by perturbation device110. In addition, the angular distribution may evolve as the beam propagates in the second fiber, depending on launch conditions and fiber characteristics. In general, fibers largely preserve the input divergence distribution, but the distribution can be broadened if the input divergence distribution is narrow and/or if the fiber has irregularities or deliberate features that perturb the divergence distribution. The various confinement regions, perturbations, and fiber features of second length of fiber108are described in greater detail below. Beams102and112are conceptual abstractions intended to illustrate how a beam may propagate through a VBC fiber100for providing variable beam characteristics and are not intended to closely model the behavior of a particular optical beam. VBC fiber100may be manufactured by a variety of methods including PCVD (Plasma Chemical Vapor Deposition), OVD (Outside Vapor Deposition), VAD (Vapor Axial Deposition), MOCVD (Metal-Organic Chemical Vapor Deposition.) and/or DND (Direct Nanoparticle Deposition). VBC fiber100may comprise a variety of materials. For example, VBC fiber100may comprise SiO2, SiO2doped with GeO2, germanosilicate, phosphorus pentoxide, phosphosilicate, Al2O3, aluminosilicate, or the like or any combinations thereof. Confinement regions may be bounded by cladding doped with fluorine, boron, or the like or any combinations thereof. Other dopants may be added to active fibers, including rare-earth ions such as Er3+(erbium), Yb3+(ytterbium), Nd3+(neodymium), Tm3+(thulium), Ho3+(holmium), or the like or any combination thereof. Confinement regions may be bounded by cladding having a lower index than the confinement region with fluorine or boron doping. Alternatively, VBC fiber100may comprise photonic crystal fibers or micro-structured fibers. VBC fiber100is suitable for use in any of a variety of fiber, fiber optic, or fiber laser devices, including continuous wave and pulsed fiber lasers, disk lasers, solid state lasers, or diode lasers (pulse rate unlimited except by physical constraints). Furthermore, implementations in a planar waveguide or other types of waveguides and not just fibers are within the scope of the claimed technology. FIG.2depicts a cross-sectional view of an example VBC fiber200for adjusting beam characteristics of an optical beam. In an example, VBC fiber200may be a process fiber because it may deliver the beam to a process head for material processing. VBC fiber200comprises a first length of fiber204spliced at junction206to a second length of fiber208. A perturbation assembly210is disposed proximal to junction206. Perturbation assembly210may be any of a variety of devices configured to enable adjustment of the beam characteristics of an optical beam202propagating in VBC fiber200. In an example, perturbation assembly210may be a mandrel and/or another device that may provide means of varying the bend radius and/or bend length of VBC fiber200near the splice. Other examples of perturbation devices are discussed below with respect toFIG.24. In an example, first length of fiber204has a parabolic-index RIP212as indicated by the left RIP graph. Most of the intensity distribution of beam202is concentrated in the center of fiber204when fiber204is straight or nearly straight. Second length of fiber208is a confinement fiber having RIP214as shown in the right RIP graph. Second length of fiber208includes confinement regions216,218and220. Confinement region216is a central core surrounded by two annular (or ring-shaped) confinement regions218and220. Layers222and224are structural barriers of lower index material between confinement regions (216,218and220), commonly referred to as “cladding” regions. In one example, layers222and224may comprise rings of fluorosilicate; in some embodiments, the fluorosilicate cladding layers are relatively thin. Other materials may be used as well and claimed subject matter is not limited in this regard. In an example, as beam202propagates along VBC fiber200, perturbation assembly210may physically act on fiber208and/or beam202to adjust its beam characteristics and generate adjusted beam226. In the current example, the intensity distribution of beam202is modified by perturbation assembly210. Subsequent to adjustment of beam202the intensity distribution of adjusted beam226may be concentrated in outer confinement regions218and220with relatively little intensity in the central confinement region216. Because each of confinement regions216,218, and/or220is isolated by the thin layers of lower index material in barrier layers222and224, second length of fiber208can substantially maintain the adjusted intensity distribution of adjusted beam226. The beam will typically become distributed azimuthally within a given confinement region but will not transition (significantly) between the confinement regions as it propagates along the second length of fiber208. Thus, the adjusted beam characteristics of adjusted beam226are largely conserved within the isolated confinement regions216,218, and/or220. In some cases, it be may desirable to have the beam226power divided among the confinement regions216,218, and/or220rather than concentrated in a single region, and this condition may be achieved by generating an appropriately adjusted beam226. In one example, core confinement region216and annular confinement regions218and220may be composed of fused silica glass, and cladding222and224defining the confinement regions may be composed of fluorosilicate glass. Other materials may be used to form the various confinement regions (216,218and220), including germanosilicate, phosphosilicate, aluminosilicate, or the like, or a combination thereof and claimed subject matter is not so limited. Other materials may be used to form the barrier rings (222and224), including fused silica, borosilicate, or the like or a combination thereof, and claimed subject matter is not so limited. In other embodiments, the optical fibers or waveguides include or are composed of various polymers or plastics or crystalline materials. Generally, the core confinement regions have refractive indices that are greater than the refractive indices of adjacent barrier/cladding regions. In some examples, it may be desirable to increase a number of confinement regions in a second length of fiber to increase granularity of beam control over beam displacements for fine-tuning a beam profile. For example, confinement regions may be configured to provide stepwise beam displacement. FIG.3illustrates an example method of perturbing fiber200for providing variable beam characteristics of an optical beam. Changing the bend radius of a fiber may change the radial beam position, divergence angle, and/or radiance profile of a beam within the fiber. The bend radius of VBC fiber200can be decreased from a first bend radius R1to a second bend radius R2about splice junction206by using a stepped mandrel or cone as the perturbation assembly210. Additionally or alternatively, the engagement length on the mandrel(s) or cone can be varied. Rollers250may be employed to engage VBC fiber200across perturbation assembly210. In an example, an amount of engagement of rollers250with fiber200has been shown to shift the distribution of the intensity profile to the outer confinement regions218and220of fiber200with a fixed mandrel radius. There are a variety of other methods for varying the bend radius of fiber200, such as using a clamping assembly, flexible tubing, or the like, or a combination thereof, and claimed subject matter is not limited in this regard. In another example, for a particular bend radius the length over which VBC fiber200is bent can also vary beam characteristics in a controlled and reproducible way. In examples, changing the bend radius and/or length over which the fiber is bent at a particular bend radius also modifies the intensity distribution of the beam such that one or more modes may be shifted radially away from the center of a fiber core. Maintaining the bend radius of the fibers across junction206ensures that the adjusted beam characteristics such as radial beam position and radiance profile of optical beam202will not return to beam202's unperturbed state before being launched into second length of fiber208. Moreover, the adjusted radial beam characteristics, including position, divergence angle, and/or intensity distribution, of adjusted beam226can be varied based on an extent of decrease in the bend radius and/or the extent of the bent length of VBC fiber200. Thus, specific beam characteristics may be obtained using this method. In the current example, first length of fiber204having first RIP212is spliced at junction206to a second length of fiber208having a second RIP214. However, it is possible to use a single fiber having a single RIP formed to enable perturbation (e.g., by micro-bending) of the beam characteristics of beam202and also to enable conservation of the adjusted beam. Such a RIP may be similar to the RIPs shown in fibers illustrated inFIGS.17,18, and/or19. FIGS.7-10provide experimental results for VBC fiber200(shown inFIGS.2and3) and illustrate further a beam response to perturbation of VBC fiber200when a perturbation assembly210acts on VBC fiber200to bend the fiber.FIGS.4-6are simulations andFIGS.7-10are experimental results wherein a beam from a SM 1050 nm source was launched into an input fiber (not shown) with a 40 micron core diameter. The input fiber was spliced to first length of fiber204. FIG.4is an example graph400illustrating the calculated profile of the lowest-order mode (LP01) for a first length of fiber204for different fiber bend radii402, wherein a perturbation assembly210involves bending VBC fiber200. As the fiber bend radius is decreased, an optical beam propagating in VBC fiber200is adjusted such that the mode shifts radially away from the center404of a VBC fiber200core (r=0 micron) toward the core/cladding interface (located at r=100 micron in this example). Higher-order modes (LPln) also shift with bending. Thus, a straight or nearly straight fiber (very large bend radius), curve406for LP01is centered at or near the center of VBC fiber200. At a bend radius of about 6 cm, curve408for LP01is shifted to a radial position of about 40 μm from the center406of VBC fiber200. At a bend radius of about 5 cm, curve410for LP01is shifted to a radial position about 50 μm from the center406of VBC fiber200. At a bend radius of about 4 cm, curve412for LP01is shifted to a radial position about 60 μm from the center406of VBC fiber200. At a bend radius of about 3 cm, curve414for LP01is shifted to a radial position about 80 μm from the center406of VBC fiber200. At a bend radius of about 2.5 cm, a curve416for LP01is shifted to a radial position about 85 μm from the center406of VBC fiber200. Note that the shape of the mode remains relatively constant (until it approaches the edge of the core), which is a specific property of a parabolic RIP. Although, this property may be desirable in some situations, it is not required for the VBC functionality, and other RIPs may be employed. In an example, if VBC fiber200is straightened, LP01mode will shift back toward the center of the fiber. Thus, the purpose of second length of fiber208is to “trap” or confine the adjusted intensity distribution of the beam in a confinement region that is displaced from the center of the VBC fiber200. The splice between fibers204and208is included in the bent region, thus the shifted mode profile will be preferentially launched into one of the ring-shaped confinement regions218and220or be distributed among the confinement regions.FIGS.5and6illustrate this effect. FIG.5illustrates an example two-dimensional intensity distribution at junction206within second length of fiber208when VBC fiber200is nearly straight. A significant portion of LP01and LPlnare within confinement region216of fiber208.FIG.6illustrates the two-dimensional intensity distribution at junction206within second length of fiber208when VBC fiber200is bent with a radius chosen to preferentially excite confinement region220(the outermost confinement region) of second length of fiber208. A significant portion of LP01and LPlnare within confinement region220of fiber208. In an example, second length of fiber208confinement region216has a 100 micron diameter, confinement region218is between 120 micron and 200 micron in diameter, and confinement region220is between 220 micron and 300 micron diameter. Confinement regions216,218, and220are separated by 10 um thick rings of fluorosilicate, providing an NA of 0.22 for the confinement regions. Other inner and outer diameters for the confinement regions, thicknesses of the rings separating the confinement regions, NA values for the confinement regions, and numbers of confinement regions may be employed. Referring again toFIG.5, with the noted parameters, when VBC fiber200is straight about 90% of the power is contained within the central confinement region216, and about 100% of the power is contained within confinement regions216and218. Referring now toFIG.6, when fiber200is bent to preferentially excite second ring confinement region220, nearly 75% of the power is contained within confinement region220, and more than 95% of the power is contained within confinement regions218and220. These calculations include LP01and two higher-order modes, which is typical in some 2-4 kW fiber lasers. It is clear fromFIGS.5and6that in the case where a perturbation assembly210acts on VBC fiber200to bend the fiber, the bend radius determines the spatial overlap of the modal intensity distribution of the first length of fiber204with the different guiding confinement regions (216,218, and220) of the second length of fiber208. Changing the bend radius can thus change the intensity distribution at the output of the second length of fiber208, thereby changing the diameter or spot size of the beam, and thus also changing its radiance and BPP value. This adjustment of the spot size may be accomplished in an all-fiber structure, involving no free-space optics and consequently may reduce or eliminate the disadvantages of free-space optics discussed above. Such adjustments can also be made with other perturbation assemblies that alter bend radius, bend length, fiber tension, temperature, or other perturbations discussed below. In a typical materials processing system (e.g., a cutting or welding tool), the output of the process fiber is imaged at or near the work piece by the process head. Varying the intensity distribution as shown inFIGS.5and6thus enables variation of the beam profile at the work piece in order to tune and/or optimize the process, as desired. Specific RIPs for the two fibers were assumed for the purpose of the above calculations, but other RIPs are possible, and claimed subject matter is not limited in this regard. FIGS.7-10depict experimental results (measured intensity distributions) to illustrate further output beams for various bend radii of VBC fiber200shown inFIG.2. InFIG.7when VBC fiber200is straight, the beam is nearly completely confined to confinement region216. As the bend radius is decreased, the intensity distribution shifts to higher diameters (FIGS.8-10).FIG.8depicts the intensity distribution when the bend radius of VBC fiber200is chosen to shift the intensity distribution preferentially to confinement region218.FIG.9depicts the experimental results when the bend radius is further reduced and chosen to shift the intensity distribution outward to confinement region220and confinement region218. InFIG.10, at the smallest bend radius, the beam is nearly a “donut mode”, with most of the intensity in the outermost confinement region220. Despite excitation of the confinement regions from one side at the splice junction206, the intensity distributions are nearly symmetric azimuthally because of scrambling within confinement regions as the beam propagates within the VBC fiber200. Although the beam will typically scramble azimuthally as it propagates, various structures or perturbations (e.g., coils) could be included to facilitate this process. For the fiber parameters used in the experiment shown inFIGS.7-10, particular confinement regions were not exclusively excited because some intensity was present in multiple confinement regions. This feature may enable advantageous materials processing applications that are optimized by having a flatter or distributed beam intensity distribution. In applications requiring cleaner excitation of a given confinement region, different fiber RIPs could be employed to enable this feature. The results shown inFIGS.7-10pertain to the particular fibers used in this experiment, and the details will vary depending on the specifics of the implementation. In particular, the spatial profile and divergence distribution of the output beam and their dependence on bend radius will depend on the specific RIPs employed, on the splice parameters, and on the characteristics of the laser source launched into the first fiber. Different fiber parameters than those shown inFIG.2may be used and still be within the scope of the claimed subject matter. Specifically, different RIPs and core sizes and shapes may be used to facilitate compatibility with different input beam profiles and to enable different output beam characteristics. Example RIPs for the first length of fiber, in addition to the parabolic-index profile shown inFIG.2, include other graded-index profiles, step-index, pedestal designs (i.e., nested cores with progressively lower refractive indices with increasing distance from the center of the fiber), and designs with nested cores with the same refractive index value but with various NA values for the central core and the surrounding rings. Example RIPs for the second length of fiber, in addition to the profile shown inFIG.2, include confinement fibers with different numbers of confinement regions, non-uniform confinement-region thicknesses, different and/or non-uniform values for the thicknesses of the rings surrounding the confinement regions, different and/or non-uniform NA values for the confinement regions, different refractive-index values for the high-index and low-index portions of the RIP, non-circular confinement regions (such as elliptical, oval, polygonal, square, rectangular, or combinations thereof), as well as other designs as discussed in further detail with respect toFIGS.26-28. Furthermore, VBC fiber200and other examples of a VBC fiber described herein are not restricted to use of two fibers. In some examples, implementation may include use of one fiber or more than two fibers. In some cases, the fiber(s) may not be axially uniform; for example, they could include fiber Bragg gratings or long-period gratings, or the diameter could vary along the length of the fiber. In addition, the fibers do not have to be azimuthally symmetric, e.g., the core(s) could have square or polygonal shapes. Various fiber coatings (buffers) may be employed, including high-index or index-matched coatings (which strip light at the glass-polymer interface) and low-index coatings (which guide light by total internal reflection at the glass-polymer interface). In some examples, multiple fiber coatings may be used on VBC fiber200. FIGS.11-16illustrate cross-sectional views of examples of first lengths of fiber for enabling adjustment of beam characteristics in a VBC fiber responsive to perturbation of an optical beam propagating in the first lengths of fiber. Some examples of beam characteristics that may be adjusted in the first length of fiber are: beam diameter, beam divergence distribution, BPP, intensity distribution, luminance, M2factor, NA, optical intensity profile, power density profile, radial beam position, radiance, spot size, or the like, or any combination thereof. The first lengths of fiber depicted inFIGS.11-16and described below are merely examples and do not provide an exhaustive recitation of the variety of first lengths of fiber that may be utilized to enable adjustment of beam characteristics in a VBC fiber assembly. Selection of materials, appropriate RIPs, and other variables for the first lengths of fiber illustrated inFIGS.11-16at least depend on a desired beam output. A wide variety of fiber variables are contemplated and are within the scope of the claimed subject matter. Thus, claimed subject matter is not limited by examples provided herein. InFIG.11first length of fiber1100comprises a step-index profile1102.FIG.12illustrates a first length of fiber1200comprising a “pedestal RIP” (i.e., a core comprising a step-index region surrounded by a larger step-index region)1202.FIG.13illustrates first length of fiber1300comprising a multiple-pedestal RIP1302. FIG.14Aillustrates first length of fiber1400comprising a graded-index profile1418surrounded by a down-doped region1404. When the fiber1400is perturbed, modes may shift radially outward in fiber1400(e.g., during bending of fiber1400). Graded-index profile1402may be designed to promote maintenance or even compression of modal shape. This design may promote adjustment of a beam propagating in fiber1400to generate a beam having a beam intensity distribution concentrated in an outer perimeter of the fiber (i.e., in a portion of the fiber core that is displaced from the fiber axis). As described above, when the adjusted beam is coupled into a second length of fiber having confinement regions, the intensity distribution of the adjusted beam may be trapped in the outermost confinement region, providing a donut shaped intensity distribution. A beam spot having a narrow outer confinement region may be useful to enable certain material processing actions. FIG.14Billustrates first length of fiber1406comprising a graded-index profile1414surrounded by a down-doped region1408similar to fiber1400. However, fiber1406includes a divergence structure1410(a lower-index region) as can be seen in profile1412. The divergence structure1410is an area of material with a lower refractive index than that of the surrounding core. As the beam is launched into first length of fiber1406, refraction from divergence structure1410causes the beam divergence to increase in first length of fiber1406. The amount of increased divergence depends on the amount of spatial overlap of the beam with the divergence structure1410and the magnitude of the index difference between the divergence structure1410and the core material. Divergence structure1410can have a variety of shapes, depending on the input divergence distribution and desired output divergence distribution. In an example, divergence structure1410has a triangular or graded index shape. FIG.15illustrates a first length of fiber1500comprising a parabolic-index central region1502surrounded by a constant-index region1504, and the constant-index region1504is surrounded by a lower-index annular layer1506. The lower-index annulus1506helps guide a beam propagating in fiber1500. When the propagating beam is perturbed, modes shift radially outward in fiber1500(e.g., during bending of fiber1500). As one or more modes shift radially outward, parabolic-index region1502promotes retention of modal shape. When the modes reach the constant-index region of the RIP1510, they will be compressed against the low-index ring1506, which may cause preferential excitation of the outermost confinement region in the second fiber (in comparison to the first fiber RIP shown inFIG.14). In one implementation, this fiber design works with a confinement fiber having a central step-index core and a single annular core. The parabolic-index portion1502of the RIP overlaps with the central step-index core of the confinement fiber. The constant-index portion1504overlaps with the annular core of the confinement fiber. The constant-index portion1504of the first fiber is intended to make it easier to move the beam into overlap with the annular core by bending. This fiber design also works with other designs of the confinement fiber. FIG.16illustrates a first length of fiber1600comprising guiding regions1604,1606,1608, and1616bounded by lower-index layers1610,1612, and1614where the indexes of the lower-index layers1610,1612, and1614are stepped or, more generally, do not all have the same value. The stepped-index layers may serve to bound the beam intensity to certain guiding regions (1604,1606,1608, and1616) when the perturbation assembly210(seeFIG.2) acts on the fiber1600. In this way, adjusted beam light may be trapped in the guiding regions over a range of perturbation actions (such as over a range of bend radii, a range of bend lengths, a range of micro-bending pressures, and/or a range of acousto-optical signals), allowing for a certain degree of perturbation tolerance before a beam intensity distribution is shifted to a more distant radial position in fiber1600. Thus, variation in beam characteristics may be controlled in a step-wise fashion. The radial widths of the guiding regions1604,1606,1608, and1616may be adjusted to achieve a desired ring width, as may be required by an application. Also, a guiding region can have a thicker radial width to facilitate trapping of a larger fraction of the incoming beam profile if desired. Region1606is an example of such a design. FIGS.17-21depict examples of fibers configured to enable maintenance and/or confinement of adjusted beam characteristics in the second length of fiber (e.g., fiber208). These fiber designs are referred to as “ring-shaped confinement fibers” because they contain a central core surrounded by annular or ring-shaped cores. These designs are merely examples and not an exhaustive recitation of the variety of fiber RIPs that may be used to enable maintenance and/or confinement of adjusted beam characteristics within a fiber. Thus, claimed subject matter is not limited to the examples provided herein. Moreover, any of the first lengths of fiber described above with respect toFIGS.11-16may be combined with any of the second length of fiber describedFIGS.17-21. FIG.17illustrates a cross-sectional view of an example second length of fiber for maintaining and/or confining adjusted beam characteristics in a VBC fiber assembly. As the perturbed beam is coupled from a first length of fiber to second length of fiber1700, the second length of fiber1700may maintain at least a portion of the beam characteristics adjusted in response to perturbation in the first length of fiber within one or more of confinement regions1704,1706, and/or1708. Fiber1700has a RIP1702. Each of confinement regions1704,1706, and/or1708is bounded by a lower index layer1710and/or1712. This design enables second length of fiber1700to maintain the adjusted beam characteristics. As a result, a beam output by fiber1700will substantially maintain the received adjusted beam as modified in the first length of fiber giving the output beam adjusted beam characteristics, which may be customized to a processing task or other application. Similarly,FIG.18depicts a cross-sectional view of an example second length of fiber1800for maintaining and/or confining beam characteristics adjusted in response to perturbation in the first length of fiber in a VBC fiber assembly. Fiber1800has a RIP1802. However, confinement regions1808,1810, and/or1812have different thicknesses than confinement regions1704,1706, and1708. Each of confinement regions1808,1810, and/or1812is bounded by a lower index layer1804and/or1806. Varying the thicknesses of the confinement regions (and/or barrier regions) enables tailoring or optimization of a confined adjusted radiance profile by selecting particular radial positions within which to confine an adjusted beam. FIG.19depicts a cross-sectional view of an example second length of fiber1900having a RIP1902for maintaining and/or confining an adjusted beam in a VBC fiber assembly configured to provide variable beam characteristics. In this example, the number and thicknesses of confinement regions1904,1906,1908, and1910are different from fiber1700and1800and the barrier layers1912,1914, and1916are of varied thicknesses as well. Furthermore, confinement regions1904,1906,1908, and1910have different indexes of refraction and barrier layers1912,1914, and1916have different indexes of refraction as well. This design may further enable a more granular or optimized tailoring of the confinement and/or maintenance of an adjusted beam radiance to particular radial locations within fiber1900. As the perturbed beam is launched from a first length of fiber to second length of fiber1900the modified beam characteristics of the beam (having an adjusted intensity distribution, radial position, and/or divergence angle, or the like, or a combination thereof) is confined within a specific radius by one or more of confinement regions1904,1906,1908and/or1910of second length of fiber1900. As noted previously, the divergence angle of a beam may be conserved or adjusted and then conserved in the second length of fiber. There are a variety of methods to change the divergence angle of a beam. The following are examples of fibers configured to enable adjustment of the divergence angle of a beam propagating from a first length of fiber to a second length of fiber in a fiber assembly for varying beam characteristics. However, these are merely examples and not an exhaustive recitation of the variety of methods that may be used to enable adjustment of divergence of a beam. Thus, claimed subject matter is not limited to the examples provided herein. FIG.20depicts a cross-sectional view of an example second length of fiber2000having RIP2002for modifying, maintaining, and/or confining beam characteristics adjusted in response to perturbation in the first length of fiber. In this example, second length of fiber2000is similar to the previously described second lengths of fiber and forms a portion of the VBC fiber assembly for delivering variable beam characteristics as discussed above. There are three confinement regions2004,2006, and2008and three barrier layers2010,2012, and2016. Second length of fiber2000also has a divergence structure2014situated within the confinement region2006. The divergence structure2014is an area of material with a lower refractive index than that of the surrounding confinement region. As the beam is launched into second length of fiber2000refraction from divergence structure2014causes the beam divergence to increase in second length of fiber2000. The amount of increased divergence depends on the amount of spatial overlap of the beam with the divergence structure2014and the magnitude of the index difference between the divergence structure2014and the core material. By adjusting the radial position of the beam near the launch point into the second length of fiber2000, the divergence distribution may be varied. The adjusted divergence of the beam is conserved in fiber2000, which is configured to deliver the adjusted beam to the process head, another optical system (e.g., fiber-to-fiber coupler or fiber-to-fiber switch), the work piece, or the like, or a combination thereof. In an example, divergence structure2014may have an index dip of about 10−5−3×10−2with respect to the surrounding material. Other values of the index dip may be employed within the scope of this disclosure and claimed subject matter is not so limited. FIG.21depicts a cross-sectional view of an example second length of fiber2100having a RIP2102for modifying, maintaining, and/or confining beam characteristics adjusted in response to perturbation in the first length of fiber. Second length of fiber2100forms a portion of a VBC fiber assembly for delivering a beam having variable characteristics. In this example, there are three confinement regions2104,2106, and2108and three barrier layers2110,2112, and2116. Second length of fiber2100also has a plurality of divergence structures2114and2118. The divergence structures2114and2118are areas of graded lower index material. As the beam is launched from the first length fiber into second length of fiber2100, refraction from divergence structures2114and2118causes the beam divergence to increase. The amount of increased divergence depends on the amount of spatial overlap of the beam with the divergence structure and the magnitude of the index difference between the divergence structure2114and/or2118and the surrounding core material of confinement regions2106and2104respectively. By adjusting the radial position of the beam near the launch point into the second length of fiber2100, the divergence distribution may be varied. The design shown inFIG.21allows the intensity distribution and the divergence distribution to be varied somewhat independently by selecting both a particular confinement region and the divergence distribution within that conferment region (because each confinement region may include a divergence structure). The adjusted divergence of the beam is conserved in fiber2100, which is configured to deliver the adjusted beam to the process head, another optical system, or the work piece. Forming the divergence structures2114and2118with a graded or non-constant index enables tuning of the divergence profile of the beam propagating in fiber2100. An adjusted beam characteristic such as a radiance profile and/or divergence profile may be conserved as it is delivered to a process head by the second fiber. Alternatively, an adjusted beam characteristic such as a radiance profile and/or divergence profile may be conserved or further adjusted as it is routed by the second fiber through a fiber-to-fiber coupler (FFC) and/or fiber-to-fiber switch (FFS) and to a process fiber, which delivers the beam to the process head or the work piece. FIGS.26-28are cross-sectional views illustrating examples of fibers and fiber RIPs configured to enable maintenance and/or confinement of adjusted beam characteristics of a beam propagating in an azimuthally asymmetric second length of fiber wherein the beam characteristics are adjusted responsive to perturbation of a first length of fiber coupled to the second length of fiber and/or perturbation of the beam by a perturbation device110. These azimuthally asymmetric designs are merely examples and are not an exhaustive recitation of the variety of fiber RIPs that may be used to enable maintenance and/or confinement of adjusted beam characteristics within an azimuthally asymmetric fiber. Thus, claimed subject matter is not limited to the examples provided herein. Moreover, any of a variety of first lengths of fiber (e.g., like those described above) may be combined with any azimuthally asymmetric second length of fiber (e.g., like those described inFIGS.26-28). FIG.26illustrates RIPs at various azimuthal angles of a cross-section through an elliptical fiber2600. At a first azimuthal angle2602, fiber2600has a first RIP2604. At a second azimuthal angle2606that is rotated 45° from first azimuthal angle2602, fiber2600has a second RIP2608. At a third azimuthal angle2610that is rotated another 45° from second azimuthal angle2606, fiber2600has a third RIP2612. First, second and third RIPs2604,2608and2612are all different. FIG.27illustrates RIPs at various azimuthal angles of a cross-section through a multicore fiber2700. At a first azimuthal angle2702, fiber2700has a first RIP2704. At a second azimuthal angle2706, fiber2700has a second RIP2708. First and second RIPs2704and2708are different. In an example, perturbation device110may act in multiple planes in order to launch the adjusted beam into different regions of an azimuthally asymmetric second fiber. FIG.28illustrates RIPs at various azimuthal angles of a cross-section through a fiber2800having at least one crescent shaped core. In some cases, the corners of the crescent may be rounded, flattened, or otherwise shaped, which may minimize optical loss. At a first azimuthal angle2802, fiber2800has a first RIP2804. At a second azimuthal angle2806, fiber2800has a second RIP2808. First and second RIPs2804and2808are different. FIG.22Aillustrates an example of a laser system2200including a VBC fiber assembly2202configured to provide variable beam characteristics. VBC fiber assembly2202comprises a first length of fiber104, second length of fiber108, and a perturbation device110. VBC fiber assembly2202is disposed between feeding fiber2212(i.e., the output fiber from the laser source) and VBC delivery fiber2240. VBC delivery fiber2240may comprise second length of fiber108or an extension of second length of fiber108that modifies, maintains, and/or confines adjusted beam characteristics. Beam2210is coupled into VBC fiber assembly2202via feeding fiber2212. Fiber assembly2202is configured to vary the characteristics of beam2210in accordance with the various examples described above. The output of fiber assembly2202is adjusted beam2214which is coupled into VBC delivery fiber2240. VBC delivery fiber2240delivers adjusted beam2214to free-space optics assembly2208, which then couples beam2214into a process fiber2204. Adjusted beam2214is then delivered to process head2206by process fiber2204. The process head can include guided wave optics (such as fibers and fiber coupler), free space optics such as lenses, mirrors, optical filters, diffraction gratings), beam scan assemblies such as galvanometer scanners, polygonal mirror scanners, or other scanning systems that are used to shape the beam2214and deliver the shaped beam to a workpiece. In laser system2200, one or more of the free-space optics of assembly2208may be disposed in an FFC or other beam coupler2216to perform a variety of optical manipulations of an adjusted beam2214(represented inFIG.22Awith different dashing than beam2210). For example, free-space optics assembly2208may preserve the adjusted beam characteristics of beam2214. Process fiber2204may have the same RIP as VBC delivery fiber2240. Thus, the adjusted beam characteristics of adjusted beam2214may be preserved all the way to process head2206. Process fiber2204may comprise a RIP similar to any of the second lengths of fiber described above, including confinement regions. FFCs can include one, two, or more lenses, but in typical examples, two lenses having the same nominal focal length are used, producing unit magnification. In most practical examples, magnification produced with an FFC is between 0.8 and 1.2, which corresponds to a ratio of focal lengths. Alternatively, as illustrated inFIG.22B, free-space optics assembly2208may change the adjusted beam characteristics of beam2214by, for example, increasing or decreasing the divergence and/or the spot size of beam2214(e.g., by magnifying or demagnifying beam2214) and/or otherwise further modifying adjusted beam2214. Furthermore, process fiber2204may have a different RIP than VBC delivery fiber2240. Accordingly, the RIP of process fiber2204may be selected to preserve additional adjustment of adjusted beam2214made by the free-space optics of assembly2208to generate a twice adjusted beam2224(represented inFIG.22Bwith different dashing than beam2214). FIG.23illustrates an example of a laser system2300including VBC fiber assembly2302disposed between feeding fiber2312and VBC delivery fiber2340. During operation, beam2310is coupled into VBC fiber assembly2302via feeding fiber2312. Fiber assembly2302includes a first length of fiber104, second length of fiber108, and a perturbation device110and is configured to vary characteristics of beam2310in accordance with the various examples described above. Fiber assembly2302generates adjusted beam2314output by VBC delivery fiber2340. VBC delivery fiber2340comprises a second length of fiber108of fiber for modifying, maintaining, and/or confining adjusted beam characteristics in a fiber assembly2302in accordance with the various examples described above (seeFIGS.17-21, for example). VBC delivery fiber2340couples adjusted beam2314into beam switch (FFS)2332, which then couples its various output beams to one or more of multiple process fibers2304,2320, and2322. Process fibers2304,2320, and2322deliver adjusted beams2314,2328, and2330to respective process heads2306,2324, and2326. In an example, beam switch2332includes one or more sets of free-space optics2308,2316, and2318configured to perform a variety of optical manipulations of adjusted beam2314. Free-space optics2308,2316, and2318may preserve or vary adjusted beam characteristics of beam2314. Thus, adjusted beam2314may be maintained by the free-space optics or adjusted further. Process fibers2304,2320, and2322may have the same or a different RIP as VBC delivery fiber2340, depending on whether it is desirable to preserve or further modify a beam passing from the free-space optics assemblies2308,2316, and2318to respective process fibers2304,2320, and2322. In other examples, one or more beam portions of beam2310are coupled to a workpiece without adjustment, or different beam portions are coupled to respective VBC fiber assemblies so that beam portions associated with a plurality of beam characteristics can be provided for simultaneous workpiece processing. Alternatively, beam2310can be switched to one or more of a set of VBC fiber assemblies. Routing adjusted beam2314through any of free-space optics assemblies2308,2316, and2318enables delivery of a variety of additionally adjusted beams to process heads2206,2324, and2326. Therefore, laser system2300provides additional degrees of freedom for varying the characteristics of a beam, as well as switching the beam between process heads (“time sharing”) and/or delivering the beam to multiple process heads simultaneously (“power sharing”). For example, free-space optics in beam switch2332may direct adjusted beam2314to free-space optics assembly2316configured to preserve the adjusted characteristics of beam2314. Process fiber2304may have the same RIP as VBC delivery fiber2340. Thus, the beam delivered to process head2306will be a preserved adjusted beam2314. In another example, beam switch2332may direct adjusted beam2314to free-space optics assembly2318configured to preserve the adjusted characteristics of adjusted beam2314. Process fiber2320may have a different RIP than VBC delivery fiber2340and may be configured with divergence altering structures as described with respect toFIGS.20and21to provide additional adjustments to the divergence distribution of beam2314. Thus, the beam delivered to process head2324will be a twice adjusted beam2328having a different beam divergence profile than adjusted beam2314. Process fibers2304,2320, and/or2322may comprise a RIP similar to any of the second lengths of fiber described above, including confinement regions or a wide variety of other RIPs, and claimed subject matter is not limited in this regard. In yet another example, free-space optics switch2332may direct adjusted beam2314to free-space optics assembly2308configured to change the beam characteristics of adjusted beam2314. Process fiber2322may have a different RIP than VBC delivery fiber2340and may be configured to preserve (or alternatively further modify) the new further adjusted characteristics of beam2314. Thus, the beam delivered to process head2326will be a twice adjusted beam2330having different beam characteristics (due to the adjusted divergence profile and/or intensity profile) than adjusted beam2314. InFIGS.22A,22B, and23, the optics in the FFC or FFS may adjust the spatial profile and/or divergence profile by magnifying or demagnifying the beam2214before launching into the process fiber. They may also adjust the spatial profile and/or divergence profile via other optical transformations. They may also adjust the launch position into the process fiber. These methods may be used alone or in combination. FIGS.22A,22B, and23merely provide examples of combinations of adjustments to beam characteristics using free-space optics and various combinations of fiber RIPs to preserve or modify adjusted beams2214and2314. The examples provided above are not exhaustive and are meant for illustrative purposes only. Thus, claimed subject matter is not limited in this regard. FIG.24illustrates various examples of perturbation devices, assemblies or methods (for simplicity referred to collectively herein as “perturbation device110”) for perturbing a VBC fiber200and/or an optical beam propagating in VBC fiber200according to various examples provided herein. Perturbation device110may be any of a variety of devices, methods, and/or assemblies configured to enable adjustment of beam characteristics of a beam propagating in VBC fiber200. In an example, perturbation device110may be a mandrel2402, a micro-bend2404in the VBC fiber, flexible tubing2406, an acousto-optic transducer2408, a thermal device2410, a piezo-electric device2412, a grating2414, a clamp2416(or other fastener), or the like, or any combination thereof. These are merely examples of perturbation devices100and not an exhaustive listing of perturbation devices100and claimed subject matter is not limited in this regard. Mandrel2402may be used to perturb VBC fiber200by providing a form about which VBC fiber200may be bent. As discussed above, reducing the bend radius of VBC fiber200moves the intensity distribution of the beam radially outward. In some examples, mandrel2402may be stepped or conically shaped to provide discrete bend radii levels. Alternatively, mandrel2402may comprise a cone shape without steps to provide continuous bend radii for more granular control of the bend radius. The radius of curvature of mandrel2402may be constant (e.g., a cylindrical form) or non-constant (e.g., an oval-shaped form). Similarly, flexible tubing2406, clamps2416(or other varieties of fasteners), or rollers250may be used to guide and control the bending of VBC fiber200about mandrel2402. Furthermore, changing the length over which the fiber is bent at a particular bend radius also may modify the intensity distribution of the beam. VBC fiber200and mandrel2402may be configured to change the intensity distribution within the first fiber predictably (e.g., in proportion to the length over which the fiber is bent and/or the bend radius). Rollers250may move up and down along a track2442on platform2434to change the bend radius of VBC fiber200. Clamps2416(or other fasteners) may be used to guide and control the bending of VBC fiber200with or without a mandrel2402. Clamps2416may move up and down along a track2442or platform2446. Clamps2416may also swivel to change bend radius, tension, or direction of VBC fiber200. Controller2448may control the movement of clamps2416. In another example, perturbation device110may be flexible tubing2406and may guide bending of VBC fiber200with or without a mandrel2402. Flexible tubing2406may encase VBC fiber200. Tubing2406may be made of a variety of materials and may be manipulated using piezoelectric transducers controlled by controller2444. In another example, clamps or other fasteners may be used to move flexible tubing2406. Micro-bend2404in VBC fiber is a local perturbation caused by lateral mechanical stress on the fiber. Micro-bending can cause mode coupling and/or transitions from one confinement region to another confinement region within a fiber, resulting in varied beam characteristics of the beam propagating in a VBC fiber200. Mechanical stress may be applied by an actuator2436that is controlled by controller2440. However, this is merely an example of a method for inducing mechanical stress in fiber200and claimed subject matter is not limited in this regard. Acousto-optic transducer (AOT)2408may be used to induce perturbation of a beam propagating in the VBC fiber using an acoustic wave. The perturbation is caused by the modification of the refractive index of the fiber by the oscillating mechanical pressure of an acoustic wave. The period and strength of the acoustic wave are related to the acoustic wave frequency and amplitude, allowing dynamic control of the acoustic perturbation. Thus, a perturbation assembly110including AOT2408may be configured to vary the beam characteristics of a beam propagating in the fiber. In an example, piezo-electric transducer2418may create the acoustic wave and may be controlled by controller or driver2420. The acoustic wave induced in AOT2408may be modulated to change and/or control the beam characteristics of the optical beam in VBC200in real-time. However, this is merely an example of a method for creating and controlling an AOT2408and claimed subject matter is not limited in this regard. Thermal device2410may be used to induce perturbation of a beam propagating in VBC fiber using heat. The perturbation is caused by the modification of the RIP of the fiber induced by heat. Perturbation may be dynamically controlled by controlling an amount of heat transferred to the fiber and the length over which the heat is applied. Thus, a perturbation assembly110including thermal device2410may be configured to vary a range of beam characteristics. Thermal device2410may be controlled by controller2450. Piezo-electric transducer2412may be used to induce perturbation of a beam propagating in a VBC fiber using piezoelectric action. The perturbation is caused by the modification of the RIP of the fiber induced by a piezoelectric material attached to the fiber. The piezoelectric material in the form of a jacket around the bare fiber may apply tension or compression to the fiber, modifying its refractive index via the resulting changes in density. Perturbation may be dynamically controlled by controlling a voltage to the piezo-electric device2412. Thus, a perturbation assembly110including piezo-electric transducer2412may be configured to vary the beam characteristics over a particular range. In an example, piezo-electric transducer2412may be configured to displace VBC fiber200in a variety of directions (e.g., axially, radially, and/or laterally) depending on a variety of factors, including how the piezo-electric transducer2412is attached to VBC fiber200, the direction of the polarization of the piezo-electric materials, the applied voltage, etc. Additionally, bending of VBC fiber200is possible using the piezo-electric transducer2412. For example, driving a length of piezo-electric material having multiple segments comprising opposing electrodes can cause a piezoelectric transducer2412to bend in a lateral direction. Voltage applied to piezoelectric transducer2412by electrode2424may be controlled by controller2422to control displacement of VBC fiber200. Displacement may be modulated to change and/or control the beam characteristics of the optical beam in VBC200in real-time. However, this is merely an example of a method of controlling displacement of a VBC fiber200using a piezo-electric transducer2412and claimed subject matter is not limited in this regard. Gratings2414may be used to induce perturbation of a beam propagating in a VBC fiber200. A grating2414can be written into a fiber by inscribing a periodic variation of the refractive index into the core. Gratings2414such as fiber Bragg gratings can operate as optical filters or as reflectors. A long-period grating can induce transitions among co-propagating fiber modes. The radiance, intensity profile, and/or divergence profile of a beam comprised of one or more modes can thus be adjusted using a long-period grating to couple one or more of the original modes to one or more different modes having different radiance and/or divergence profiles. Adjustment is achieved by varying the periodicity or amplitude of the refractive index grating. Methods such as varying the temperature, bend radius, and/or length (e.g., stretching) of the fiber Bragg grating can be used for such adjustment. VBC fiber200having gratings2414may be coupled to stage2426. Stage2426may be configured to execute any of a variety of functions and may be controlled by controller2428. For example, stage2426may be coupled to VBC fiber200with fasteners2430and may be configured to stretch and/or bend VBC fiber200using fasteners2430for leverage. Stage2426may have an embedded thermal device and may change the temperature of VBC fiber200. FIG.25illustrates an example process2500for adjusting and/or maintaining beam characteristics within a fiber without the use of free-space optics to adjust the beam characteristics. In block2502, a first length of fiber and/or an optical beam are perturbed to adjust one or more optical beam characteristics. Process2500moves to block2504, where the optical beam is launched into a second length of fiber. Process2500moves to block2506, where the optical beam having the adjusted beam characteristics is propagated in the second length of fiber. Process2500moves to block2508, where at least a portion of the one or more beam characteristics of the optical beam are maintained within one or more confinement regions of the second length of fiber. The first and second lengths of fiber may be comprised of the same fiber, or they may be different fibers. With reference toFIGS.29A-29C, a variable beam characteristics (VBC) apparatus2900includes a disc2902. The disc2902is a perturbation assembly having circular, elliptical, or other curved cross-section defining a perimeter surface2904that serves as a fiber bending or fiber shaping surface. Fiber guides2906,2908are situated at the perimeter surface2904to urge a section of a first fiber2910toward the perimeter surface2904. The fiber guides2906,2908are secured to spokes2907,2909that are connected to permit the fiber guides2906,2908be rotatable about an axis2912. A separation of the guides2906,2908along the perimeter surface2904defines an angle θ that is associated with a length of a section of the first fiber2910that conforms to or is urged to contact the perimeter surface2904. Rotation of one or both of the guides2906,2908permits selection of a suitable length. In some examples, a fiber is secured to a guide such as the guide2908, and rotation of the guide wraps a fiber about a fiber bending surface, thereby selecting a fiber length to be bent based on rotation of a guide. In such examples, a tension mechanism can be provided so that the fiber unwinds from a fiber bending surface as the guide rotates to unwrap the fiber. The guides2906,2908can include surfaces that press fibers toward the fiber bending surface. For example, the guides2906,2908can be made of or include an elastic portion of rubber, foam, cloth, fibers, or other material than can be urged against a fiber without compromising fiber integrity and to accommodate sharp surface irregularities that could damage fibers. The fiber bending surface such as the perimeter surface2904can be provided with a similar material along the entire surface or only at portions expected to be used in conforming fibers. Alternatively, the guides2906,2908can include grooves such as a groove2916that retains a fiber and may or may not press the fiber against the fiber bending surface. For guides that are rotatable, grooves may extend around the entire perimeter so that a fiber is retained in the groove as the guide rotates and travels along the fiber bending surface. The first fiber2910is typically connected to a second fiber2920with a splice2918such as a fusion splice (shown in possible two locations inFIG.29A). In some examples, a single fiber can be used, but generally two different fibers are used having different refractive index profiles. The guides2906,2908then urge a section of the second fiber into a bent path along the perimeter surface2904(along with the splice2918). In some examples, the spokes2907,2909are rigid, but in other examples, elastic members such as springs can be used (or spokes can include an elastic portion) so that the guides2906,2908are pulled toward the perimeter surface2904. In many practical examples, only one guide is used, but one, two, three, or more can be used to select portions of one or more fibers to be conformed to the fiber bending surface2904. For example, sections of the first fiber2910and the second fiber2920can be independently selected to be urged toward the perimeter surface using respective pairs of guides. Locations of the guides2906,2908can be controlled using motor2930that is coupled to the spokes2907,2909to rotate to establish the angle θ. A controller2932is coupled to the motor2930so that the guides2906,2908can be computer or processor controlled, or controlled manually. In some examples, the controller2932includes a non-transitory computer readable medium that includes a calibration table in which the angle θ and associated beam characteristics are stored. In systems having multiple guides, each can be arranged to be independently moved, and sections of one or more fibers can be selected. In the example ofFIGS.29A-29C, a single bend radius is associated with a fiber bending surface, but in other examples, series of different bend radii can be used, each defined with a corresponding step formed as, for example, a portion of a cylinder, or on a tapered surface such as a cone or portion thereof. Arcuate or other curved surfaces can be used as well. Guides can be situated to direct fibers to a fiber bending or shaping surface having a particular curvature as well as selecting a length of fiber to be shaped into that curvature. Fiber sections can be bent at a plurality of surface areas having associated curvatures and section lengths can be varied for each curvature. Cylindrical curvatures are shown inFIGS.29A-29C, but curvatures along multiple directions such as spherical or ellipsoidal curvatures can be used. The perimeter surface2904is an exterior surface of the disc2902, but in other examples, interior surfaces of rings, hollow cylinders, or other shapes can be used as fiber bending or shaping surfaces, and guides situated to adjust fiber shape with respect to such interior surfaces. In the disclosed examples, an optical fiber that includes a length of a first optical fiber and a second optical fiber that are fusion spliced is bent at or near the fusion splice so as to vary a spatial beam profile or other beam characteristic produced in the first fiber or the second fiber. More efficient adjustment of spatial beam profile is typically achieved if the fusion splice is included in the bent portion of the fiber. However, the fusion splice can be located sufficiently close to the bent portion. Typically, the fusion splice should be situated within a length of less than about 2, 5, 10, 50, 100, 500, or 1000 times a core diameter of either fiber. Sufficient fiber lengths can also depend on fiber numerical aperture as well. One possible explanation for the utility of bending either the first fiber or the second fiber is that bending of a fiber near a launch point, which is at the spliced junction2918, can produce a variable spatial beam profile that propagates some distance before collapsing to an original beam shape. In a receiving (second) fiber, bending near a splice can perturb a spatial power distribution from the launching (first) fiber, and thus variably couple the received power into a selected spatial power distribution. The disclosure is not limited to operation in accordance with operation in this way, and this explanation is only provided as one potential explanation for convenience. InFIG.29A, the perturbation assembly disc2902is disposed proximal to the spliced junction2918. Alternatively, a perturbation assembly may not be disposed near a splice. Moreover, a splice may not be needed at all, for example the fiber2910may be a single fiber, a first length of fiber and second length of fiber could be spaced apart, or secured with a small gap (air-spaced or filled with an optical material, such as optical cement or an index-matching material). In some examples, the bend radius of a fiber is changed from a first bend radius R1to a second bend radius R2by using a stepped mandrel or a cone in a perturbation assembly. Fiber portions having different bend radii can be independently selected. Changing a bend radius of a fiber may change the radial beam position, divergence angle, and/or radiance profile, or other beam characteristics of a beam within the fiber. In an example shown in a sectional view inFIG.30, a disk3002defines a perimeter (fiber bending) surface3004that is provided with grooves3010,3011. Typically, the disk3002includes a central bore3006for insertion of a rotatable shaft (not shown). A guide3008includes protrusions3016,3017that can be inserted in the grooves3010,3011so that the guide3008is movable along the perimeter surface3004. A fiber3014is shown situated in a groove3015in the guide3008. In other examples, guides can have dovetail shaped protrusions to fit into correspond grooves in a disk or other support. Alternatively, grooves can be provided in the guide, and protrusions in the disk, or any combination thereof as may be convenient. With reference toFIG.31, a VBC apparatus3100includes an ellipsoidal disk3102having a perimeter (fiber bending) surface3104. Guides3106,3107are situated to select a length of a fiber3108that conforms to the fiber bending surface3104. As shown, the guide3106is fixed with respect to the perimeter surface3104, and the guide3107is configured to be movable along the perimeter surface3104. In the example ofFIG.31, the guide3107is secured with an elastic member3110so as to be rotatable about an axis3112. The perimeter surface3104is defined by an ellipse and thus has a varying radius of curvature, and the elastic member3110is selected to permit the guide3107to accommodate varying distances from the axis3112to the perimeter surface3104. FIG.32illustrates an additional fiber bending surface3202that is formed on a substrate3200. A surface3206opposite the fiber bending surface3202can be planar, or have a convex or concave curvature. A guide3208is situated to urge a fiber against the fiber bending surface3202, and one, two, three, or more such guides can be used. As discussed above, the guide3208can be retained by a groove and be slidable, or can be coupled to an elastic member that urges the guide3208toward the fiber bending surface3202. The fiber bending surface3202can have various simple or complex curvatures, and can be convex, concave, or planar in at least some portions. The guide3208can be spherical or cylindrical and arranged to roll along the fiber bending surface3204. In some examples, the guide3208is situated to urge a fiber3210to contact the fiber bending surface3202, to change a bend angle of the fiber3210, or bend the fiber3210while leaving a gap3212between the fiber3210and the fiber bending surface3202proximate the guide3208. Referring toFIGS.33A-33B, a guide3304is situated to urge a fiber3306toward a fiber bending surface3308. The fiber3306can be secured with respect to the fiber bending surface3308with a clip3310or otherwise fixed so that a length of fiber conformed to the fiber bending surface3208is determined by a position of the guide3304. As shown in the sectional view ofFIG.33B, the fiber3306is retained in a channel3312, and the guide3304includes protrusions3320,3321that correspond to grooves3330,3331in the fiber bending surface3308. With reference toFIG.34, a section3402of a disk defines a fiber bending surface3404. A clamp3406secures a fiber3408to the fiber bending surface3404and a guide3410is movable along the fiber bending surface3404to control a fiber length that is urged toward the fiber bending surface3404. The guide3410can move along the surface in grooves and/or be secured to an axis that permits rotation. As shown inFIG.35, a portion3502of ring defines a fiber bending surface3504. A clamp3506and a guide3510are provided to adjust a fiber length that is conformed to the fiber bending surface3504. The guide3510can be slidable along the fiber bending surface3504in grooves or otherwise, or coupled to a spoke to rotate along an axis. In some examples, a fiber bending surface is rotatable or otherwise adjustable so that a separation of a clamp fixed with respect to the fiber bending surface and a guide is adjustable. For example, as shown inFIG.35, a spoke3512can permit movement of the guide3510along the fiber bending surface3504and/or a spoke3514can be coupled to permit rotation of the ring3502with respect to the guide3510. Such rotation or movement of a fiber bending surface can be accomplished by rotation of a disk, cylinder, or other shape that defines the fiber bending surface. As shown inFIG.36, a VBC apparatus3600includes a flexible plate3602that is situated to be flexed against fixed supports3604,3606by a linear actuator3608that urges a bearing3610toward the flexible plate3602. A fiber3612is secured to the flexible plate3602or otherwise situated so as to bend in response to flexing of the flexible plate3602. FIGS.37A-37Billustrate a spool3700that includes a groove or channel3704that is configured to retain one or more loops of a fiber3702. Rotation of the spool3700(or the fiber about the spool3700) permits adjustment of a beam perturbation applied by the fiber3702. Other arrangements can be provided that permit varying a number of wraps of a fiber on a substrate, and typically a section of a cylinder can suffice. A controller is generally provided to select a number of wraps (turns) by controlling a stepper motor or other motor, but in some examples, the number of turns can be adjusted manually. While it may be convenient that the fiber3702contact a radially innermost portion of the groove3704, this is not required. With reference toFIGS.38A-38B, a VBC device3800includes a cylinder3804that is situated to press a fiber loop3802towards a first jaw3806and a second jaw3808in response to translation of a rod3812that is secured to the cylinder3804. One or more springs such as representative spring3810are situated to urge one or both of the jaws3806,3808toward the fiber3802and the cylinder3804.FIG.38Ashows the fiber loop3802without deformation for convenient illustration; with the configuration ofFIG.38B, substantial bending of the fiber loop3802would be obtained. Various shapes can be used to press the fiber loop3802such as cylindrical, spherical, ellipsoidal, arcuate, or other shapes, and a cylinder is shown for convenient illustration. FIGS.39A-39Dillustrate fiber shape with various engagements of the mechanism ofFIGS.38A-38B. InFIG.39A, a fiber remains in a loop3900without bending or deformation.FIGS.39B-39Cshow fiber sections3902,3904,3906that contact the jaws3806,3808and the cylinder3804as engagement of the mechanism is increased. The shape of the loop3900changes as well. FIG.40illustrates a VBC apparatus4000for perturbing beam characteristics that includes a first set4002and a second set4004of cylinders or other suitable shapes that are situated opposite each other. A fiber4008is situated between the first set4002and the second set4004so as to be bent or deformed as the first set4002and the second set3004are urged toward each other. InFIG.40, cylinders of the same shape are shown, but one or more of the cylinders of either set can have different diameters, and different shapes can be used for each surface of each set. A plurality of fiber shaping surfaces can be defined on a single substrate, if convenient, as shown inFIG.41. A plate4100includes elliptical or other protrusions4101,4102,4103,4104that provide fiber shaping surfaces. Cylindrical, arcuate, spherical, parabolic, or other shapes can be used. FIG.42illustrates a VBC apparatus4200that is similar to that ofFIG.36but in which a flexible plate4202is pulled against stops4204,4206with a linear actuator4208that is coupled to the flexible plate4202with an elastic or rigid coupling4210. A fiber4212is situated to conform to a shape of the flexible plate4202. In a further example shown inFIGS.43A-43B, a beam perturbation mechanism4300includes a cylinder4304having a central bore4306that can accommodate a drive shaft. An outer surface4305of the cylinder4304serves as a fiber shaping surface. InFIG.43B, a fiber4302is shown as having been wrapped about the cylinder4304several times. Rotation of the cylinder4304can be used to provide a selected beam perturbation, either manually, or with a processor-based control system that can store beam perturbation characteristics as a function of rotation angle in one or more non-transitory computer-readable media. FIGS.44A-44Billustrate a VBC device4400that includes a substrate4402formed at least in part of an ionic polymer composite (IPC) and having a first major surface4404and second major surface4405. Electrodes4406,4408are situated on or at the first major surface4404and the second major surface4405, respectively. In some cases there are intervening layers such as non-conductive layers, protective layers, or other layers needed for fabrication or use, but such layers are not shown. A serpentine fiber loop4410is secured to the first major surface4404and is shaped to have elongated portions such as elongated portion4411that extends along an X-axis of a right handed Cartesian coordinate system4450. As shown in the sectional view ofFIG.44B, application of an electric field to the substrate4402in response to a voltage applied to the electrodes4406,4408produces a Z-directed deformation so that the first major surface4404is bowed or bent as surface4404A; such deformation produces beam perturbations in the fiber loop4410. Other deformations in other directions can be produced, and straight fiber lengths, circular loops, partial loops, serpentine lengths, and other arrangements of fibers can be oriented on either the first major surface4404or the second major surface4405along the X-direction, the Y-direction, or arbitrarily oriented. In another example illustrated inFIG.45, a VBC device4500includes an IPC substrate4502to which fiber serpentine loops4504,4505(or circular loops or fibers arranged in other shapes) are secured so as to be subject to flexing of the IPC substrate4502. Electrodes such as electrode4506are provided at ends of the IPC substrate4502, but can be situated in other portions or cover the substrate4502. Fiber ends4510,4511can be used to couple optical beams into and out of the beam perturbation device4500. As in other examples discussed above, the fiber serpentine loops4504,4505can be of a single fiber (a first fiber) or a first fiber and a second fiber with a splice. FIG.46illustrates a VBC system4600that includes input optics4601that couple one or more beams to a beam perturbation device4602and output optics4604which receive one or more perturbed beams for delivery to a substrate, or for other use. A control system4608can include control circuits, processors such as microprocessors or other programmable logic devices, memory such as RAM or ROM that stores processor-executable instructions for control of the beam perturbation device4602including, for example, one or more calibration tables containing beam perturbations as functions of beam perturbation device drive level. In some cases, the beam perturbation device4602can include one or more actuators or motors such as linear or stepper motors, piezoelectric stages, piezoelectric actuators, piezobending motors, bi-metallic strips (with thermal control), rotary motors, or voice coil motors. Alternatively, the control system can include a digital to analog convertor (DAC) for setting drive levels to the beam perturbation device. For example, IPC-based beam perturbation devices are responsive to applied voltages that can be provided by a DAC. A user interface (UI)4612is typically provided that can include one or more computer input or pointing devices such as a mouse, trackpad, keyboard, or touchscreen for setting, adjusting, and recording and storing beam perturbation values. In some cases, control is via remote network connection and the control system4608includes a wired or wireless network interface. The UI4612can also include switches, potentiometers, and other devices for use in controlling the beam perturbation device4602. In some examples, the beam perturbation device4602includes a control system. In some examples, a sensor4610is situated to determine beam perturbation or a condition of the beam perturbation device. The sensor4610is coupled to the control system4608to correct errors and drifts in beam perturbations, and/or to verify that the beam perturbation device is operating as intended. For example, VBC apparatus that include an ionic polymer layer can be provided with one or more additional electrodes that are coupled to an amplifier or other circuit to produce a signal indicative of layer deformation. This signal can be used to stabilize ionic polymer deformation. In other VBC apparatus, position, rotation, distance or other sensors can be included so that perturbations produced by a perturbation device can be detected and controlled to maintain a selected perturbation. FIG.47Aillustrates a VBC apparatus4700in which a fiber4702is secured to or guided by supports4704,4706. A fiber deflection member4708(shown for purposes of illustration as having a circular cross-section) is situated to deflect an end portion4703of the fiber4702. The end portion4703can include a splice region4704in which a first fiber and a second fiber are spliced. The fiber deflection member4708is situated to push against the fiber4702to increase fiber deflection and pull the fiber to decrease fiber deflection, but can be situated to push to decrease deflection and pull to increase deflection. In another example shown inFIG.47B, a VBC apparatus4720includes a fiber4722that is in contact with, secured to, or otherwise restrained by a support4724. A fiber deflection member4728is situated to deflect the fiber4722at a location at, near, or in a splice region4730in which a first fiber portion and a second fiber portion are spliced together. The fiber deflection members4708,4728can have various shapes and sizes and can be coupled to piezoelectric devices, linear motors, or other actuators that provide displacement. In another example shown inFIG.47C, a VBC apparatus4750includes a fiber4752that is in contact with, secured to, or otherwise restrained by supports4754,4756. A fiber deflection member4758is situated to deflect the fiber4752at a location at, near, or in a splice region4760in which a first fiber portion and a second fiber portion are spliced together. The VBC apparatus4700,4720,4750do not include a fiber bending surface. Such a surface is convenient is some embodiments as shown above, but is not required. In the examples ofFIGS.47A-47C, fiber deflections are used. The fiber deflection members4708,4728,4758can have various shapes and sizes and can be coupled to piezoelectric devices, linear motors, or other actuators to provide displacements. Having described and illustrated the principles of the disclosed technology with reference to the illustrated embodiments, it will be recognized that the illustrated embodiments can be modified in arrangement and detail without departing from such principles. The particular arrangements above are provided for convenient illustration, and other arrangements can be used. | 91,988 |
11858843 | DETAILED DESCRIPTION The FIGURE shows a glass pane1, which is subjected to annealing in the device shown. The underside of the glass pane1lies on rollers2, which are mounted so as to rotate about axes3. The glass pane1can be transported on these rollers2or also moved back and forth, by driving the rollers2accordingly, which is not shown in detail. The rollers2are provided with a coating which can be a strip consisting of aramid or Kevlar or another appropriate material. The choice of coating is determined by the high temperature of the heated glass coming from the furnace, which is between 600 and 700° C. A flow channel4, which extends over the width of the glass pane and is designed continuous, is situated between two adjacent rollers2. As shown in the FIGURE, the sides8of the flow channel4extend between adjacent rollers2so that the cooling air6emerges from the flow channels4in the direction toward the underside of the glass pane1in the region of the joining plane of the axes3of rollers2or even after them, i.e., closer to the underside of the glass pane1. As shown in the FIGURE, the flow channels4are initially wide and then increasingly narrow in the direction toward the glass pane1so that a tapering flow channel is formed that extends over the entire width of the device, i.e., the length of the rollers2and the width of the glass pane1. The tapering structure of these flow channels4corresponds roughly to an inverted “V”. Since the rollers2are situated between adjacent flow channels4, which, since they carry the glass pane1, extend right up to it, the individual flow channels are shown in the FIGURE by the arrows indicating the air flow. Each flow parcel has a flow channel4that supplies the cooling air6. This is then reflected on the underside of a glass pane1and directed outward in the direction toward the rollers2and then deflected downward so that it flows laterally from the flow channel4. The top of the glass pane1facing away from rollers2is also exposed to cooling air7, which flows from identically or similarly designed flow channels5that are arranged above the glass pane1and also have roughly the cross-sectional shape of a “V” so that they form a continuous flow channel via which cooling air7is blown onto the upper surface of the glass pane1. The upper flow channels5also extend over the entire width of the device, i.e., the length of the rollers2and the width of the glass pane1. The upper flow nozzles5are arranged so that they are roughly flush with the lower opposite flow channels. There are no rollers2above the glass pane1for forming a natural partition between the flow channels5. For this reason, partitions formed by wall elements9are formed between the upper flow channels5, whose distance to the glass panes1is as small as possible during operation of the device and is a maximum of 10 mm. The wall elements9run parallel to the flow channels5. Owing to the arrangement, flow parcels are formed both beneath the glass pane1and above the glass pane1. During operation of the device, cooling air6is guided in the direction of the underside of the glass pane1by the flow channels4arranged beneath the glass pane1. This cooling air6is marked by flow arrows. The cooling air6strikes the underside of the glass pane1approximately orthogonally, is deflected therefrom to both sides and then strikes the top of coated rollers2. Owing to continuous coating of the rollers2, a fully closed flow cell is created here and the cooling air6is then diverted downward and guided out into the open on both outer sides of the flow channel4. Flow occurs similarly on the top of glass pane1. The cooling air7is blown out from the flow channels5downward in the direction of the top of glass pane1, diverted from there leftward and rightward until it reaches the wall elements9extending just above the top of glass pane1. The largest portion of the cooling air7is then diverted upward on these wall elements9and reaches the outside via the outer sides of the flow channel5. By means of the arrangement according to the invention, defined flow parcels are produced both beneath the glass pane1and above the glass pane1, which are formed beneath the glass pane1by two adjacent rollers2and above the glass pane1by two adjacent wall elements9. Due to the continuous, very wide flow channels4and5, it is also possible to guide a considerable amount of air at low speed, i.e., a high volume of air at low pressure, onto both sides of the glass pane1, which in turn enables a laminar flow at high cooling performance. By eliminating any turbulence and by means of this laminar flow, not only is a more uniform cooling of the glass pane1and therefore a lower optical anisotropy guaranteed, but also a higher efficiency of the cooling performance, which requires up to 50% less energy than known systems. A significant improvement in tensile bending strength of the treated glass panes is also obtained by applying the device according to the invention. Due to the more uniformly applied prestressing in the glass, the limit stresses leading to breakage are not reached as early as in the method according to the prior art. | 5,159 |
11858844 | DETAILED DESCRIPTION Embodiments of the present disclosure will be described in detail below. The embodiments described below are exemplary, and are only intended to explain the present disclosure rather than being construed as limitation to the present disclosure. Where specific techniques or conditions are not indicated in the examples, the procedures shall be carried out in accordance with the techniques or conditions described in the literatures in the field or in accordance with the product specification. The reagents or instruments for which no manufacturers are noted are all common products commercially available from the market. One aspect of present disclosure provides a glass composite. According to an embodiment of the present disclosure, referring toFIG.1, the glass composite includes a first glass member1and a second glass member2which are partially connected with each other at the surfaces. The glass composite has a light transmittance no lower than 95% of the light transmittance of the one, with the lower light transmittance, of the first glass member and the second glass member. For example, the glass composite has a light transmittance not lower than 95%, 96%, 97%, 98%, 99%, or 100% of the light transmittance of the one, with the lower light transmittance, of the first glass member and the second glass member. Specifically, if the light transmittance of the first glass member is greater than the light transmittance of the second glass member, then the light transmittance of the glass composite is not less than 95% of the light transmittance of the second glass member. If the light transmittance of the first glass member is lower than the light transmittance of the second glass member, then the light transmittance of the glass composite is not less than 95% of the light transmittance of the first glass member. Therefore, the glass composite has high light transmittance, good optical performance, and almost no bubbles or fantasy colors; and by means of the connection between the first glass member and the second glass member, various complex and fine shapes and structures can be attained, including, for example, but not limited to, a special-shaped structure and a six-sided-ring enveloped structure. It should be noted that the light transmittance of a glass member is often related to the thickness of the glass member. When the difference in thickness is not large and the thickness has no obvious influence on the light transmittance, with reference to “the glass composite has a light transmittance not lower than 95% of the light transmittance of the one, with the lower light transmittance, of the first glass member and the second glass member” as described herein, the influence of thickness on the glass and the glass composite can be ignored. For example, this can be that the light transmittance at the bonding position of the first glass member and the second glass member in the glass composite is not lower than 95% of the light transmittance of the one, with the lower light transmittance, of the first glass member and the second glass member. If the thickness of the first glass member or the second glass member is large and the thickness has an obvious influence on the light transmittance, “the glass composite has a light transmittance not lower than 95% of the light transmittance of the one, with the lower light transmittance, of the first glass member and the second glass member” as described herein may be that the light transmittance at the bonding position of the first glass member and the second glass member in the glass composite is not lower than 95% of the light transmittance of the same glass member having the same or close thickness at the bonding position and with the lower light transmittance, of the first glass member and the second glass member. According to an embodiment of the present disclosure, the material of the first glass member or the second glass member includes, but is not limited to, aluminosilicate (such as Corning glass, etc.), borosilicate (such as Schott glass, etc.), cover glass (including high-alumina high-alkali aluminosilicate glass and soda-lime silica glass, etc.), touch screen substrate glass (such as alkali and heavy metal (arsenic, antimony, and barium)-free alkaline earth sodium pyroborate-aluminosilicate glass, soda glass and neutral borosilicate glass), and TFT display screen substrate glass (including but not limited to Corning Eagle XG, Eagle XG Silm, Willow and other brands of alkali and heavy metal (arsenic, antimony, and barium)-free alkaline earth sodium pyroborate-aluminosilicate glass). Flexible selections can be made by those skilled in the art according to actual needs, as long as the requirements can be met. According to an embodiment of the present disclosure, the specific structure and shape of the glass composite are not particularly limited, and may be a sheet structure, various complex 2.5-dimensional structures, or 3-dimensional structures. According to an embodiment of the present disclosure, the contact surfaces of the first glass member and the second glass member can be a flat surface, a curved surface, or a combination of a flat surface and a curved surface, as long as the two can be brought into contact with each other without clearance. For example, if the activated surface of the first glass member is an upwardly bulged curved surface, then the activated surface of the second glass member is correspondingly an upwardly depressed curved surface. The specific shape and structure can be flexibly selected by those skilled in the art according to actual needs. In this way, the requirements of use in different situations can be met, so as to expand the scope of application of glass members. According to some embodiments of the present disclosure, referring toFIGS.6and7, the first glass member in the glass composite is a sheet glass member10, and the second glass member in the glass composite is a frame-shaped glass member20. The frame-shaped glass member20is connected to the outer peripheral edge of the sheet glass member10. Further, referring toFIG.8, the outer surfaces30at the position where the sheet glass member10and the frame-shaped glass member20are connected are a curved surface. According to other embodiments of the present disclosure, referring toFIG.10, the first glass member in the glass composite is a first sheet glass member11and the second glass member is a second sheet glass member21. The shape of the second sheet glass member21includes rectangle, square, circle (seeFIG.9for the schematic structure), polygons or irregular shapes. Specifically, the surfaces of the first sheet glass member11and the second sheet glass member21may be partially in contact, or part of the surface of the first sheet glass member11is in contact with a whole surface of the second sheet glass member21(seeFIGS.10and11for the schematic structure). Of course, it is to be understood by those skilled in the art that in addition to the cases shown inFIGS.8,10and11, other shapes and modes of connection are also contemplated in the scope of protection of the present disclosure. According to an embodiment of the present disclosure, referring toFIGS.10and11, the surface with a larger area of the first sheet glass member11is connected to the surface with a larger area of the second sheet glass member21. According to some embodiments of the present disclosure, referring toFIGS.12-15, the first glass member in the glass composite is a first frame-shaped glass member12and the second glass member is a second frame-shaped glass member21. Specifically, the shapes of the first frame-shaped glass member and the second frame-shaped glass member are not particularly limited. Referring toFIG.12, they can be a circle, a box, a curved frame, or a frame having straight and curved lines in combination. The position of connection of the first frame-shaped glass member and the second frame-shaped glass member is also not particularly limited. They can be laminated and connected vertically (seeFIGS.13and14for the schematic structure), or connected horizontally side by side (seeFIG.15for the schematic structure), and have an aligned arrangement (seeFIG.13and the upper panel ofFIG.15for the schematic structure), or staggered arrangement (see the lower panels ofFIGS.14and15for the schematic structure). Of course, those skilled in the art can understand that the shape and structure of the glass composite described above are only illustrative and should not be construed as limiting the present disclosure. The specific shape and structure of the glass composite can be flexibly selected according to the requirements in practical application. According to an embodiment of the present disclosure, at least one of the first glass member and the second glass member is formed by a plurality of sub-glass members, and at least part of the surfaces of two adjacent sub-glass members are connected. Therefore, a glass composite formed by connecting three, four or more glass members can be achieved, which makes it easier to form complex and fine structures and shapes, thus expanding the scope of application of glass. According to an embodiment of the present disclosure, the material forming the sub-glass member may be the same as the material forming the first glass member or the second glass member described above, and the two adjacent sub-glass members are connected in the same mode as does between the first glass member and the second glass member. That is, the light transmittance of the first glass member or the second glass member formed by a plurality of the sub-glass members is not lower than 95% of the light transmittance of the sub-glass member. As a result, a complex and fine special-shaped structure is achieved. The light transmittance of the glass composite is substantially not affected, and the optical performance is better. It is applicable to an electronic device, and even an all-glass appearance of an electronic device can be realized therewith. According to an embodiment of the present disclosure, the number of sub-glass members is not particularly limited, and can be flexibly selected by those skilled in the art according to actual needs as long as the requirements can be met, According to an embodiment of the present disclosure, under the same conditions, the rate of corrosion by hydrofluoric acid at the interface where the first glass member and the second glass member are connected is greater than the rate of corrosion of the first glass member and the second glass member by hydrofluoric acid. Thus, the existence of the bonding interface can be effectively detected. In some embodiments of the present disclosure, referring toFIG.1,FIG.2andFIG.3, the first glass member and the second glass member are connected to form a contact interface, a cross section along the direction perpendicular to the contact interface is defined as the first cross section (seeFIG.2for the schematic structure). After the first cross section is brought into contact with hydrofluoric acid, a crevice3appears in the contact interface (seeFIG.3for the schematic structure, where the crevice shape shown inFIG.3is merely illustrative, and should not be construed as limiting the present disclosure; and it can be understood by those skilled in the art that the specific crevice shape can be various geometric shapes or irregular random shapes depending on the etching process with hydrofluoric acid). Specifically, the first cross section is obtained after cutting the glass composite (for ease of observation, the first cross section obtained after cutting is polished to remove the burrs, to achieve a better observation effect) and there is no crevice when observed visually by naked eyes or under a microscope at a magnification of 500×. After the first cross section is corroded in a hydrofluoric acid solution having a mass concentration of 5%-40% for 30 s-1200 s (for example, 30 s, 1 min, 5 min, 10 min, 15 min, and 20 min), the compounding interface of the first glass member and the second glass member is corroded to form a crevice having a width W of 0.1-300 μm, for example, 0.1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 165 μm, 170 μm, 175 μm, 180 μm, 185 μm, 190 μm, 195 μm, 200 μm, 205 μm, 210 μm, 215 μm, 220 μm, 225 μm, 230 μm, 235 μm, 240 μm, 245 μm, 250 μm, 255 μm, 260 μm, 265 μm, 270 μm, 275 μm, 280 μm, 285 μm, 290 μm, 295 μm, and 300 μm. In some specific embodiments of the present disclosure, after the first cross section described herein is brought into contact with hydrofluoric acid having a mass concentration of 5%, 10%, 20% and 40% for 300 s respectively, the width of the crevice is respectively 0.1-30 μm (for example, 0.1 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm), 0.5-50 μm (for example, 0.5 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, and 50 μm), 0.5-100 μm (for example, 0.5 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, and 100 μm), and 2-100 μm (for example, 2 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, and 100 μm). After the first cross section is brought into contact with hydrofluoric acid having a mass concentration of 5%, 10%, 20%, and 40% for 600 s respectively, the width of the crevice is respectively 1-50 μm (for example, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, and 50 μm), 1-80 μm (for example, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, and 85 μm), 3-120 μm (for example, 3 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 105 μm, 110 μm, 115 μm, and 120 μm) and 5-120 μm (for example, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 105 μm, 110 μm, 115 μm, and 120 μm). It should be noted that in the embodiments of present disclosure, the width of the crevice given depends on the specific glass material, experimental conditions and test conditions used by the inventor, and the width varies with different glass materials, experimental conditions or test conditions. According to an embodiment of the present disclosure, in order to further improve the light transmittance of the glass composite to meet the requirements of use in the display field (such as the display screen), at least one surface of the first glass member or the second glass member can be provided with an anti-reflection (AR) film, to further improve the light transmittance of the glass composite and enable the glass composite to achieve a light transmittance comparable to or higher than that of the first glass member or the second glass member. According to an embodiment of the present disclosure, the glass composite can be used in a protective cover plate or casing for an electronic product, as well as in a casing of a wearable device or in automotive glass. According to an embodiment of the present disclosure, referring toFIG.4, the glass composite can be prepared through a process comprising the following steps: S100: Activate at least a part of the surface of the first glass member and at least a part of the surface of the second glass member, respectively, to form an activated surface. According to an embodiment of the present disclosure, referring toFIG.5, the method further includes before the activation treatment: S110: Clean the surface to be activated of the first glass member and the surface to be activated of the second glass member. In some embodiments of the present disclosure, the cleaning may include: washing the glass member with an acid detergent (such as hydrofluoric acid, sulfuric acid or peroxyacetic acid), an alkaline detergent (such as sodium carbonate or calcium hypochlorite), an organic reagent (such as acetone, or trichloroethylene) or plasma; and drying in some embodiments of the present disclosure. In some embodiments of the present disclosure, the glass member can be washed with trichloroethylene. This is beneficial to remove the oil stain on the surfaces of the glass members, to facilitate the progression of subsequent steps. According to an embodiment of the present disclosure, the activation can suitably produce unsaturated chemical bonds on the surface of the first glass member and the surface of the second glass member. Therefore, after the activation, unsaturated chemical bonds with higher energy are generated on the surface of the first glass member or the second glass member, so when the two are infinitely close to each other, the unsaturated chemical bonds on the surfaces of the glass members are bonded to each other to form a stable saturated chemical bond. The inner unity of the glass composite obtained is high, and the bonding force between the first glass member and the second glass member is strong, whereby the final glass composite has an almost unaffected light transmittance and good performance. It should be noted that the phrase “unsaturated chemical bond” used herein refers to a chemical bond that contains an unpaired electron or lone pair of electrons, and generally has a high energy and cannot exist stably. For example, it can be a metal atom linked with an oxygen atom having a lone pair of electrons contained in the glass member, where the metal atom can specifically be any metal atom contained in the glass, including, for example, but not limited to aluminum-oxygen unsaturated bond, sodium-oxygen unsaturated bond, potassium-oxygen unsaturated bond, and calcium-oxygen unsaturated bond. It can also be a non-metallic atom linked with an oxygen atom having a lone pair of electrons in the glass member. The non-metallic atom can specifically be any non-metallic atom in the glass member, including, for example, but not limited to, silicon-oxygen unsaturated bond, and boron-oxygen unsaturated bond. It can also be a metal atom or non-metal atom having an unpaired electron or empty orbital (easy to bond with a lone pair of electrons), for example, aluminum, sodium, potassium, or calcium that contains an unpaired electron or has an empty orbital; or it can also be a silicon dangling bond, or an oxygen dangling bond. “Saturated chemical bond” refers to a chemical bond that does not contain an unpaired electron, generally has a low energy, and can exist stably. Specifically, it can be a chemical bond formed after the above-mentioned unsaturated bond is bonded, including, but not limited to, silicon-oxygen-silicon bond and the like. According to an embodiment of the present disclosure, the activation is carried out by at least one of: a. treatment with an activation solution that is acidic or basic; b. plasma treatment; and c. UV treatment. For example, it is possible to adopt treatment with an activation solution, plasma treatment or UV treatment alone, treatment with an activation solution and plasma treatment in combination, plasma treatment and UV treatment in combination, treatment with an activation solution and UV treatment in combination, or treatment with an activation solution, plasma treatment and UV treatment in combination. Therefore, the operation is simple, convenient, and easy to implement, an activated surface can be efficiently formed on the surfaces of the first glass member and the second glass member, the activation effect is better, and the bonding force between the first glass member and the second glass member can be significantly improved. According to an embodiment of the present disclosure, wherein the treatment with an activation solution comprising the specific method of activation includes, but is not limited to, dropping the activation solution onto the surfaces to be activated of the first glass member and the second glass member, or immersing the first glass member and the second glass member in the activation solution. The plasma treatment includes: the first glass member and the second glass member are positioned in a plasma treatment device, and then the surfaces of the first glass member and the second glass member are activated by plasma generated by an inert gas (for example, one of nitrogen, argon, and helium, or a mixture thereof), a hydrogen-containing gas or an oxygen-containing gas under the action of electrical discharge, high-frequency electromagnetic oscillation, shock wave, and high-energy radiation. The UV treatment includes: the first glass member and second glass member can be directly irradiated with ultraviolet light, or the first glass member and the second glass member can be irradiated with ultraviolet light in the presence of ozone, whereby ozone can provide highly active atomic oxygen to form a volatile substance with free radicals generated after the dissociation of the dirt and thus enable an activated surface. According to an embodiment of the present disclosure, the activation solution contains: an acid (including, for example, but not limited to, at least one of sulfuric acid, hydrochloric acid, hydrogen fluoride, ammonium bifluoride, nitric acid, and acetic acid) or a alkali (including, for example, but not limited to, at least one of sodium carbonate, sodium bicarbonate, potassium hydroxide, sodium hydroxide and aqueous ammonia); and an auxiliary agent, including at least one of an oxidizing agent (for example, at least one of potassium dichromate, hydrofluoric acid, hydrochloric acid and hydrogen peroxide), an alcohol (including, for example, but not limited to, ethanol and methanol), an organic acid (including, for example, but not limited to, acetic acid), a carbohydrate (including, for example, but not limited to, glucose), an amino acid, and a surfactant (including, for example, but not limited to, sodium dodecyl sulfonate). Therefore, the activation solution can create a better acidic or basic environment, with which unsaturated chemical bonds with higher energy can be formed on the surfaces of the glass members, which is beneficial to the subsequent steps. According to an embodiment of the present disclosure, the activation solution is acidic or basic. Therefore, the activation operation is simple and convenient, and can be accomplished easily, and the activation effect is better. According to an embodiment of the present disclosure, when the activation solution is acidic, the activation solution further includes an oxidizing agent (such as potassium dichromate, potassium permanganate, nitric acid, and hydrogen peroxide, etc.), to improve the activation ability of the activation solution, so as to form unsaturated chemical bonds on the surface of the glass member easily. According to an embodiment of the present disclosure, the pH of the activation solution is not greater than 4 (such as 1, 2.5, 3, 3.5, and 4, etc.), or the pH of the activation solution is 10-14 (such as 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, and 14 etc.). When the pH of the activation solution is within the above range, more unsaturated chemical bonds can be formed, which is beneficial to the compounding between the first glass member and the second glass member. If the activation solution is excessively highly acidic or basic, the surface roughness of the glass member is affected, making the light transmittance of the glass composite relatively low; and if the activation solution is excessively lowly acidic or basic, the activation effect on the surface of the glass member is poor, and few unsaturated chemical bonds are obtained. In some embodiments of the present disclosure, the raw materials for forming the activation solution include hydrogen peroxide and sulfuric acid. In this manner, the activation effect of the activation solution is better, and more unsaturated chemical bonds are obtained, which is more conducive to the compounding between the first glass member and the second glass member; and the glass composite thus obtained has almost no bubbles or fantasy colors. In some specific embodiments of the present disclosure, the activation solution is a mixture of hydrogen peroxide and sulfuric acid in a volume ratio of (1:3) to (3:7) (such as 1:3, 1:2.8, 1:2.6, 1:2.5, and 1:2.3). As such, the activation solution is relatively highly acidic or oxidative, which promotes the activation of the surface of the glass member to generate more unsaturated chemical bonds, so a better activation effect is achieved. Compared with other ranges of mixing ratio, when the volume ratio of hydrogen peroxide and sulfuric acid is within the above range, the activation effect is better, the light transmittance of the obtained glass composite is higher, and the fantasy color is less. In some other embodiments of the present disclosure, the raw materials for forming the activation solution include potassium dichromate and sulfuric acid, including, for example, but not limited to, a mixture of potassium dichromate and sulfuric acid in a weight ratio of (1-3):4 (such as 1:4, 1.5:4, 2:4, 2.5:4, and 3:4). In some embodiments of the present disclosure, the raw materials for forming the activation solution include hydrofluoric acid and ammonium bifluoride, for example, a mixed solution of hydrofluoric acid and ammonium bifluoride having a mass concentration of 5%-40% (such as 5%, 10%, 15%, 20, 25%, 30%, 35%, and 40%). As a result, the surface activation of the glass member is promoted to generate more unsaturated chemical bonds, and the activation effect is better. In some embodiments of the present disclosure, the raw materials for forming the activation solution include aqueous ammonia and hydrogen peroxide. In some specific embodiments of the present disclosure, the activation solution is a mixed solution of aqueous ammonia and hydrogen peroxide in a volume ratio of (1:1)-(1:5) (for example, 1:1, 1:2, 1:3, 1:4, and 1:5). As such, the activation solution is relatively highly oxidative, which promotes the activation of the surface of the glass member to generate more unsaturated chemical bonds, so a better activation effect is achieved. According to an embodiment of the present disclosure, the raw materials for forming the basic activation solution include sodium hypochlorite and aqueous ammonia. In some embodiments of the present disclosure, the basic activation solution includes a mixture of 5-20 wt % of sodium hypochlorite, 5-30 wt % of aqueous ammonia, and 50-90 wt % of deionized water, in which the content of sodium hypochlorite can be 5 wt %, 10 wt %, 15 wt % or 20 wt %, the content of aqueous ammonia can be 5 wt %, 10 wt %, 15 wt %, 20 wt %, 25 wt % or 30 wt %, and the content of deionized water can be 50 wt %, 55 wt %, 60 wt %, 65 wt %, 70 wt %, 75 wt %, 80 wt % or 90 wt %. As a result, the activation solution allows more unsaturated chemical bonds to be exposed on the surface of the glass member, and the activation effect is better. According to an embodiment of the present disclosure, the UV treatment includes UV irradiation of the surfaces of the first glass member and the second glass member for 0.5-15 h (for example, 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h, 1.0 h, 1.1 h, 1.2 h, 1.3 h, 1.4 h, 1.5 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h, and 15 h); or UV irradiation, in the presence of ozone, of the surfaces of the first glass member and the second glass member for 5-20 min (for example, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min, 19 min, and 20 min). In this manner, more unsaturated chemical bonds are generated and exposed on the surface of the glass member, and the activation effect is better. According to an embodiment of the present disclosure, the plasma treatment includes treating the surfaces of the first glass member and the second glass member for 10-30 min (such as 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min, 19 min, 20 min, 21 min, 22 min, 23 min, 4 min, 25 min, 26 min, 27 min, 28 min, 29 min or 30 min) by at least one of O2plasma and N2/H2plasma at an excitation frequency of 10 MHz-15 MHz (such as 10.25 MHz, 10.5 MHz, 11 MHz, 11.25 MHz, 11.5 MHz, 11.75 MHz, 12 MHz, 13 MHz, 13.8 MHz, 14 MHz, 14.5 MHz, and 15 MHz). As a result, more unsaturated chemical bonds are generated and exposed on the surface of the glass member, and the activation effect is better. It should be noted that the phrase “N2/H2plasma” used herein refers to a mixed plasma of N2and H2. Specifically, the activation can be performed by O2plasma alone, N2/H2plasma alone, or O2plasma and N2/H2plasma in combination. According to an embodiment of the present disclosure, the activation is carried out at room temperature to 200° C. For example, the activation can take place at 25° C., 40° C., 50° C., 60° C., 70° C., 80° C., 90° C., 100° C., 110° C., 130° C., 150° C., 170° C., 190° C., or 200° C. In this way, the activation in the above temperature range is more conducive to the formation of more unsaturated chemical bonds, and the activation effect is better. Compared with the above temperature range, if the activation temperature is too high, the activation solution is easier to volatilize, so the service life is short, and the activation effect is poor; and if the activation temperature is too low, the activation effect of the glass is poor. According to an embodiment of the present disclosure, since the unsaturated chemical bonds formed after the activation are extremely active and prone to reaction with oxygen in the air, and thus have a short residence time, the first glass member and the second glass member are positioned in a vacuum environment in a period of time from the completion of the activation to the completion of the contact. As a result, the unsaturated chemical bonds formed after the activation will not contact and react with oxygen in the air, thus extending the residence time of the unsaturated chemical bonds. This is beneficial to the subsequent steps, and improves the bonding strength between the first glass member and the second glass member. In some embodiments of the present disclosure, the activation can be directly performed in a vacuum environment, or the first glass member and the second glass member can also be positioned in a vacuum environment after the activation, until the contact is completed. Therefore, the activity of unsaturated chemical bonds are maintained as much as possible, thereby significantly improving the bonding strength between the first glass member and the second glass member. According to an embodiment of the present disclosure, the activated surface obtained after the activation has a smaller water contact angle, for example, not more than 10 degrees, such as 1 degree, 2 degrees, 3 degrees, 4 degrees, 5 degrees, 6 degrees, 7 degrees, 8 degrees, 9 degrees, or 10 degrees, etc. This shows that the activated surface is formed with more unsaturated chemical bonds having higher energy, which facilitates the improvement of the bonding between the first glass member and the second glass member. According to an embodiment of the present disclosure, the surface roughness (RA) of the first glass member and the second glass member is not greater than 0.2 μm, such as 0.2 μm, 0.18 μm, 0.16 μm, 0.15 μm, 0.12 μm, 0.1 μm, 0.08 μm, 0.05 μm and so on. This further contributes to the improvement of the bonding strength between the first glass member and the second glass member, thus improving the strength of the obtained glass composite. In some other embodiments of the present disclosure, the surface roughness of the first glass member and the second glass member is not greater than 0.2 μm, and the activated surface after the activation has a contact angle with water drops of not greater than 10 degrees. This further contributes to the improvement of the bonding strength between the first glass member and the second glass member, thus improving the strength of the obtained glass composite. S200: Contact the activated surface of the first glass member with the activated surface of the second glass member to form a glass composite. According to an embodiment of the present disclosure, the contact causes the unsaturated chemical bonds on the activated surface of the first glass member to bond to the unsaturated chemical bonds on the activated surface of the second glass member to form a stable saturated chemical bond. In this way, a new saturated chemical bond is formed at the contact position, which not only improves the compounding strength of the first glass member and the second glass member, but also improves the inner unity of the glass composite, thereby improving the optical performance of the glass composite. According to an embodiment of the present disclosure, when the aforementioned contact is made, the unsaturated chemical bonds are bonded on the compounding interface to form a new saturated chemical bond. It should be noted that the compounding interface refers to a contact interface formed by contacting the activated surface of the first glass member with the activated surface of the second glass member. According to an embodiment of the present disclosure, the above-mentioned contact can be made with heating, and the first glass member and the second glass member need to be heated. In some embodiments of the present disclosure, the heated area can be the same as the area of the first glass member, or the same as the area of the second glass member. In some specific embodiments of the present disclosure, heating takes place at the position where the second glass member and the first glass member are overlapped. As such, the first glass member and the second glass member can be effectively heated and fixed together; and the heat utilization rate is high, the energy consumption is reduced, and the influence of heating on other parts of the glass member is minimized. According to an embodiment of the present disclosure, the contact takes place at a first predetermined temperature, where the first predetermined temperature does not exceed the softening points of the first glass member and the second glass member. There is almost no surface scald, distortion and unevenness caused by an excessively high temperature, so that the final glass composite has an almost unaffected light transmittance, and an aesthetic appearance. It should be noted that the softening point of glass member refers to the temperature at which the glass member starts to soften, and the expression “the first predetermined temperature does not exceed the softening points of the first glass member and the second glass member” used herein means that the first predetermined temperature does not exceed the lower one of the softening point of the first glass member and the softening point of the second glass member. In some embodiments of the present disclosure, the first predetermined temperature is between 200-900° C., such as 200° C., 250° C., 300° C., 350° C., 400° C., 450° C., 500° C., 550° C., 600° C., 650° C., 700° C., 750° C., 800° C., 850° C., and 900° C., etc. Therefore, the first predetermined temperature does not exceed the softening point of the glass members. Due to the low temperature, there is no scald on the outer surface of the glass, no softening of glass occurs, and no deformation or unevenness occurs on the glass surface, whereby the light transmittance of the final glass composite is enhanced, and the glass composite has an aesthetic appearance. If the first predetermined temperature is too high, the glass member is easy to be softened, and scald, deformation, and unevenness may occur to the outer surface. A too high temperature is not conducive to the formation of new saturated chemical bonds between the two glass members, affecting the optical performance of the glass composite. If the first predetermined temperature is too low, the bonding strength between the glass members is low, such that the strength of the formed glass composite is low. In some specific embodiments of the present disclosure, the first predetermined temperature is between 250-750° C., such as 200° C., 250° C., 300° C., 350° C., 400° C., 450° C., 500° C., 550° C., 600° C., 650° C., 700° C., and 750° C., etc. This is more conducive to the compounding between the first glass member and the second glass member, and there is almost no surface distortion and unevenness caused by an excessively high temperature. Therefore, the finally obtained glass composite has a higher light transmittance and an aesthetic appearance. According to an embodiment of the present disclosure, the contact is carried out under pressure. It is more advantageous to weld the first glass member and the second glass member together under pressure to form a stronger glass composite, and there are almost no bubbles or fantasy colors in the glass composite. In some embodiments of the present disclosure, the pressure is 0.05-10 MPa, for example, 0.1 MPa, 0.5 MPa, 1.0 MPa, 1.5 MPa, 2.0 MPa, 3.0 MPa, 5.0 MPa, 7.0 MPa, and 9.0 MPa, etc. Therefore, the first glass member and the second glass member are more effectively bonded, and the strength of the glass composite is higher. If the pressure is too large, the glass surface is prone to indentation, and the glass structure is easily deformed. If the pressure is too small, the bonding force between the glass members is relatively low, and bubbles and fantasy colors are likely to appear in the glass composite. In some specific embodiments of the present disclosure, the glass composite can be prepared through a process comprising the following steps:Step 1: cleaning a first glass member and a second glass member with a detergent to remove oil stain, and blow drying;Step 2: activating the cleaned first glass member and second glass member in an activation solution, heating from room temperature to 200° C. for a period of time, cooling naturally, washing off the residual solution on the surface with pure water, and blow drying, to obtain the first glass member and the second glass member having activated surfaces, where the activation mainly aims to increase the unsaturated chemical bonds on the surface of the glass members that are bonded to form a new stable saturated chemical bond when compounded, to promote the subsequent compounding process; andStep 3: contacting the activated surface of the first glass member with the activated surface of the second glass member, heating to a temperature below the glass softening point, and applying a pressure at the same time to compound at least part of the surfaces of the first glass member and the second glass member to form a glass composite. The present inventors find that the method is simple, convenient, and easy to implement. After the activation, a new saturated chemical bond is formed between the first glass member and the second glass member. The bonding force is stronger, and the formed glass composite has high strength and high inner unity. Moreover, the glass composite has a relatively flat surface, an aesthetic appearance, and an almost unaffected optical performance, the light transmittance is high, and there is almost no fantasy colors and bubbles. In another aspect of present disclosure, present disclosure provides a casing. According to an embodiment of the present disclosure, at least a part of the casing is formed by the glass composite described above. Therefore, the casing has high light transmittance, good optical performance, and almost no bubbles or fantasy colors, can attain a special-shaped structure, meet the requirements of use in different situations, and have a wide scope of application. Moreover, the preparation method of the casing is simple and easy to operate, thereby overcoming the problem that glass is unlikely to be processed into complex shapes due to its brittleness. The casing can be effectively used in various electronic products (such as mobile phones, and tablet computers, etc.), so as to solve the problem of signal shielding by a metal casing. The casing can be well applied to 5G communication devices, and can give the electronic products more aesthetic and diverse appearances. According to an embodiment of the present disclosure, the casing is formed by the glass composite described above. Specifically, there are no restrictions on the specific shape, connection mode, and connection position of the first glass member and the second glass member, and flexible selections can be made by those skilled in the art according to the requirements during use. According to an embodiment of the present disclosure, there are no particular restrictions on the specific shape, and structure of the casing, and flexible selections can be made by those skilled in the art according to the requirements of actual products. In some embodiments of the present disclosure, the first glass member and the second glass member may specifically be of a 2D structure, a 2.5D structure or a 3D structure. The contact surfaces of the first glass member and the second glass member can be a flat surface, a curved surface, or a combination of a flat surface and a curved surface, as long as the two can be brought into contact with each other without clearance. For example, if the activated surface of the first glass member is an upwardly bulged curved surface, then the activated surface of the second glass member is correspondingly an upwardly depressed curved surface. The specific shape and structure can be flexibly selected by those skilled in the art according to actual needs. Specifically, the first glass member and the second glass member can be each independently a sheet glass member, a frame-shaped glass member (that is, a closed ring-shaped glass member, for example, circular ring-shaped glass, rectangular ring-shaped glass, or ring-shaped glass with an outer peripheral edge having straight and curved lines in combination), or a bar-like glass member (such as long bar, round bar, or irregular polygonal bar). In some specific embodiments, referring toFIGS.6A(rectangular ring-shaped glass) and6B (circular ring-shaped glass), the first glass member is a sheet glass member, and the second glass member is a frame-shaped glass member, where the frame-shaped glass member is compounded to the outer peripheral edge of the sheet glass member (seeFIG.7A) or the frame-shaped glass member is compounded to the outer peripheral face of the sheet glass member (seeFIG.7B). In some other specific embodiments, referring toFIG.6C, the first glass member is a sheet glass member, and the second glass member is a bar-shaped glass member, where the bar-shaped glass member is compounded to the outer peripheral edge of the sheet glass member (where specifically, the bar-shaped glass member can be compounded to the outer peripheral edge at one, two or more sides; and seeFIG.7Afor the schematic structure of the cross section where the bar-shaped glass member is compounded to two opposing outer peripheral edges), or a frame-shaped glass member is compounded to the outer peripheral face of the sheet glass member (where specifically, the frame-shaped glass member can be compounded to the outer peripheral face at one, two or more sides; and seeFIG.7Bfor the schematic structure of the cross section where the frame-shaped glass member is compounded to two opposing outer peripheral faces). Of course, the foregoing is only an exemplary description of the casing structure of the present disclosure, and cannot be understood as a limitation of the present disclosure. Accordingly, a glass casing having a stereoscopic structure can be achieved, and various complex 2.5D (two-dimensional), 3D (three-dimensional), and special-shaped structures can be obtained as needed. Moreover, the preparation method of the casing is simple and easy to operate, thereby overcoming the problem that glass is unlikely to be processed into complex shapes due to its brittleness. The casing can be effectively used in various electronic products (such as mobile phones, and tablet computers, etc.), so as to solve the problem of signal shielding by a metal casing. The casing can give the electronic products more aesthetic and diverse appearances. According to an embodiment of the present disclosure, the inner surface and/or the outer surface of the position where the first glass member and the second glass member are connected is a flat surface, a curved surface, or a combination of a flat surface and a curved surface. Specifically, after the first glass member and the second glass member are compounded, the corresponding position on the outer surface of the composite can be processed to obtain any shape that meets the requirements of use. According to an embodiment of the present disclosure, the outer surface of the position where the first glass member and the second frame-shaped glass member are connected is a flat surface, a curved surface, or a combination of a flat surface and a curved surface. Specifically, after the first glass member and the second glass member are compounded, the corresponding position on the outer surface of the composite can be processed to obtain any shape that meets the requirements of use. According to some embodiments of the present disclosure, referring toFIG.8, the outer surface30of the position where the first glass member10and the second glass member20are connected is a curved surface. Thus, a 3D curved glass casing is obtained. According to an embodiment of the present disclosure, referring toFIG.9, the frame-shaped glass member20and the sheet glass member10in the casing can form a structure where the position where the sheet glass member and the frame-shaped glass member are connected has an inner right-angled structure (a inFIG.9); the position where the sheet glass member and the frame-shaped glass member are connected has an internal step structure (b inFIG.9); the outer surface of the position where the sheet glass member and the frame-shaped glass member are connected is a curved surface (c inFIG.9); the frame-shaped glass member has an inner surface that is an outwardly bulged curved surface (f inFIG.9); the frame-shaped glass member has an inner surface that is an inclined surface that gradually tilts inwards (d inFIG.9); the frame-shaped glass member has an inner surface that is an inclined surface that gradually tilts outwards (e inFIG.9); and the frame-shaped glass member has an inner surface that is an inwardly bulged curved surface (g inFIG.9). According to an embodiment of the present disclosure, there are no particular restrictions on the specific size of the casing, and flexible selections can be made by those skilled in the art according to the requirements. In another aspect of present disclosure, present disclosure provides a display device. According to an embodiment of the present disclosure, the display device includes the glass composite described above. Therefore, the display device has aesthetic appearance, high light transmittance, and good display effect. It is to be understood that the glass composite can be a protective cover plate or a back casing of a display device, or can be a base in a color filter substrate or an array substrate, which can be selected according to actual conditions. According to an embodiment of the present disclosure, the type of the display device is not particularly limited, and includes, for example, but is not limited to, a liquid crystal display device or an OLED display device. The display device may include, in addition to the glass composite, a structure that a conventional display device need to have, such as an array substrate, a color filter substrate, and an electrode, which will not be described here. In another aspect of present disclosure, present disclosure provides a terminal device. According to an embodiment of the present disclosure, the terminal device includes the display device described above. The present inventors find that the terminal device is aesthetically pleasant, has high strength, can achieve an all-glass appearance, and has good performance. According to an embodiment of the present disclosure, the terminal device includes at least one of a mobile phone, a tablet computer, a notebook computer, a virtual reality (VR) device, an augmented reality (AR) device, a wearable device, and a game console. Therefore, the scope of application is wide and can satisfy the consumers' consumption experience. It should be noted that in addition to the display device, the terminal device may also include a structure that a conventional terminal device needs to have, such as a CPU, a connecting circuit, and a packaging structure, which are not described here. According to an embodiment of the present disclosure, in a general method for preparing the glass composites, the glass members are usually heated to above the softening point and then pressed by a jig to press the glass members together. The glass composite obtained by this method has indentations at the welds, which seriously reduce the optical performance of the glass composite and makes the light transmittance poor. In present disclosure, the first glass member or the second glass member is activated in the activation solution so that the unsaturated chemical bonds are exposed on the surface of the glass member. Then the first glass member and the second glass member are pressed together at a low temperature (lower than the softening point of the glass member), to obtain a glass composite with high bonding strength, almost no indentations on the surface, and good optical performance. Specifically, for example, the obtained glass composite having a thickness of 0.7-0.8 mm has a light transmittance in the visible light band of up to 90% or more. The examples of the present disclosure are described in detail below. EXAMPLES Activation Examples Activation Example 1 60 g of K2Cr2O7was dissolved in 270 g of water, and 44 ml of concentrated sulfuric acid was slowly added. A first glass member and a second glass member were soaked in the prepared mixed acid solution (for 2 h at room temperature or for 30 min at 50° C.). The glass members were removed, and the residual chromium ions on the surfaces were washed off with a 10% nitric acid solution. Then the glass members were washed with pure water for 10 min and then blow dried. In this way, the surfaces of the glass members were activated. The surface roughness of the glass members before activation was 0.612 nm. Activation Example 2 20 g of K2Cr2O7was dissolved in 270 g of water, and 44 ml of concentrated sulfuric acid was slowly added. A first glass member and a second glass member were soaked in the prepared mixed acid solution (for 6 h at room temperature or for 150 min at 50° C.). The glass members were removed, and the residual chromium ions on the surfaces were washed off with a 10% nitric acid solution. Then the glass members were washed with pure water for 10 min and then blow dried. In this way, the surfaces of the glass members were activated. The surface roughness of the glass members before activation was 0.592 nm. Activation Example 3 30 g of K2Cr2O7was dissolved in 270 g of water, and 44 ml of concentrated sulfuric acid was slowly added. A first glass member and a second glass member were soaked in the prepared mixed acid solution (for 5 h at room temperature or for 120 min at 50° C.). The glass members were removed, and the residual chromium ions on the surfaces were washed off with a 10% nitric acid solution. Then the glass members were washed with pure water for 10 min and then blow dried. In this way, the surfaces of the glass members were activated. The surface roughness of the glass members before activation was 0.589 nm. Activation Example 4 40 g of K2Cr2O7was dissolved in 270 g of water, and 44 ml of concentrated sulfuric acid was slowly added. A first glass member and a second glass member were soaked in the prepared mixed acid solution (for 4 h at room temperature or for 90 min at 50° C.). The glass members were removed, and the residual chromium ions on the surfaces were washed off with a 10% nitric acid solution. Then the glass members were washed with pure water for 10 min and then blow dried. In this way, the surfaces of the glass members were activated. The surface roughness of the glass members before activation was 0.659 nm. Activation Example 5 50 g of K2Cr2O7was dissolved in 270 g of water, and 44 ml of concentrated sulfuric acid was slowly added. A first glass member and a second glass member were soaked in the prepared mixed acid solution (for 3 h at room temperature or for 60 min at 50° C.). The glass members were removed, and the residual chromium ions on the surfaces were washed off with a 10% nitric acid solution. Then the glass members were washed with pure water for 10 min and then blow dried. In this way, the surfaces of the glass members were activated. The surface roughness of the glass members before activation was 0.192 nm. Activation Example 6 A first glass member and a second glass member were soaked in a mixed solution containing 10% hydrofluoric acid and 10% ammonium bifluoride at room temperature for 30 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. The surface roughness of the glass members before activation was 0.751 nm. Activation Example 7 A first glass member and a second glass member were soaked in a mixed solution containing 10% hydrofluoric acid and 10% ammonium bifluoride at room temperature for 35 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. The surface roughness of the glass members before activation was 0.526 nm. Activation Example 8 A first glass member and a second glass member were soaked in a mixed solution containing 5% hydrofluoric acid and 5% ammonium bifluoride at room temperature for 40 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. The surface roughness of the glass members before activation was 0.450 nm. Activation Example 9 A first glass member and a second glass member were soaked in a mixed solution containing 15% hydrofluoric acid and 15% ammonium bifluoride at room temperature for 30 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. The surface roughness of the glass members before activation was 0.654 nm. Example 10 The glass members were soaked in a mixed solution containing 20% hydrofluoric acid and 20% ammonium bifluoride at room temperature for 25 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. The surface roughness of the glass members before activation was 0.539 nm. Example 11 The glass members were soaked in a mixed solution containing 25% hydrofluoric acid and 25% ammonium bifluoride at room temperature for 20 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. The surface roughness of the glass members before activation was 0.238 nm. Example 12 The glass members were soaked in a mixed solution containing 30% hydrofluoric acid and 30% ammonium bifluoride at room temperature for 15 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. The surface roughness of the glass members before activation was 0.886 nm. Example 13 The glass members were soaked in a mixed solution containing 35% hydrofluoric acid and 35% ammonium bifluoride at room temperature for 10 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. The surface roughness of the glass members before activation was 0.556 nm. Example 14 The glass members were soaked in a mixed solution containing 40% hydrofluoric acid and 40% ammonium bifluoride at room temperature for 5 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. The surface roughness of the glass members before activation was 0.842 nm. Activation Example 15 A first glass member and a second glass member were washed with a mixed solution of hydrofluoric acid, sulfuric acid, and the surfactant sodium dodecyl sulfonate, blow dried, then positioned in a mixed solution of hydrogen peroxide and sulfuric acid (1:3), heated at 80° C. for 1 h, and cooled naturally. The residual solution on the surfaces was washed off with pure water and then the glass members were blow dried. In this way, the surfaces of the glass members were activated. The surface roughness of the glass members before activation was 0.610 nm. Activation Example 16 A first glass member and a second glass member were washed with a mixed solution of hydrofluoric acid, sulfuric acid, and the surfactant sodium dodecyl sulfonate, blow dried, then positioned in a mixed solution of hydrogen peroxide and sulfuric acid (1:2.8), heated at 80° C. for 1 h, and cooled naturally. The residual solution on the surfaces was washed off with pure water and then the glass members were blow dried. In this way, the surfaces of the glass members were activated. The surface roughness of the glass members before activation was 0.741 nm. Activation Example 17 A first glass member and a second glass member were washed with a mixed solution of hydrofluoric acid, sulfuric acid, and the surfactant sodium dodecyl sulfonate, blow dried, then positioned in a mixed solution of hydrogen peroxide and sulfuric acid (1:2.6), heated at 80° C. for 1 h, and cooled naturally. The residual solution on the surfaces was washed off with pure water and then the glass members were blow dried. In this way, the surfaces of the glass members were activated. The surface roughness of the glass members before activation was 0.843 nm. Activation Example 18 A first glass member and a second glass member were washed with a mixed solution of hydrofluoric acid, sulfuric acid, and the surfactant sodium dodecyl sulfonate, blow dried, then positioned in a mixed solution of hydrogen peroxide and sulfuric acid (1:2.5), heated at 80° C. for 1 h, and cooled naturally. The residual solution on the surfaces was washed off with pure water and then the glass members were blow dried. In this way, the surfaces of the glass members were activated. The surface roughness of the glass members before activation was 0.431 nm. Activation Example 19 A first glass member and a second glass member were washed with a mixed solution of hydrofluoric acid, sulfuric acid, and the surfactant sodium dodecyl sulfonate, blow dried, then positioned in a mixed solution of hydrogen peroxide and sulfuric acid (1:2.3), heated at 80° C. for 1 h, and cooled naturally. The residual solution on the surfaces was washed off with pure water and then the glass members were blow dried. In this way, the surfaces of the glass members were activated. The surface roughness of the glass members before activation was 0.607 nm. Activation Example 20 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. 60 g of K2Cr2O7was dissolved in 270 g of water, and 44 ml of concentrated sulfuric acid was slowly added. A first glass member and a second glass member were soaked in the prepared mixed acid solution (for 2 h at room temperature or for 30 min at 50° C.). The glass members were removed, and the residual chromium ions on the surfaces were washed off with a 10% nitric acid solution. Then the glass members were washed with pure water for 10 min and then blow dried. In this way, the surfaces of the glass members were activated. Activation Example 21 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. 20 g of K2Cr2O7was dissolved in 270 g of water, and 44 ml of concentrated sulfuric acid was slowly added. A first glass member and a second glass member were soaked in the prepared mixed acid solution (for 6 h at room temperature or for 150 min at 50° C.). The glass members were removed, and the residual chromium ions on the surfaces were washed off with a 10% nitric acid solution. Then the glass members were washed with pure water for 10 min and then blow dried. In this way, the surfaces of the glass members were activated. Activation Example 22 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. 30 g of K2Cr2O7was dissolved in 270 g of water, and 44 ml of concentrated sulfuric acid was slowly added. A first glass member and a second glass member were soaked in the prepared mixed acid solution (for 5 h at room temperature or for 120 min at 50° C.). The glass members were removed, and the residual chromium ions on the surfaces were washed off with a 10% nitric acid solution. Then the glass members were washed with pure water for 10 min and then blow dried. In this way, the surfaces of the glass members were activated. Activation Example 23 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. 40 g of K2Cr2O7was dissolved in 270 g of water, and 44 ml of concentrated sulfuric acid was slowly added. A first glass member and a second glass member were soaked in the prepared mixed acid solution (for 4 h at room temperature or for 90 min at 50° C.). The glass members were removed, and the residual chromium ions on the surfaces were washed off with a 10% nitric acid solution. Then the glass members were washed with pure water for 10 min and then blow dried. In this way, the surfaces of the glass members were activated. Activation Example 24 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. 50 g of K2Cr2O7was dissolved in 270 g of water, and 44 ml of concentrated sulfuric acid was slowly added. A first glass member and a second glass member were soaked in the prepared mixed acid solution (for 3 h at room temperature or for 60 min at 50° C.). The glass members were removed, and the residual chromium ions on the surfaces were washed off with a 10% nitric acid solution. Then the glass members were washed with pure water for 10 min and then blow dried. In this way, the surfaces of the glass members were activated. Activation Example 25 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. A first glass member and a second glass member were soaked in a mixed solution containing 10% hydrofluoric acid and 10% ammonium bifluoride at room temperature for 30 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. Activation Example 26 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. A first glass member and a second glass member were soaked in a mixed solution containing 10% hydrofluoric acid and 10% ammonium bifluoride at room temperature for 35 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. Activation Example 27 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. A first glass member and a second glass member were soaked in a mixed solution containing 5% hydrofluoric acid and 5% ammonium bifluoride at room temperature for 40 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. Activation Example 28 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. A first glass member and a second glass member were soaked in a mixed solution containing 15% hydrofluoric acid and 15% ammonium bifluoride at room temperature for 30 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. Activation Example 29 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. A first glass member and a second glass member were soaked in a mixed solution containing 20% hydrofluoric acid and 20% ammonium bifluoride at room temperature for 25 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. Activation Example 30 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. A first glass member and a second glass member were soaked in a mixed solution containing 25% hydrofluoric acid and 25% ammonium bifluoride at room temperature for 20 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. Activation Example 31 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. A first glass member and a second glass member were soaked in a mixed solution containing 30% hydrofluoric acid and 30% ammonium bifluoride at room temperature for 15 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. Activation Example 32 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. A first glass member and a second glass member were soaked in a mixed solution containing 35% hydrofluoric acid and 35% ammonium bifluoride at room temperature for 10 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. Activation Example 33 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. A first glass member and a second glass member were soaked in a mixed solution containing 40% hydrofluoric acid and 40% ammonium bifluoride at room temperature for 5 min. Then, the glass members were washed with pure water at room temperature for 20 min and then dried. Detection Means after Activation The first glass members and second glass members obtained in all the above activation examples were determined for the contact angle with water drops. Specifically, water was dropped on the activated surface of clean first glass member and second glass member. If the water droplets can expand and wet the surface and the water droplets are visually observed to be round and evenly infiltrate the surface, or the contact angle of water with the glass is determined by a contact angle tester to be less than or equal to 10°, then the glass surface is considered to be clean and activated. The test results show that the contact angle (i.e. contact angle with water drops) of the activated surfaces of the first glass member and the second glass member obtained in all the activation examples is less than or equal to 10°. Specifically, the activated surfaces in Activation Examples 1-33 have respectively a contact angle of 3°, 2°, 3°, 3°, 2°, 3°, 2°, 2°, 3°, 3°, 3°, 2°, 3°, 2°, 2°, 3°, 1°, 3°, 2°, 3°, 2°, 2°, 3°, 1°, 3°, 4°, 2°, 3°, 1°, 4°, 2°, 2°, and 3°. Compounding Example 1 In this example, the first glass member and the second glass member are both made of Corning GG3 glass with a thickness of 0.7 mm (having a visible light transmittance of 91%-93%). The method for compounding the first glass member (sheet glass member) and the second glass member (rectangular frame-shaped glass member) is as follows. The first glass member and the second glass member were activated following the method in Activation Example 15. The surface-activated first glass member and second glass member were put into a vacuum box or a vacuum bag and evacuated (that is, coupling). The second glass member was positioned to the outer peripheral edge of the first glass member by a positioning fixture, CCD or other positioning methods, during which caution was taken to avoid foreign objects or fingers touching the activated surfaces, to avoid contamination of the activated surface causing defects. After coupling, the glass members were heated to 650° C. and a pressure of 0.4 MPa was applied. The temperature and pressure were maintained for 3 hrs, and then the glass members were slowly cooled. In this way, the first glass member and the second glass member were compounded together, and a casing was obtained (seeFIG.6Afor the schematic structure). In the example, the obtained casing has a light transmittance of more than 91% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are visually observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member (seeFIG.17). The bonding strength was tested. The test sample is schematically shown inFIG.1(where the length L of the glass member1and2is 24 mm, the width W1is 12 mm, and the length L1of the overlapping area of the two glass members is 6 mm). The test method is schematically shown inFIG.16. Specifically the sample was stretched at a speed of 5 mm/min by a universal material testing machine until the glass was broken. Test results: When the tensile force is 150 N (i.e., the bonding strength is 2.08 MPa), there is no change at the bonding position, but the first glass member and the second glass member are broken, indicating that the two pieces of glass are compounded into one. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces are observed visually by naked eyes or under a microscope at a magnification of 500× (seeFIG.18). This indicates that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 10% for 5 min. The compounding interface of the first glass member and the second glass member was corroded. A crevice having a width of 10-50 μm was visually observed. Comparative Example 1 The casing was prepared according to the method of Compounding Example 1, except that the first glass member and the second glass member were not activated. The casing obtained is observed to have obvious fantasy colors and large bubbles (seeFIG.19). The bonding strength was tested by the method of Compounding Example 1. The bonding strength is 10 N. The casing was cut along a direction vertical to the compounding interface. Compounding crevices exist at positions on the compounding interface where bubbles and fantasy colors are present (seeFIG.20). By a steel ball of 32 g falling from a height of 1 meter, the casing was broken, and the glass partially cracked at positions on the compounding interface, indicating that the compounding effect is poor. This indicates that the bonding strength at positions where the bubbles and fantasy colors are present is poor, and the casing is easily broken. This indicates that the bonding strength at positions where the bubbles and fantasy colors are present is poor, and the casing is easily broken. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. Crevices are observed visually, indicating that the compounding effect is poor. Comparative Example 2 The casing was prepared according to the method of Compounding Example 1, except that no activation was performed, and the first glass member and the second glass member were coupled and heated to a temperature above the softening point of the first glass member and the second glass member. The casing is observed to have obvious indentations and impressions at the compounding interface, the deformation is serious, the light transmittance is only about 85% for visible light (wavelength band 380-720 nm), and the local transmittance is less than or equal to 75%, causing a serious impact on the optical performance. The bonding strength was tested by the test method of Compounding Example 1. The bonding strength is consistent with that in Compounding Example 1. By this method, a similar compounding effect is obtained, which, however, cannot meet the appearance requirement. Compounding Example 2 In this example, the first glass member and the second glass member are both made of Corning GG5 glass with a thickness of 1 mm (having a visible light transmittance of 91%-93%). The method for compounding the first glass member (sheet glass member) and the second glass member (circular frame-shaped glass member) is as follows. The first glass member and the second glass member were activated following the method in Activation Example 1. The surface-activated first glass member and second glass member were coupled and heated to 750° C., and then a pressure of 2 MPa was applied. The temperature and pressure were maintained for 5 hrs, and then the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together, and a casing was obtained (seeFIG.6Bfor the schematic structure). In the example, the obtained casing has a light transmittance of 91% or more for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are visually observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member. The bonding strength was tested according to the method in Compounding Example 1. The test result shows that when the tensile force is 155 N (that is, 2.15 MPa), there is no change at the bonding position, but the first glass member and the second glass member are broken, indicating that the two pieces of glass are compounded into one. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicated that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 10% for 5 min. The compounding interface of the first glass member and the second glass member was corroded. A crevice having a width of 1-10 μm was visually observed. Comparative Example 3 The glass composite was prepared according to the method of Compounding Example 2, except that the first glass member and the second glass member were not activated. The casing obtained is observed to have obvious fantasy colors and large bubbles. The bonding strength was tested by the method of Compounding Example 2. The bonding strength is 20 N, indicating that the casing has poor bonding strength and tends to break at the positions where bubbles and fantasy colors are present. Comparative Example 4 The glass composite was prepared according to the method of Compounding Example 2, except that no activation was performed, and the first glass member and the second glass member were coupled and heated to a temperature above the softening point of the first glass member and the second glass member. The casing is observed to have obvious indentations and impressions at the compounding interface, the deformation is serious, and the light transmittance is only 85% or less for visible light (wavelength band 380-720 nm), causing a serious impact on the optical performance. The bonding strength was tested by the test method of Compounding Example 2. The bonding strength is consistent with that in Compounding Example 2. By this method, a similar compounding effect is obtained, which, however, cannot meet the appearance requirement. Compounding Example 3 In this example, the first glass member and the second glass member are both made of Schott glass with a thickness of 3 mm (having a visible light transmittance of 91%-95%). The method for compounding the first glass member (sheet glass member) and the second glass member (bar-shaped glass member) is as follows. The first glass member and the second glass member were activated following the method in Activation Example 2. The surface-activated first glass member and second glass member were coupled and heated to 700° C., and a pressure of 1 MPa was applied. The temperature and pressure were maintained for 4 hrs, and then the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together, and a casing was obtained (seeFIG.6Cfor the schematic structure). In the example, the obtained casing has a light transmittance of 91% or more for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are visually observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member. The bonding strength was tested according to the method in Compounding Example 1. The test result shows that when the tensile force is 160 N (that is, 2 at 0.22 MPa), there is no change at the bonding position, but the first glass member and the second glass member are broken, indicating that the two pieces of glass are compounded into one. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicated that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 5% for 5 min. The compounding interface of the first glass member and the second glass member was corroded. A crevice having a width of 0.5-2 μm was visually observed. Comparative Example 5 The glass composite was prepared according to the method of Compounding Example 3, except that the first glass member and the second glass member were not activated. The casing obtained is observed to have obvious fantasy colors and large bubbles. The bonding strength was tested by the method of Compounding Example 3. The bonding strength is 15 N, indicating that the casing has poor bonding strength and tends to break at the positions where bubbles and fantasy colors are present. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. Crevices are observed at positions where fantasy colors and bubbles are present, indicating that the compounding effect is poor. Comparative Example 6 The glass composite was prepared according to the method of Compounding Example 3, except that no activation was performed, and the first glass member and the second glass member were coupled and heated to a temperature above the softening point of the first glass member and the second glass member. The casing is observed to have obvious indentations and impressions at the compounding interface, the deformation is serious. The bonding strength was tested by the test method of Compounding Example 3. The bonding strength is consistent with that in Compounding Example 3. By this method, a similar compounding effect is obtained, which, however, cannot meet the appearance requirement. Compounding Example 4 The process was the same as that in Compounding Example 1, except that the first glass member and the second glass member were treated by the method as described in Activation Example 20. The obtained casing has a light transmittance of 93% or more for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are visually observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member. The bonding strength was tested according to the method in Compounding Example 1. The test result shows that when the tensile force is 164 N (that is, 2.28 MPa), there is no change at the bonding position, but the first glass member and the second glass member are broken, indicating that the two pieces of glass are compounded into one. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicated that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 10% for 5 min. The compounding interface of the first glass member and the second glass member was corroded. A crevice having a width of 10-50 μm was visually observed. Activation Example 34 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were treated for 1 h in a mixed solution of aqueous ammonia and hydrogen peroxide (volume ratio 1:1) at 40° C. The residual solution on the surface was washed off for 10 min with pure water. Then the glass members were blow dried. In this way, the surfaces of the glass members were activated. The surface roughness of the glass members before activation was 0.543 nm. Activation Example 35 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were treated for 50 min in a mixed solution of aqueous ammonia and hydrogen peroxide (1:2) at 40° C. The residual solution on the surface was washed off for 10 min with pure water. Then the glass members were blow dried. In this way, the surfaces of the glass members were activated. The surface roughness of the glass members before activation was 0.285 nm. Activation Example 36 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were treated for 40 min in a mixed solution of aqueous ammonia and hydrogen peroxide (1:3) at 40° C. The residual solution on the surface was washed off for 10 min with pure water. Then the glass members were blow dried. In this way, the surfaces of the glass members were activated. The surface roughness of the glass members before activation was 0.369 nm. Activation Example 37 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were treated for 30 min in a mixed solution of aqueous ammonia and hydrogen peroxide (1:4) at 40° C. The residual solution on the surface was washed off for 10 min with pure water. Then the glass members were blow dried. In this way, the surfaces of the glass members were activated. The surface roughness of the glass members before activation was 0.745 nm. Activation Example 38 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were treated for 20 min in a mixed solution of aqueous ammonia and hydrogen peroxide (1:5) at 40° C. The residual solution on the surface was washed off for 10 min with pure water. Then the glass members were blow dried. In this way, the surfaces of the glass members were activated. The surface roughness of the glass members before activation was 0.943 nm. Activation Example 39 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were treated for 30 min in a mixed solution of sodium hypochlorite and aqueous ammonia (containing, in percentage by weight, 5% of sodium hypochlorite, 15% of aqueous ammonia, and 80% of deionized water) at room temperature. The residual solution on the surface was washed off for 10 min with pure water. Then the glass members were blow dried. In this way, the surfaces of the glass members were activated. Activation Example 40 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were treated for 20 min in a mixed solution of sodium hypochlorite and aqueous ammonia (containing, in percentage by weight, 10% of sodium hypochlorite, 30% of aqueous ammonia, and 60% of deionized water) at room temperature. The residual solution on the surface was washed off for 10 min with pure water. Then the glass members were blow dried. In this way, the surfaces of the glass members were activated. Activation Example 41 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were treated for 60 min in a mixed solution of sodium hypochlorite and aqueous ammonia (containing, in percentage by weight, 5% of sodium hypochlorite, 5% of aqueous ammonia, and 90% of deionized water) at room temperature. The residual solution on the surface was washed off for 10 min with pure water. Then the glass members were blow dried. In this way, the surfaces of the glass members were activated. Activation Example 42 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were treated for 15 min in a mixed solution of sodium hypochlorite and aqueous ammonia (containing, in percentage by weight, 20% of sodium hypochlorite, 30% of aqueous ammonia, and 50% of deionized water) at room temperature. The residual solution on the surface was washed off for 10 min with pure water. Then the glass members were blow dried. In this way, the surfaces of the glass members were activated. Detection Means after Activation The first glass members and second glass members obtained in all the above activation examples were determined for the contact angle with water drops. Specifically, water was dropped on the surface of clean first glass member and second glass member. If the water droplets can expand and wet the surface and the water droplets are visually observed to be round and evenly infiltrate the surface, or the contact angle of water with the glass is determined by a contact angle tester to be less than or equal to 10°, then the glass surface is considered to be clean and activated. The test results show that the contact angle (i.e. contact angle with water drops) of the first glass member and the second glass member obtained in Activation Examples 34-42 is less than or equal to 10°, and specifically 3°, 3°, 1°, 2°, 2°, 3°, 2°, 3°, and 1°. Compounding Example 5 In this example, the first glass member and the second glass member are both made of Corning GG3 glass with a thickness of 0.7 mm (having a visible light transmittance of 91%-93%). The method for compounding the first glass member (sheet glass member) and the second glass member (rectangular frame-shaped glass member) was as follows. At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were treated for 50 min in a mixed solution of aqueous ammonia and hydrogen peroxide (1:2) at 40° C. The residual solution on the surface was washed off for 10 min with pure water. Then the glass members were blow dried. In this way, the surfaces of the glass members were activated. The surface-activated first glass member and second glass member were brought into contact and heated to 700° C., and a pressure of 0.5 MPa was applied. The temperature and pressure were maintained for 2 hrs. In this way, the glass members were partially or totally compounded together, and a casing was obtained, seeFIG.6Afor the schematic structure. In the example, the obtained casing has a light transmittance of 92% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The casing surface is flat and smooth, and there are no visible bubbles, impurity spots, fantasy colors, and other defects at the compounding position. The casing was cut along a direction vertical to the compounding surface, and no compounding crevice is observed at the compounding interface. The bonding strength was tested by the method of Compounding Example 1. The results show that the bonding strength is 151 N (i.e. 2.1 MPa), there is no change at the bonding position, and the glass members are broken, indicating that the two pieces of glass are compounded into one. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicates that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 10% for 5 min. The first glass member and the second glass were visually observed to have crevices having a width of 10-50 μm. Compounding Example 6 In this example, the first glass member and the second glass member are both made of Schott glass (having a visible light transmittance of 91%-93%). The method for compounding the first glass member (sheet glass member) and the second glass member (rectangular frame-shaped glass member) was as follows. At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were treated for 40 min in a mixed solution of aqueous ammonia and hydrogen peroxide (1:3) at 40° C. The residual solution on the surface was washed off for 10 min with pure water. Then the glass members were blow dried. In this way, the surfaces of the glass members were activated. The surface-activated first glass member and second glass member were brought into contact and heated to 610° C., and a pressure of 1 MPa was applied. The temperature and pressure were maintained for 2 hrs, and then the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together, and a casing was obtained (seeFIG.6Afor the schematic structure). In the example, the obtained casing has a light transmittance of 91% for visible light, which shows that the optical performance is better, and the performance during use is better. The compounding position of the first glass member and the second glass member has no obvious bubbles and fantasy colors. The bonding strength was tested according to the test method in Compounding Example 1. The test result shows that when the tensile force is 159 N (that is, 2.21 MPa), there is no change at the bonding position, but the first glass member or the second glass member is broken, indicating that the two pieces of glass are compounded into one. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicates that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 40% for 2 min. It is visually observed that obvious crevices are formed at the compounding interface in the cross section. Compounding Example 7 In this example, the first glass member and the second glass member are both made of Schott glass (having a visible light transmittance of 91%-93%). The method for compounding the first glass member (sheet glass member) and the second glass member (bar-shaped glass member) is as follows. At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were treated for 60 min in a mixed solution of sodium hypochlorite and aqueous ammonia (containing, in percentage by weight, 10% of sodium hypochlorite, 30% of aqueous ammonia, and 60% of deionized water) at room temperature. The residual solution on the surface was washed off for 10 min with pure water. Then the glass members were blow dried. In this way, the surfaces of the glass members were activated. The surface-activated first glass member and second glass member were brought into contact and heated to 450° C., and a pressure of 1.5 MPa was applied. The temperature and pressure were maintained for 5 hrs. Then, the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together, and a casing was obtained, seeFIG.6Cfor the schematic structure. In the example, the obtained casing has a light transmittance of 91.5% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are visually observed to be flat and smooth, and the compounding position of the first glass member and the second glass member has no obvious bubbles and fantasy colors. The bonding strength was tested according to the test method in Compounding Example 1. The test result shows that when the tensile force is 155 N (that is, 2.15 MPa), there is no change at the bonding position, but the first glass member or the second glass member is broken, indicating that the two pieces of glass are compounded into one. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicates that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 20% for 5 min. It is visually observed that obvious crevices having a width of 0.5-20 μm are formed at the compounding interface in the cross section. Compounding Example 8 In this example, the first glass member and the second glass member are both made of Schott glass (having a visible light transmittance of 91%-93%). The first glass member is of a curved glass shape, and the second glass member is of a curved glass shape. The surface of the first glass member is an upwardly bulged curved surface, and the surface of the second glass member is an upwardly depressed curved surface. The surfaces of the portions at which the two glass members need to be compounded have the same radius of curvature, and continuous contact can be achieved without crevices. The method for compounding the first glass member and the second glass member is as follows. At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were treated for 40 min in a mixed solution of sodium hypochlorite and aqueous ammonia (containing, in percentage by weight, 20% of sodium hypochlorite, 30% of aqueous ammonia, and 50% of deionized water) at room temperature. The residual solution on the surface was washed off for 10 min with pure water. Then the glass members were blow dried. In this way, the surfaces of the glass members were activated. The surface-activated first glass member and second glass member were brought into contact and heated to 250° C., and a pressure of 2.0 MPa was applied. The temperature and pressure were maintained for 6 hrs. Then, the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together. In the example, the obtained casing has a light transmittance of more than 92.5% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member. The bonding strength was tested according to the method in Compounding Example 1. The bonding strength is 130 N, there is no change at the compounding position, but the glass member is broken. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicates that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 15% for 5 min. It is visually observed that obvious crevices are formed at the compounding interface in the cross section. Compounding Example 9 In this example, the first glass member and the second glass member are both made of Schott glass (having a visible light transmittance of 91%-93%). The first glass member is of a curved glass shape, and the second glass member is of a curved glass shape. The surface of the first glass member is an upwardly bulged curved surface, and the surface of the second glass member is an upwardly depressed curved surface. The surfaces of the portions at which the two glass members need to be compounded have the same radius of curvature, and continuous contact can be achieved without crevices. The method for compounding the first glass member and the second glass member is as follows. First, the organic pollutant was removed from the first glass member and second glass member by an organic solvent, and then the impurities on the surfaces were removed by using an alkaline detergent with a pH of 14. The first glass member and second glass member were activated for 30 min by immersing in a solution containing, in percentage by weight, 20% of sodium hypochlorite, 30% of aqueous ammonia, and 50% of deionized water at 30° C. The surface-activated first glass member and second glass member were brought into contact and heated to 750° C., and a pressure of 0.05 MPa was applied. The temperature and pressure were maintained for 3 hrs. Then, the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together. In the example, the obtained casing has a light transmittance of more than 91% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member. The bonding strength was tested according to the method in Compounding Example 1. The bonding strength is 135 N, there is no change at the bonding position, but the glass member is broken. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicated that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 30% for 3.5 min. The compounding interface of the first glass member and the second glass member was evenly corroded at a rate that is higher than the corrosion rate of the first glass member and the second glass member. It is visually observed that crevices are formed at the compounding interface in the cross section. Compounding Example 10 In this example, the first glass member and the second glass member are both made of Corning GG3 glass with a thickness of 0.7 mm (having a visible light transmittance of 91%-93%). The first glass member is of a curved glass shape, and the second glass member is of a curved glass shape. The surface of the first glass member is an upwardly bulged curved surface, and the surface of the second glass member is an upwardly depressed curved surface. The surfaces of the portions at which the two glass members need to be compounded have the same radius of curvature, and continuous contact can be achieved without crevices. The method for compounding the first glass member and the second glass member is as follows. The first glass member and the second glass member were activated following the method in Activation Example 34. The surface-activated first glass member and second glass member were brought into contact and heated to 550° C., and a pressure of 1.0 MPa was applied. The temperature and pressure were maintained for 3 hours, and then the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together. In the example, the obtained casing has a light transmittance of more than 91% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are visually observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member. The bonding strength was tested according to the method in Compounding Example 1. The bonding strength is 130 N, there is no change at the bonding position, but the glass member is broken. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicated that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 5% for 20 min. The compounding interface of the first glass member and the second glass member was corroded. Crevices were visually observed. Activation Example 43 The oil stains on the surfaces were removed by washing the first glass member and second glass member with trichloroethylene for 20 min, and then the first glass member and second glass member were irradiated with ultraviolet light for 0.5 h to obtain glass members with clean and activated surfaces. Activation Example 44 The oil stains on the surfaces were removed by washing the first glass member and second glass member with trichloroethylene for 20 min, and then the first glass member and second glass member were irradiated with ultraviolet light for 0.8 h to obtain glass members with clean and activated surfaces. Activation Example 45 The oil stains on the surfaces were removed by washing the first glass member and second glass member with trichloroethylene for 20 min, and then the first glass member and second glass member were irradiated with ultraviolet light for 1 h to obtain glass members with clean and activated surfaces. Activation Example 46 The oil stains on the surfaces were removed by washing the first glass member and second glass member with trichloroethylene for 20 min, and then the first glass member and second glass member were irradiated with ultraviolet light for 1.2 h to obtain glass members with clean and activated surfaces. The surface roughness of the glass members before activation was 0.203 nm. Activation Example 47 The oil stains on the surfaces were removed by washing the first glass member and second glass member with trichloroethylene for 20 min, and then the first glass member and second glass member were irradiated with ultraviolet light for 1.5 h to obtain glass members with clean and activated surfaces. Activation Example 48 The oil stains on the surfaces were removed by washing the first glass member and second glass member with trichloroethylene for 20 min, and then the cleaned glass members were positioned in an ozone-generating device and irradiated with ultraviolet light for 5 min. This is because ozone provides highly reactive atomic oxygen, which can form a volatile substance with free radicals generated after the dissociation of the dirt and thus enable an activated surface. Activation Example 49 The oil stains on the surfaces were removed by washing the first glass member and second glass member with trichloroethylene for 20 min, and then the cleaned glass members were positioned in an ozone-generating device and irradiated with ultraviolet light for 8 min. Activation Example 50 The oil stains on the surfaces were removed by washing the first glass member and second glass member with trichloroethylene for 20 min, and then the cleaned glass members were positioned in an ozone-generating device and irradiated with ultraviolet light for 10 min. Activation Example 51 The oil stains on the surfaces were removed by washing the first glass member and second glass member with trichloroethylene for 20 min, and then the cleaned glass members were positioned in an ozone-generating device and irradiated with ultraviolet light for 15 min. Activation Example 52 The oil stains on the surfaces were removed by washing the first glass member and second glass member with trichloroethylene for 20 min, and then the cleaned glass members were positioned in an ozone-generating device and irradiated with ultraviolet light for 20 min. Activation Example 53 The oil stains on the surfaces were removed by washing the first glass member and second glass member with trichloroethylene for 20 min, and then the first glass member and second glass member were irradiated with ultraviolet light for 12 h to obtain glass members with clean and activated surfaces. Detection Means after Activation The first glass members and second glass members obtained in all the above activation examples were determined for the contact angle with water drops. Specifically, water was dropped on the activated surface of clean first glass member and second glass member. If the water droplets can expand and wet the surface and the water droplets are visually observed to be round and evenly infiltrate the surface, or the contact angle of water with the glass is determined by a contact angle tester to be less than or equal to 10°, then the glass surface is considered clean and activated. The test results show that the contact angle (i.e. contact angle with water drops) of the activated surfaces of the first glass member and the second glass member obtained in all the activation examples is less than or equal to 10°. Specifically, the activated surfaces in Activation Examples 43-53 have respectively a contact angle of 4°, 2°, 3°, 3°, 3°, 4°, 2°, 3°, 2°, 3°, and 2°. Compounding Example 11 In this example, the first glass member and the second glass member are both made of Corning GG3 glass with a thickness of 0.7 mm (having a visible light transmittance of 91%-93%). The method for compounding the first glass member (sheet glass member) and the second glass member (rectangular frame-shaped glass member) is as follows. The first glass member and the second glass member were activated following the method in Activation Example 43. The surface-activated first glass member and second glass member were put into a vacuum box or a vacuum bag and evacuated, to contact the lower surface of the first glass member with the upper surface of the second glass member. The second glass member was positioned to the outer peripheral edge of the first glass member by a positioning fixture, CCD or other positioning methods, during which caution was taken to avoid foreign objects or fingers touching the activated surfaces, to avoid contamination of the activated surface causing defects. The glass members were heated to 650° C. and a pressure of 0.3 MPa was applied. The temperature and pressure were maintained for 3 hours, and then the glass members were slowly cooled. In this way, the first glass member and the second glass member were compounded together, and a casing was obtained, seeFIG.6Afor the schematic structure. In the example, the obtained casing has a light transmittance of more than 90% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are visually observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member (seeFIG.9). The bonding strength was tested according to the method in Compounding Example 1. The test result shows that when the tensile force is 151 N (that is, 2.1 MPa), there is no change at the bonding position, but the first glass member and the second glass member are broken, indicating that the two pieces of glass are compounded into one. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicated that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 10% for 5 min. The compounding interface of the first glass member and the second glass member was corroded. A crevice having a width of 10-50 μm was visually observed. Compounding Example 12 In this example, the first glass member and the second glass member are both made of Corning GG5 glass with a thickness of 1 mm (having a visible light transmittance of 91%-93%). The method for compounding the first glass member (sheet glass member) and the second glass member (rectangular frame-shaped glass member) was as follows. The first glass member and the second glass member were activated following the method in Activation Example 44. The surface-activated first glass member and second glass member were brought into contact at the activated surfaces and heated to 700° C., and a pressure of 1 MPa was applied. The temperature and pressure were maintained for 3 hours, and then the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together, and a casing was obtained, seeFIG.6Afor the schematic structure. In the example, the obtained casing has a light transmittance of 90% or more for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are visually observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member. The bonding strength was tested according to the method in Compounding Example 1. The test result shows that when the tensile force is 156 N (that is, 2.16 MPa), there is no change at the bonding position, but the first glass member and the second glass member are broken, indicating that the two pieces of glass are compounded into one. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicated that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 10% for 5 min. The compounding interface of the first glass member and the second glass member was corroded. A crevice having a width of 1-20 μm was visually observed. Compounding Example 13 In this example, the first glass member and the second glass member are both made of Corning GG3 glass with a thickness of 3 mm (having a visible light transmittance of 91%-95%). The method for compounding the first glass member (sheet glass member) and the second glass member (bar-shaped glass member) is as follows. The first glass member and the second glass member were activated following the method in Activation Example 43. The surface-activated first glass member and second glass member were brought into contact at the activated surfaces and heated to 750° C., and a pressure of 2 MPa was applied. The temperature and pressure were maintained for 4 hrs, and then the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together, and a casing was obtained, seeFIG.6Cfor the schematic structure. In the example, the obtained casing has a light transmittance of 90% or more for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are visually observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member. The bonding strength was tested according to the method in Compounding Example 1. The test result shows that when the tensile force is 161 N (that is, 2.23 MPa), there is no change at the bonding position, but the first glass member and the second glass member are broken, indicating that the two pieces of glass are compounded into one. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicated that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 5% for 5 min. The compounding interface of the first glass member and the second glass member was corroded. A crevice having a width of 0.1-30 μm was visually observed. Compounding Example 14 In this example, the first glass member and the second glass member are both made of Schott glass with a thickness of 3 mm (having a visible light transmittance of 91%-95%). The first glass member is of a flat glass shape, and the second glass member is of a curved glass shape. The method for compounding the first glass member and the second glass member is as follows. The first glass member and the second glass member were activated following the method in Activation Example 46. The surface-activated first glass member and second glass member were brought into contact at the activated surfaces and heated to 750° C., and then a pressure of 2 MPa was applied. The temperature and pressure were maintained for 4 hrs, and then the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together. In the example, the obtained casing has a light transmittance of 90% or more for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are visually observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member. The bonding strength was tested according to the method in Compounding Example 1. The test result shows that when the tensile force is 161 N (that is, 2.23 MPa), there is no change at the bonding position, but the first glass member and the second glass member are broken, indicating that the two pieces of glass are compounded into one. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicated that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 5% for 5 min. The compounding interface of the first glass member and the second glass member was corroded. A crevice having a width of 0.2-2 μm was visually observed. Compounding Example 15 In this example, the first glass member and the second glass member are both made of Schott glass with a thickness of 3 mm (having a visible light transmittance of 91%-95%). The first glass member is of a curved glass shape, and the second glass member is of a flat glass shape. The method for compounding the first glass member and the second glass member is as follows. The first glass member and the second glass member were activated following the method in Activation Example 47. The surface-activated first glass member and second glass member were brought into contact at the activated surfaces and heated to 750° C., and then a pressure of 2 MPa was applied. The temperature and pressure were maintained for 4 hrs, and then the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together. In the example, the obtained casing has a light transmittance of 90% or more for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are visually observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member. The bonding strength was tested according to the method in Compounding Example 1. The test result shows that when the tensile force is 161 N (that is, 2.23 MPa), there is no change at the bonding position, but the first glass member and the second glass member are broken, indicating that the two pieces of glass are compounded into one. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicated that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 5% for 5 min. The compounding interface of the first glass member and the second glass member was corroded. A crevice having a width of 0.2-2 μm was visually observed. Compounding Example 16 In this example, the first glass member and the second glass member are both made of Schott glass with a thickness of 3 mm (having a visible light transmittance of 91%-95%). The first glass member is of a curved glass shape, and the second glass member is of a curved glass shape. The surface of the first glass member is an upwardly bulged curved surface, and the surface of the second glass member is an upwardly depressed curved surface. The surfaces of the portions at which the two glass members need to be compounded have the same radius of curvature, and continuous contact can be achieved without crevices. The method for compounding the first glass member and the second glass member is as follows. The first glass member and the second glass member were activated following the method in Activation Example 48. The surface-activated first glass member and second glass member were brought into contact at the activated surfaces and heated to 750° C., and then a pressure of 2 MPa was applied. The temperature and pressure were maintained for 4 hours, and then the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together. In the example, the obtained casing has a light transmittance of 90% or more for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are visually observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member. The bonding strength was tested. The test sample is schematically shown inFIG.8(where the length L of the glass member1and2is 24 mm, the width W1is 12 mm, and the length L1of the overlapping area of the two glass members is 6 mm). The test method is schematically shown inFIG.9. Specifically, the sample was stretched at a speed of 5 mm/min by a universal material testing machine until the glass was broken. Test results: When the tensile force is 161 N (i.e., 2.23 MPa), there is no change at the bonding position, but the first glass member and the second glass member are broken, indicating that the two pieces of glass are compounded into one. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicated that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 5% for 5 min. The compounding interface of the first glass member and the second glass member was corroded. A crevice having a width of 0.2-2 μm was visually observed. Compounding Example 17 In this example, the first glass member and the second glass member are both made of Schott glass with a thickness of 3 mm (having a visible light transmittance of 91%-95%). The method for compounding the first glass member and the second glass member is as follows. The first glass member and the second glass member were activated following the method in Activation Example 49. The surface-activated first glass member and second glass member were brought into contact at the activated surfaces and heated to 750° C., and then a pressure of 2 MPa was applied. The temperature and pressure were maintained for 4 hours, and then the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together. In the example, the obtained casing has a light transmittance of 90% or more for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are visually observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member. The bonding strength was tested according to the method in the compounding examples. The test result shows that when the tensile force is 161 N (that is, 2.23 MPa), there is no change at the bonding position, but the first glass member and the second glass member are broken, indicating that the two pieces of glass are compounded into one. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicated that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 5% for 5 min. The compounding interface of the first glass member and the second glass member was corroded. A crevice having a width of 0.2-2 μm was visually observed. Compounding Example 18 In this example, the first glass member and the second glass member are both made of Schott glass with a thickness of 3 mm (having a visible light transmittance of 91%-95%). The method for compounding the first glass member and the second glass member is as follows. The first glass member and the second glass member were activated following the method in Activation Example 50. The surface-activated first glass member and second glass member were brought into contact at the activated surfaces and heated to 750° C., and then a pressure of 2 MPa was applied. The temperature and pressure were maintained for 4 hours, and then the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together. In the example, the obtained casing has a light transmittance of 90% or more for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are visually observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member. The bonding strength was tested according to the method in the compounding examples. The test result shows that when the tensile force is 161 N, there is no change at the bonding position, but the first glass member and the second glass member are broken, indicating that the two pieces of glass are compounded into one. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicated that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 5% for 5 min. The compounding interface of the first glass member and the second glass member was corroded. A crevice having a width of 0.2-2 μm was visually observed. Compounding Example 19 In this example, the first glass member and the second glass member are both made of Schott glass with a thickness of 3 mm (having a visible light transmittance of 91%-95%). The method for compounding the first glass member and the second glass member is as follows. The first glass member and the second glass member were activated following the method in Activation Example 51. The surface-activated first glass member and second glass member were brought into contact at the activated surfaces and heated to 750° C., and then a pressure of 2 MPa was applied. The temperature and pressure were maintained for 4 hours, and then the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together. In the example, the obtained casing has a light transmittance of 90% or more for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are visually observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member. The bonding strength was tested according to the method in the compounding examples. The test result shows that when the tensile force is 161 N, there is no change at the bonding position, but the first glass member and the second glass member are broken, indicating that the two pieces of glass are compounded into one. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicated that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 5% for 5 min. The compounding interface of the first glass member and the second glass member was corroded. A crevice having a width of 0.2-2 μm was visually observed. Compounding Example 20 In this example, the first glass member and the second glass member are both made of Schott glass with a thickness of 3 mm (having a visible light transmittance of 91%-95%). The method for compounding the first glass member and the second glass member is as follows. The first glass member and the second glass member were activated following the method in Activation Example 52. The surface-activated first glass member and second glass member were brought into contact at the activated surfaces and heated to 750° C., and then a pressure of 2 MPa was applied. The temperature and pressure were maintained for 4 hours, and then the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together. In the example, the obtained casing has a light transmittance of 90% or more for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are visually observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member. The bonding strength was tested according to the method in the compounding examples. The test result shows that when the tensile force is 161 N, there is no change at the bonding position, but the first glass member and the second glass member are broken, indicating that the two pieces of glass are compounded into one. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicated that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 5% for 5 min. The compounding interface of the first glass member and the second glass member was corroded. A crevice having a width of 0.2-2 μm was visually observed. Activation Example 54 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were positioned in a plasma dry cleaner, and washed with O2plasma for 10 min at an excitation frequency of 13.56 MHz, to remove the organics on the surfaces and activate the surfaces. Activation Example 55 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were positioned in a plasma dry cleaner, and washed with N2/H2plasma for 10 min at an excitation frequency of 13.56 MHz, to remove the organics on the surfaces and activate the surfaces. Activation Example 56 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were positioned in a plasma dry cleaner, washed with O2plasma for 5 min at an excitation frequency of 13.56 MHz to remove the organics on the surfaces, and washed with N2/H2plasma for 5 min, to remove the oxides on the surfaces and activate the surfaces. Activation Example 57 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were positioned in a plasma dry cleaner, washed with O2plasma for 10 min at an excitation frequency of 13.56 MHz to remove the organics on the surfaces, and washed with N2/H2plasma for 5 min, to remove the oxides on the surfaces and activate the surfaces. Activation Example 58 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were positioned in a plasma dry cleaner, washed with O2plasma for 5 min at an excitation frequency of 13.56 MHz to remove the organics on the surfaces, and washed with N2/H2plasma for 10 min, to remove the oxides on the surfaces and activate the surfaces. Activation Example 59 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were positioned in a plasma dry cleaner, washed with O2plasma for 10 min at an excitation frequency of 13.56 MHz to remove the organics on the surfaces, and washed with N2/H2plasma for 10 min, to remove the oxides on the surfaces and activate the surfaces. The surface roughness of the glass members before activation was 0.512 nm. Activation Example 60 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were positioned in a plasma dry cleaner, washed with O2plasma for 10 min at an excitation frequency of 13.56 MHz to remove the organics on the surfaces, and washed with N2/H2plasma for 15 min, to remove the oxides on the surfaces and activate the surfaces. Activation Example 61 At room temperature, a first glass member and a second glass member were respectively washed in acetone, a peracetic acid solution or a calcium hypochlorite solution in sequence for 30 min, removed, washed with pure water and dried. The washed first glass member and second glass member were positioned in a plasma dry cleaner, washed with O2plasma for 15 min at an excitation frequency of 13.56 MHz to remove the organics on the surfaces, and washed with N2/H2plasma for 15 min, to remove the oxides on the surfaces and activate the surfaces. Detection Means after Activation The first glass members and second glass members obtained in all the above activation examples were determined for the contact angle with water drops. Specifically, water was dropped on the activated surface of clean first glass member and second glass member. If the water droplets can expand and wet the surface and the water droplets are visually observed to be round and evenly infiltrate the surface, or the contact angle of water with the glass is determined by a contact angle tester to be less than or equal to 10°, then the glass surface is considered to be clean and activated. The test results show that the contact angle (i.e. contact angle with water drops) of the activated surfaces of the first glass member and the second glass member obtained in all the activation examples is less than or equal to 10°. Specifically, the activated surfaces in Activation Examples 54-61 have respectively a contact angle of 7°, 5°, 4°, 4°, 3°, 2°, 3°, and 2°. Compounding Example 21 In this example, the sheet glass member (first glass member) and the rectangular frame-shaped glass member (second glass member) are both made of Schott glass (having a visible light transmittance of 91%-93%). The method for compounding the sheet glass member and the frame-shaped glass member is as follows. The sheet glass member and the frame-shaped glass member were activated following the method in Activation Example 59. The surface-activated sheet glass member and frame-shaped glass member were put into a vacuum box or a vacuum bag and evacuated (that is, coupling). The frame-shaped glass member was positioned to the outer peripheral edge of the sheet glass member by a positioning fixture, CCD or other positioning methods, during which caution was taken to avoid foreign objects or fingers touching the activated surfaces, to avoid contamination of the activated surface causing defects. After coupling, the glass members were heated to 600° C. and a pressure of 0.84 MPa was applied. The temperature and pressure were maintained for 2 hrs, and then the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together, and a casing was obtained, seeFIG.6Afor the schematic structure. In the example, the obtained casing has a light transmittance of more than 91% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the sheet glass member and the frame-shaped glass member are observed to be flat and smooth, and no obvious bubbles or fantasy colors are visually observed at the compounding position of the sheet glass member and the frame-shaped glass member (seeFIG.9). The bonding strength was tested according to the method in Compounding Example 1. The result shows that the bonding strength is 140 N (that is, 1.94 MPa), there is no change at the bonding position, but the glass member is broken. The casing obtained above was cut along the thickness direction at the bonding position where the sheet glass member and the frame-shaped glass member were connected to form a cross section, and the cross section was polished. No compounding traces or crevices were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicates that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 40% for 2 min. It is visually observed that obvious crevices are formed at the compounding interface in the cross section. Compounding Example 22 In this example, the sheet glass member (first glass member) and the rectangular frame-shaped glass member (second glass member) are both made of Corning GG3 glass (having a visible light transmittance of 91%-93%). The method for compounding the sheet glass member and the frame-shaped glass member is as follows. The sheet glass member and the frame-shaped glass member were activated following the method in Activation Example 59. The surface-activated sheet glass member and frame-shaped glass member were coupled, heated to 450° C. and a pressure of 1.0 MPa was applied. The temperature and pressure were maintained for 3 hours, and then the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together, and a casing was obtained, seeFIG.6Afor the schematic structure. In the example, the obtained casing has a light transmittance of more than 91% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the sheet glass member and the frame-shaped glass member are observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the sheet glass member and the frame-shaped glass member. The bonding strength was tested according to the method in Compounding Example 1. The bonding strength is 135 N (that is, 1.88 MPa), there is no change at the bonding position, but the glass member is broken. The casing obtained above was cut along the thickness direction at the bonding position where the sheet glass member and the frame-shaped glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicates that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 20% for 5 min. It is visually observed that obvious crevices having a width of 20-100 μm are formed at the compounding interface in the cross section. Compounding Example 23 In this example, the sheet glass member (first glass member) and the circular frame-shaped glass member (second glass member) are both made of Schott glass (having a visible light transmittance of 91%-93%). The method for compounding the sheet glass member and the frame-shaped glass member is as follows. The sheet glass member and the frame-shaped glass member were activated following the method in Activation Example 59. The surface-activated sheet glass member and frame-shaped glass member were coupled and heated to 250° C., and a pressure of 2.0 MPa was applied. The temperature and pressure were maintained for 3 hours, and then the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together, and a casing was obtained (seeFIG.6Afor the schematic structure). In the example, the obtained casing has a light transmittance of more than 91% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the sheet glass member and the frame-shaped glass member are observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the sheet glass member and the frame-shaped glass member. The bonding strength was tested according to the method in Compounding Example 1. The bonding strength is 130 N (that is, 1.8 MPa), there is no change at the bonding position, but the glass member is broken. The casing obtained above was cut along the thickness direction at the bonding position where the sheet glass member and the frame-shaped glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicates that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 15% for 5 min. It is visually observed that obvious crevices are formed at the compounding interface in the cross section. Compounding Example 24 In this example, the sheet glass member (first glass member) and the bar-shaped glass member (second glass member) are both made of Schott glass (having a visible light transmittance of 91%-93%). The method for compounding the sheet glass member and the frame-shaped glass member is as follows. The sheet glass member and the bar-shaped glass member were activated following the method in Activation Example 59. The surface-activated sheet glass member and bar-shaped glass member were coupled, heated to 750° C. and a pressure of 0.05 MPa was applied. The temperature and pressure were maintained for 3 hours, and then the glass members were slowly cooled. In this way, the glass members were partially or totally compounded together, and a casing was obtained, seeFIG.6Cfor the schematic structure. In the example, the obtained casing has a light transmittance of more than 91% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the sheet glass member and the bar-shaped glass member are observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the sheet glass member and the bar-shaped glass member. The bonding strength was tested according to the method in Compounding Example 1. The bonding strength is 135 N, there is no change at the bonding position, but the glass member is broken. The casing obtained above was cut along the thickness direction at the bonding position where the sheet glass member and the bar-shaped glass member were connected to form a cross section, and the cross section was polished. No compounding traces were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicated that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 30% for 3.5 min. The compounding interface of the sheet glass member and the bar-shaped glass member was evenly corroded at a rate that is higher than the corrosion rate of the sheet glass member and the bar-shaped glass member. It is visually observed that crevices are formed at the compounding interface in the cross section. Compounding Example 25 The process was the same as that in Compounding Example 21, except that the sheet glass member (first glass member) and the frame-shaped glass member (second glass member) were activated by the method as described in Activation Example 54. In the example, the obtained casing has a light transmittance of more than 91% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the sheet glass member and the frame-shaped glass member are observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the sheet glass member and the frame-shaped glass member. The bonding strength was tested. The test result shows that the bonding strength is 129 N (that is, 1.8 MPa), there is no change at the bonding position, but the glass member is broken. The casing obtained above was cut along the thickness direction at the bonding position where the sheet glass member and the frame-shaped glass member were connected to form a cross section, and the cross section was polished. No compounding traces or crevices were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicates that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 30% for 3 min. It is visually observed that obvious crevices are formed at the compounding interface in the cross section. Compounding Example 26 The process was the same as that in Compounding Example 21, except that the sheet glass member (first glass member) and the frame-shaped glass member (second glass member) were activated by the method as described in Activation Example 55. In the example, the obtained casing has a light transmittance of more than 91% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the sheet glass member and the frame-shaped glass member are observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the sheet glass member and the frame-shaped glass member. The bonding strength was tested. The results show that the bonding strength is 131 N (that is, 1.82 MPa), there is no change at the bonding position, but the glass member is broken. The casing obtained above was cut along the thickness direction at the bonding position where the sheet glass member and the frame-shaped glass member were connected to form a cross section, and the cross section was polished. No compounding traces or crevices were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicates that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 20% for 4 min. It is visually observed that obvious crevices are formed at the compounding interface in the cross section. Compounding Example 27 The process was the same as that in Compounding Example 21, except that the sheet glass member (first glass member) and the frame-shaped glass member (second glass member) were activated by the method as described in Activation Example 56. In the example, the obtained casing has a light transmittance of more than 91% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the sheet glass member and the frame-shaped glass member are observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the sheet glass member and the frame-shaped glass member. The bonding strength was tested. The test results show that the bonding strength is 145 N (that is, 2.0 MPa), there is no change at the bonding position, but the glass member is broken. The casing obtained above was cut along the thickness direction at the bonding position where the sheet glass member and the frame-shaped glass member were connected to form a cross section, and the cross section was polished. No compounding traces or crevices were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicates that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 15% for 7 min. It is visually observed that obvious crevices are formed at the compounding interface in the cross section. Compounding Example 28 The process was the same as that in Compounding Example 21, except that the sheet glass member (first glass member) and the frame-shaped glass member (second glass member) were activated by the method as described in Activation Example 57. In the example, the obtained casing has a light transmittance of more than 91% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the sheet glass member and the frame-shaped glass member are observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the sheet glass member and the frame-shaped glass member. The bonding strength was tested. The test results show that the bonding strength is 148 N (that is, 2.05 MPa), there is no change at the bonding position, but the glass member is broken. The casing obtained above was cut along the thickness direction at the bonding position where the sheet glass member and the frame-shaped glass member were connected to form a cross section, and the cross section was polished. No compounding traces or crevices were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicates that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 25% for 8 min. It is visually observed that obvious crevices are formed at the compounding interface in the cross section. Compounding Example 29 The process was the same as that in Compounding Example 21, except that the sheet glass member (first glass member) and the frame-shaped glass member (second glass member) were activated by the method as described in Activation Example 58. In the example, the obtained casing has a light transmittance of more than 91% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the sheet glass member and the frame-shaped glass member are observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the sheet glass member and the frame-shaped glass member. The bonding strength was tested. The test results show that the bonding strength is 149 N (that is, 2.06 MPa), there is no change at the bonding position, but the glass member is broken. The casing obtained above was cut along the thickness direction at the bonding position where the sheet glass member and the frame-shaped glass member were connected to form a cross section, and the cross section was polished. No compounding traces or crevices were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicates that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 35% for 5 min. It is visually observed that obvious crevices are formed at the compounding interface in the cross section. Compounding Example 30 The process was the same as that in Compounding Example 21, except that the sheet glass member (first glass member) and the frame-shaped glass member (second glass member) were activated by the method as described in Activation Example 60. In the example, the obtained casing has a light transmittance of more than 91% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the sheet glass member and the frame-shaped glass member are observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the sheet glass member and the frame-shaped glass member. The bonding strength was tested. The test results show that the bonding strength is 150 N (that is, 2.08 MPa), there is no change at the bonding position, but the glass member is broken. The casing obtained above was cut along the thickness direction at the bonding position where the sheet glass member and the frame-shaped glass member were connected to form a cross section, and the cross section was polished. No compounding traces or crevices were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicates that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 10% for 10 min. It is visually observed that obvious crevices are formed at the compounding interface in the cross section. Compounding Example 31 The process was the same as that in Compounding Example 21, except that the sheet glass member (first glass member) and the frame-shaped glass member (second glass member) were activated by the method as described in Activation Example 61. In the example, the obtained casing has a light transmittance of more than 91% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the sheet glass member and the frame-shaped glass member are observed to be flat and smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the sheet glass member and the frame-shaped glass member. The bonding strength was tested. The test results show that the bonding strength is 151 N (that is, 2.10 MPa), there is no change at the bonding position, but the glass member is broken. The casing obtained above was cut along the thickness direction at the bonding position where the sheet glass member and the frame-shaped glass member were connected to form a cross section, and the cross section was polished. No compounding traces or crevices were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicates that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 5% for 10 min. It is visually observed that obvious crevices are formed at the compounding interface in the cross section. Compounding Example 32 The process was the same as that in Compounding Example 21, except that the first glass member is of a curved glass shape, and the second glass member is of a curved glass shape; the surface of the first glass member is an upwardly bulged curved surface, and the surface of the second glass member is an upwardly depressed curved surface; and the surfaces of the portions at which the two glass members need to be compounded have the same radius of curvature, and continuous contact can be achieved without crevices. In the example, the obtained casing has a light transmittance of more than 91% for visible light (wavelength band 380-720 nm), which shows that the optical performance is better, and the performance during use is better. The outer surfaces of the first glass member and the second glass member are observed to be smooth, and there are no obvious bubbles or fantasy colors at the compounding position of the first glass member and the second glass member. The bonding strength was tested. The test results show that the bonding strength is 140 N (that is, 1.94 MPa), there is no change at the bonding position, but the glass member is broken. The casing obtained above was cut along the thickness direction at the bonding position where the first glass member and the second glass member were connected to form a cross section, and the cross section was polished. No compounding traces or crevices were observed visually by naked eyes or under a microscope at a magnification of 500×. This indicates that the compounding effect is good. The cross section was corroded in a hydrofluoric acid solution with a mass concentration of 5% for 10 min. It is visually observed that obvious crevices are formed at the compounding interface in the cross section. In the description of the present disclosure, it can be understood that, terms “first” and “second” are used only for a purpose of description, and shall not be construed as indicating or implying relative importance or implying a quantity of indicated technical features. Therefore, the features defined by “first”, and “second” may explicitly or implicitly include one or more features. In the description of the present disclosure, unless otherwise specifically limited, “a plurality of” means two or more than two. In the description of the present specification, the description of the reference terms “an embodiment”, “some embodiments”, “specific example”, “some examples” or the like means that specific features, structures, materials or characteristics described in combination with the embodiment are included in at least one embodiment of the present disclosure. In the present specification, the illustrative expression of the above terms is not necessarily referring to the same embodiment or example. Moreover, the described specific features, structures, materials or characteristics may be combined in any suitable manners in one or more embodiments. In addition, where there are no contradictions, the various embodiments or examples described in this specification and features of various embodiments or examples can be combined by those skilled in the art. Although the embodiments of the present disclosure have been shown and described above, it can be understood that the foregoing embodiments are exemplary and should not be understood as limitation to the present disclosure. A person of ordinary skill in the art can make changes, modifications, replacements, or variations to the foregoing embodiments within the scope of the present disclosure. | 165,216 |
11858845 | LIST OF REFERENCE CHARACTERS 1Flat body2Substrate3Layer structure4Sunlight5Back electrode layer6Absorber layer7Buffer layer8Front electrode layer9Adhesive layer10Cover plate11Outer surface12Solar cell13Inner surface14Module rear side15Structured area16,16′ Optical interference layer17Segment19Opaque coating20Multi-angle colorimeter21Rear side element22First area23Second area24Mask25First zone26Second zone27Outer side28Inner side DETAILED DESCRIPTION OF THE EMBODIMENTS InFIG.1, a flat body according to the invention as a whole denoted with the reference number1is schematically illustrated in a cross-sectional view In this case, the flat body1is, for example, in the form of a solar module with a composite pane structure. The cross-sectional view is perpendicular to the module surface. The flat body1comprises a cover plate10(e.g. front glass) and a substrate2on the back, which are firmly connected to each other by an adhesive layer9(e.g. lamination foil). Solar cells12(silicon wafer or thin film solar cells) are located on the substrate2. The coloring element for the flat body1is the coated cover plate10, whose outer surface11faces against the incident light and whose inner surface13is connected to the solar cells12via the adhesive layer9. The outer surface11of the cover plate10is located on its outer side27, the inner surface13on its inner side28. The substrate2with solar cells12forms an opaque rear side element21, whose inherent color is essentially determined by the solar cells12. In the edge areas and between the solar cells12, however, the color can also be determined by contacting strips and edge sealing or, in the case of wafer solar cells, by the back foil. The cover plate10here is a glass pane with the lowest possible absorption and consists, for example, of soda lime glass. The outer surface11and/or the inner surface13of the cover plate10are structured (e.g. by etching, sandblasting or rolling during the drawing method) and in addition, outer surface11and/or inner surface13have at least one optical interference layer, which is not shown inFIG.2and is explained in more detail below (seeFIGS.5and6). The flat body1can be used as an integrated part of a building envelope or free-standing wall, especially as a facade element. FIG.2shows an exemplary structure of a passive flat body1, which is to be used as an integrated component of a building envelope or free-standing wall, in particular as a facade element, and only fulfils a structural function. The flat body1comprises a transparent cover plate10and an opaque rear side element21. The cover plate10is configured as inFIG.1. The above embodiments apply analogously. It would also be possible to configure the cover plate10itself as a composite body, whereby it consists of a transparent core embedded in another transparent material (e.g. sandwich-like), which has the same optical refractive index as the core. The outer surface11and inner surface13are then formed by this material. This is not shown inFIG.2. The rear side element21is here, for example, in the form of an opaque coating19of the inner surface13, which extends over the entire inner surface13. The opaque coating19can consist of one or more layers. As coating, for example, lacquers, polymer layers, polymer films or inorganic layers of metal oxide powders, carbon or semiconductor materials can be used. The layer thickness of the rear side element21can be freely selected as long as the desired optical properties of the coating are guaranteed. If necessary, the rear side element21can be protected from environmental influences by a rear side cover, for example in the form of a further coating or film. In its embodiment as a coating, the rear side element21is non-load-bearing, so that the cover plate10has to meet the specific requirements for use as a facade element. In particular, the mechanical load-bearing capacity and the possibility of a suitable connection to the building structure must be ensured, for example by using frames, clamps or rear side rails. For this purpose, the cover plate10preferably consists of refined glass, such as thermally tempered glass, toughened safety glass (ESG), or partially tempered glass (TVG). The coating is opaque and can, for example, have a pre-defined color, so that the background color of the coating can create an overall color impression of the flat body1in the desired manner. It is equally possible for the rear side element21to be achromatic, dark and matt for this purpose. FIG.3illustrates a variant of the passive flat body1ofFIG.2, according to which the rear side element21is an independent body with a defined spatial shape, which is firmly connected to the inner surface13of the cover plate10here, for example, by means of a transparent adhesive layer9(e.g. laminating foil). In principle, any suitable joining technique can be used to firmly connect the cover plate and rear side element21, e.g. gluing or potting Advantageous are joining techniques where the transparent material used for joining (e.g. adhesive layer, laminating foil or potting material) has a refractive index of greater than 1.4 and less than 1.6. Otherwise, the resulting color of the flat body1may be changed in an undesired way. For example, the rear side element21is configured in the form of a flat plate, which forms a composite body with the cover plate10. The rear side element21is preferably load-bearing and has suitable mechanical properties for this purpose in order to ensure the load-bearing capacity of the flat body1either by itself or in combination with the cover plate10. The flat body1created in this way can be easily connected to a building as a facade element and must meet the overall requirements as a facade element in a building envelope. The rear side element21, for example, consists of a fiber composite material, glass, stone, metal or ceramic and can be coated in particular with a paint, for example a ceramic screen printing ink or organic glass paint or a suitable inorganic thin film, to provide a desired background color. It is also possible that the material of the rear side element21itself already has a desired color. For example, the rear side element21consists of a glass colored in the glass matrix. It is also possible to use CIGS thin-films, which are a waste product from the series production of thin-film solar modules, to achieve a particularly homogeneous color impression of a facade in combination with CIGS thin-film solar modules used as facade elements. The layer structure3for the solar cells12has no power generating function. A glass rear side element21can be easily connected to a glass cover plate10using conventional lamination methods. For example, the rear side element21is a metal plate, a metal foil or consists of a metal composite material. The metal plate or foil can be treated, for example, by anodizing or coating to produce the desired optical properties. The rear side element21can equally consist of building materials suitable for outdoor use, for example fiber cement plates, concrete plates, textile-reinforced or fiber-reinforced concrete shells, wood/wood fiber materials, plastics or other non-metallic composite materials. The surface of the material can be configured with the appropriate coloring technology to achieve the desired optical properties. The cover plate10is configured as inFIG.1. The above embodiments apply analogously. With reference toFIG.4, the exemplary structure of a thin-film solar module is explained in more detail inFIG.1The flat body1in the form of a thin-film solar module comprises a plurality of solar cells12which are serially interconnected in an integrated form, of which only two are shown in a simplified form. It goes without saying that in the flat body1there is usually a large number of solar cells12(for example approx. 100-150) connected in series. The flat body1has a composite pane structure in substrate configuration. It comprises the backside substrate2with a layer structure3of thin films applied to it, whereby the layer structure3is arranged on a light-entry side surface of the substrate2. The substrate2is here, for example, configured as a rigid, flat glass plate with a relatively high light transmittance, whereby other electrically insulating materials with the desired strength and inert behavior towards the method steps performed can be used equally well. The layer structure3comprises an opaque back electrode layer5arranged on the surface of the substrate2, which for example consists of an opaque metal such as molybdenum (Mo) and was applied to the substrate2by vapor deposition or magnetic field-assisted cathode sputtering. The back electrode layer5, for example, has a layer thickness in the range of 300 nm to 600 nm. On the back electrode layer5, a photovoltaic active (opaque) absorber layer6is deposited, which consists of a semiconductor whose band gap is capable of absorbing as much sunlight as possible. The absorber layer6, for example, consists of a conductive chalcopyrite semiconductor, for example a compound of the group Cu(ln/Ga)(S/Se)?, especially sodium (Na)-doped Cu(In/Ga)(S/Se)2. In the above formula, indium (In) and gallium (Ga) as well as sulfur (S) and selenium (Se) may be present optionally or in combination. The absorber layer6has a layer thickness which is, for example, in the range of 1-5 μm and is in particular about 2 μm. For the production of the absorber layer6, different layers of material are typically applied, e.g. by sputtering, which are then thermally converted into the compound semiconductor by heating in a furnace, if necessary in an S- and/or Se containing atmosphere (RTP=Rapid Thermal Processing). Experts are well acquainted with this method of manufacturing a compound semiconductor, so it is not necessary to go into it in detail here. A buffer layer7is deposited on the absorber layer6, which in this case consists of a single layer of cadmium sulfide (CdS), indium sulfide (InxSy) or zinc oxysulfide (ZnOS) and optionally a single layer of intrinsic zinc oxide (i-ZnO) or zinc magnesium oxide (ZnMgO), which is not shown inFIG.1. A front electrode layer8is applied to the buffer layer7, for example by sputtering. The front electrode layer8is transparent for radiation in the visible spectral range (“window electrode”), so that the incident sunlight4(illustrated by arrows inFIG.1) is only slightly attenuated. The front electrode layer8, for example, is based on a doped metal oxide, for example n-conducting aluminum (Al)-doped zinc oxide (ZnO). Such a front electrode layer8is generally referred to as TCO layer (TCO=Transparent Conductive Oxide) The layer thickness of the front electrode layer8, for example, is about 1000 nm Together with the buffer layer7and the absorber layer6, the front electrode layer8forms a heterojunction (i.e. a sequence of layers of the opposite conductivity type). The buffer layer7can cause an electronic matching between the absorber layer6and the front electrode layer8. To protect against environmental influences, the (plastic) adhesive layer9is applied to the layer structure3and serves to encapsulate the layer structure3. Bonded to the adhesive layer9is the sunlight-transparent front or light-entry side cover plate10, which in this case, for example, takes the form of a rigid (flat) glass plate made of extra-white glass with low iron content. The cover plate10is used for sealing and mechanical protection of the layer structure3. The cover plate10has the inner surface13facing the solar cells12and the outer surface11facing away from the solar cells12, which is also the module surface or module top side. Via the outer surface11, the thin-film solar module can absorb sunlight4to generate an electrical voltage at resulting voltage connections (+,−). A current path is illustrated inFIG.4by serially arranged arrows. The cover plate10and the substrate2are firmly connected (“laminated”) to each other by the adhesive layer9, whereby the adhesive layer9here, for example, is formed as a thermoplastic adhesive layer that becomes plastically deformable when heated and firmly connects the cover plate10and the substrate2to each other when cooled. The adhesive layer9can be provided in the production method as a laminating film and consists here, for example, of PVB. The cover plate10and the substrate2with the solar cells12embedded in the adhesive layer9together form a laminated composite. The module rear side14is given by the surface of substrate2facing away from the solar cells12. For the formation and series connection of the solar cells12, the layer structure3is structured using a suitable structuring technology, for example laser writing and/or mechanical ablation. For this purpose, it is common practice to insert direct sequences of three structuring lines P1-P2-P3each into the layer structure (stack)3. Here, at least the back electrode layer5is subdivided by first structuring lines P1, thus creating the back electrodes of the solar cells12Second structuring lines P2are used to divide at least the absorber layer6, thus creating the photovoltaic active areas (absorbers) of the solar cells12. Third patterning lines P3divide at least the front electrode layer8, creating the front electrodes of the solar cells12. By means of the second structuring line P2, the front electrode of a solar cell12is electrically connected to the back electrode of an adjacent solar cell12, whereby the front electrode contacts the back electrode directly, for example. In the example ofFIG.4, the trenches of the first structuring lines P1are filled by material of the absorber layer6. The trenches of the second structuring lines P2are filled by material of the front electrode layer8and the trenches of the third structuring lines P3are filled by the adhesive layer9. Each direct sequence of first, second and third structuring lines P1-P2-P3forms a structuring zone for series connection of two immediately adjacent solar cells12. The invention also covers solar modules based on silicon wafer cells and any other technology for the production of solar cells. FIG.5shows an enlarged section of the cover plate10of the flat body1illustrated inFIGS.1to4. The outer surface11of the cover plate10is structured in an area15, which in this example covers the complete outer surface11, i.e. outer surface11and structured area15are identical. The inner surface13is not structured Directly on the outer surface11, a first optical interference layer16is partially arranged. In the structured area15, the outer surface11has a height profile with mountains and valleys. More than 50% of the outer surface11consists of flat segments17, whose planes are each inclined to the plane of the cover plate10, i.e. have an angle different from zero. A mean height sublayer between the highest points (peaks) and lowest points (valleys) of the outer surface11is at least 5 μm and, for example, a maximum of 20% of the thickness of the transparent cover plate10. Relative to the plane of the cover plate10, at least 20% of the segments17have an angle of inclination in the range from greater than 0° to a maximum of 15°, at least 3 0° % of the segments have an angle of inclination in the range from greater than 15° to a maximum of 45° and less than 30% of the seg-merits17have an angle of inclination greater than 45°. In the example ofFIG.3, all segments have a maximum tilt angle of 45°. The first optical interference layer16is thin and has a layer thickness in the range of 0.1 to several (e.g. 5) micrometers. In addition, the first optical interference layer16has a refractive index of greater than 1.7, preferably greater than 2.0 and especially preferred greater than 2.3, as well as the lowest possible absorption in relation to the incident light. The first optical interference layer16can be single or multi-layered, i.e. consist of one or more refractive layers. Each refractive layer has a specific refractive index and consists of the same material. For example, the optical interference layer16consists of MgO, SiONx, Si3N4, ZrO2, TiOxand/or SiC. The electrical conductivity of the individual refractive layers, especially of the first optical interference layer16, should be as low as possible. The first optical interference layer16does not cover the outer surface11completely, but only partially. Specifically, the outer surface11is composed of a first area22covered by the first optical interference layer16and a second area23not covered by the first optical interference layer16. In particular, the first optical interference layer16can extend over and completely cover the entire outer surface11, with the exception of the second area23. The second area23and the first area22overlap with the structured area15when viewed vertically through the cover plate10, i.e as seen in a vertical projection (vertical extension) of the structured area15onto an (imaginary) surface parallel to the plane GE of the cover plate10, and as seen in a vertical projection (vertical extension) of the second area23and the first area22, respectively, on the same surface of the cover plate10, the first area23and the second area22overlap and are advantageously located within the structured area15. For example, the surface parallel to the plane GE is the inner surface13. FIG.5shows an example of the plane GE of cover plate10. The plane GE results from the essentially planar shape of the cover plate10. The drawn plane GE is only exemplary and may have a different position. In this example, where the inner surface13is not structured, the plane GE is parallel to the inner surface13. With respect to the structured outer surface11, the plane GE is parallel to an imaginary surface of the outer surface11created by averaging the segments17. In the first area22of the outer surface11, which is covered by the first optical interference layer16, a filtered reflection of light rays within a given or predeterminable wavelength range occurs, which is explained in more detail below. In the second area23of the outer surface11not covered by the first optical interference layer16, essentially no such filtered reflection occurs. A color effect by the optical interference layer16is therefore only present in the first area22of the outer surface11. In any case, there is a contrast. FIG.6shows a variant of the cover plate10ofFIG.5. To avoid unnecessary repetition, only the differences toFIG.5are explained and otherwise reference is made to the explanations inFIG.5. Accordingly, the first optical interference layer16is not located on the outer surface11of the cover plate10, but only on the unstructured inner surface13of the cover plate10. Analogous toFIG.5, the inner surface13has a first area22covered by the first optical interference layer16and a second area23not covered by the first optical interference layer16. Reference is now made toFIGS.7A-7F, where a schematic cross-sectional view illustrates an exemplary production of the cover plate10ofFIG.6. Accordingly, the outer surface11is structured and the inner surface13is not structured. The optical interference layer16is only applied to the inner surface13. The intermediate stages of the cover plate10during its manufacture are illustrated. For the sake of simplicity, the structuring of the outer surface11has been omitted.FIG.8also shows a flow chart of the successive steps performed in this method. Step i): According to a first alternative, a transparent cover plate10(front glass) is provided, which already has a structured area15on the outer surface11(FIG.7A). Step i′). According to a second alternative, a non-structured transparent cover plate10is provided, which is provided with a structured area15after provision. The method thus comprises providing a non-structured transparent cover plate10with an outer surface11intended to face an external environment and an opposite inner surface13, and forming a structured area15with a light-scattering structure in at least one surface selected from outer and inner surfaces (FIG.7A). In the present case, the formation of the structured area15can take place at any time, since the first optical interference layer16and the structured area15are located on different surfaces of the cover plate10. In the variant ofFIG.5, it would be necessary to form the structured area15already before applying mask24. It goes without saying that a cover plate10, which already has a structured area15, can be provided with a structured area15again after provision. In the first alternative according to step i), the formation of a structured area15with a light-scattering structure in at least one surface selected from the outer and inner surface can be provided as an option. Step ii): Subsequently, a mask24is applied to part of the inner surface13of the cover plate10. The mask24does not cover a first area22of the inner surface13, but covers a second area23of the inner surface13. The second area23, preferably the complete second area23, has an overlap with the structured area15when viewed vertically through the cover plate10(FIG.7B). Step iii): Subsequently, a (first) optical interference layer16for reflecting light within a given wavelength range is applied to the inner surface13, which is partially covered by the mask24. The optical interference layer16is applied to the mask24and at least partially to the first area22of the inner surface13not covered by the mask24(FIG.7C). Step iv): Subsequently, the mask24is removed, whereby the optical interference layer16applied to the mask24is also removed (FIG.7D). By following steps i) to iv) above, a cover plate10with the configuration ofFIG.6can be produced. According to a particularly preferred embodiment of the method, a further step v) is optionally carried out: Step v) Here, at least one further optical interference layer16′ for reflecting light within a specified wavelength range is applied to the second area23of the inner surface13and at least partially, in particular completely, to the already applied optical interference layer16. The cover plate10thus formed is illustrated inFIG.7E. The first optical interference layer16applied only partially in the first area22leads to a local color effect of the cover plate10, corresponding to the reflection of light within a given wavelength range of the optical interference layer16. In the installed state of the cover plate10, the color of the flat body1in the first area22results from a combination of the color conditioned by the first optical reflection layer16and the background color of the rear side element21. In the embodiments ofFIGS.5and6, there is no first optical interference layer16in the second area23. In the installed state of the cover plate10, the local color effect in the second area23is mainly due to the background color of the rear side element21, whose color can be seen through the transparent cover plate10. In the embodiment ofFIG.7E, the second area23contains the additional (second) optical interference layer16′. In the first area22the two optical interference layers16,16′ are superimposed. In the installed state of the cover plate10, the color of the flat body1in the second area23results from a combination of the color caused by the optical reflection layer16′ and the background color of the rear side element21. In the first area22, the color results from a combination of the color caused by the two optical reflection layers16,16′ superimposed on each other and the background color of the rear side element21. As illustrated inFIG.7F, the cover plate10may have at least one additional (third) optical interference layer16″, which may in particular be applied to the outer surface11and/or inner surface13over the entire surface. The third optical interference layer16″ is applied to the first area22and the second area23of the inner surface13. The third optical interference layer16″ can be provided as an alternative or supplement to the second optical interference layer16′. As shown inFIG.9by means of a view of the flat body1with cover plate10, the surface of flat body1can have two colors in all embodiments. This allows patterns (here: bars) or characters (here: “A-3”) that encode information, especially text, to be set off against a background of a different color. InFIG.9, the viewer looks at the cover plate10from above. In the embodiments of the cover plate10ofFIGS.5and6, a first color in the first area22results from a combination of the color effect of the optical interference layer16and the background color of the rear side element21and a second color in the second area23results from the background color of the rear side element21. The color in the first area22can be freely selected. When configuring the cover plate10ofFIG.7E, a first color in the first area22results from a combination of the color effect of the two optical interference layers16,16′ and the background color of the rear side element21and a second color in the second area23results from a combination of the color effect of the optical interference layer16′ applied later and the background color of the rear side element21. Both the first color in the first area22and the second color in the second area23are selectable within a large color space within the limits of the physical degrees of freedom (layer thicknesses, refractive indices). InFIG.9, the patterns and characters correspond to the second area23and the differently colored background corresponds to the first area22, but it is equally possible that the patterns and characters correspond to the first area22and the differently colored background corresponds to the second area23. In the following, the function of the structuring of the outer surface11of the cover plate10is described in detail. First, considerFIG.10, which illustrates typical lighting conditions for a flat body1configured as a facade element According to this, light from the sun S hits the cover plate10directly and is reflected at the gloss angle (angle of incidence=angle of reflection, relative to the surface normal of the plane of the cover plate). The incident light beam E and the light beam R reflected at the gloss angle are shown. In addition to the reflected light beam R, the incident light is also diffusely scattered outside the gloss angle due to the configuration according to the invention of at least one structured side inside or outside and the interference layer on the inside. Two diffusely scattered light beams R′ are shown as examples. The color effect results from reflection, scattering and interference. If an observer B stands in front of the flat body1and looks vertically at the cover plate10in front of him, his eye only rarely encounters the directly reflected light R (i.e. the observer is usually not standing at the gloss angle) This is illustrated inFIG.10, where the observer B is outside the gloss angle and sees only the diffusely scattered light beam R′. On a smooth cover plate without structured areas inside or outside, the intensity of the diffusely scattered light R′ is relatively low and shows a very strong angle dependence. Only when the diffusely scattered portion is sufficiently large, a clear color with satisfactory intensity (brightness, L-value) is obtained. The basic principle of the mode of action of the inclined segments17of the structured area15is illustrated inFIG.11, which shows as an example the different light paths for an observer B looking perpendicularly at the glass surface or outer surface11of the flat body1. Shown are three segments17with different inclinations to the schematically illustrated plane GE of the cover plate10, as well as the light rays E hitting the segments17, which are reflected by the segments17in each case at the local gloss angle to the observer B (reflected light rays R). The central segment17is arranged parallel to the plane GE, whereby the incident light beam E hits the segment17vertically and is reflected vertically to the observer B (reflected beam R). For the central segment17, the gloss angle and the local gloss angle are identical. For the two adjacent segments17, the incident light rays E each have an angle different from zero to the surface normal on the plane GE and also hit the observer B in the local gloss angle. Due to the different inclinations of the segments17, light from different directions is reflected in each case in the local gloss angle of the segments17to the observer B looking perpendicularly on the module surface. In the example ofFIG.11, the angles of incidence and reflection are 45° maximum. InFIG.12a situation is shown where the observer B looks at the plane GE of the cover plate10at an angle of 45° to the surface normal. As inFIG.11, three segments17with different inclinations to the plane GE of the cover plate10are shown as an example, as well as the light rays E hitting the segments17, which are reflected by the segments17at the local glancing angle to the observer B (reflected light rays R). Due to the different inclinations of the segments17, light from different directions is reflected at the local gloss angle to the observer B looking at the surface. In the example ofFIG.12, the angles of incidence and reflection are 67.5° maximum. Basically, if the values of the gloss angle are relatively large, the reflected light n is shifted towards shorter wavelengths. This spectral shift can be reduced, for example, by a higher refractive index of the optical interference layer. However, the effect on the color visible to the human eye depends on the complex weighting of the spectrum with the sensitivity curves of the human eye. In the case of relatively steep surface inclinations, multiple reflections can also occur on adjacent facets. FIG.13shows a situation where the light source and accordingly the incident light rays are always inclined at an angle of 45° to the plane GE of cover plate10. The observer B observes the surface of the flat body1at different angles. The angles given inFIG.13are to be understood as follows: Angle of incidence (relative to plane GE of cover plate10)/angle of observation or reflection (deviation from the angle of gloss relative to surface normal on plane GE). The degree character “°” is not specified.FIG.13shows an example of four segments17with different inclinations to plane GE. Only in one segment17, whose plane is parallel to the plane of cover plate10, the observer B is located at the gloss angle with respect to plane GE: 45/0. This means that the incident light beam has an angle of 45′ to plane GE, the reflected light beam has an angular deviation of zero from the gloss angle. For the other segments17, the observer B is outside the gloss angle. In the two left-hand segments17(45/90, 45/45), the observer observes the surface of the flat body1at an angle of 90° and 45° to the gloss angle, respectively, and the light is incident at an angle of 45° to the plane GE. In the right segment17(45/−15), the observer is at an angle of −15° to the glancing angle. Due to the differently inclined segments17and the resulting reflection in the local gloss angle, light is reflected with sufficient intensity towards the observer B even if the observer is not located in the gloss angle, relative to the plane GE of cover plate10. FIG.14shows a situation in which the observer B observes the surface of the flat body1always at an angle of 45° to the module surface or plane GE of the cover plate10.FIG.14shows an example of four segments17with different inclinations to the plane GE Only in one segment17, whose plane is parallel to the plane GE, the observer B is located at the gloss angle: 45/0. In the other segments17, the observer B is located outside the gloss angle. In the two left-hand segments17(45/90, 45/45), the observer B observes the surface of the flat body1at an angle of 45°, whereby the light is incident at a deviation of 90° or 45° relative to the gloss angle. In the right segment17(45/−15) the light is incident at an angle of −15° relative to the gloss angle. Due to the differently inclined segments17and the resulting reflection in the local gloss angle, light is reflected with sufficient intensity towards the observer B even if light is incident outside the gloss angle. In the flat body1according to the invention, a homogeneous color impression in a specifiable wavelength range can be achieved by structuring the outer surface11of the cover plate10in combination with the at least one coloring optical interference layer16,16′, whereby the color impression is far less dependent on angle in comparison to a non-structured surface. FIG.15shows the reflection at the optical interference layer16,16′ with layer thickness d. The incident light beam E is reflected both at the interface atmospheric interference layer (R1) and at the interface interference layer-cover plate (R2). If the path difference of the two light beams R1, R2corresponds to a multiple of the wavelength of the incident light beam, constructive interference occurs, while destructive interference occurs if the path difference is a multiple of half the wavelength. When illuminated with white light, the optical interference layer9thus acts as a color filter, since constructive interference, depending on the refractive index n and layer thickness d, only occurs for light of a suitable wavelength. Here a is the angle of the reflected rays R1, R2to the surface normal. The light rays R′ exemplify the reflected light outside the gloss angle, which can occur in the structured area15if the roughness of the interface between the interference layer and the cover plate is too large. In order to fulfill the interference condition, it is necessary that the scattering centers are each smaller than the wavelength and layer thickness. This can be achieved by the minimum surface area of the segments17and their maximum roughness, as claimed in the invention. If the outer surface11of the cover plate10is coated with an optical interference layer16, consisting of an inorganic, chemically inert and hard layer such as Si3N4, this results in a high scratch resistance, chemical resistance and dirt-repellent effect for the flat body1. In addition, the use of photocatalytic layers such as TiO2can result in a self-cleaning effect. Climatic tests have also shown that interference layers of materials such as Si3N4or TiO2also prevent the corrosion of a glass cover plate by damp heat. Reference is now made toFIG.16, which illustrates an embodiment of cover plate1. To avoid unnecessary repetition, only the differences to the embodiment ofFIG.5are described and otherwise reference is made to the above explanations. With this embodiment, the structured area15of the outer surface11has first zones25and second zones26Here, the first zones25are configured in such a way that the segments17have a mean roughness that is less than 15% of the layer thickness d of the optical interference layer16on the outer surface11. In the embodiment ofFIG.5, this applies to the entire structured area15. In contrast, the mean roughness in the second zones26is so high that interference in the optical interference layer16is prevented. For example, the mean roughness of the segments17in the second zones26is more than 50% of the layer thickness of the optical interference layer16Therefore, the flat body1has a homogeneous color in the first zones25, which results from the color filter effect of the optical interference layer16. In the second zones26, the optical interference layer16has no color filter effect due to the lack of constructive interference, and thus there is essentially a surface that corresponds to the flat body1without optical interference layer16. Therefore, the flat body1can be provided with a homogeneous color in the first zones25. InFIG.16, the second zones16are schematically illustrated by a greater roughness. For reasons of simplified representation, the first zone22, which does not contain an optical interference layer16, is not shown. For the at least one additional optical interference layer16′, the explanations apply analogously. The function of the structured outer surface11in combination with the interference layer16on the inside is explained in detail inFIG.17in accordance with the embodiment ofFIG.6. For the sake of simplicity, the first area22, which does not contain an optical interference layer16, is not shown. It shows examples of different light paths for differently inclined segments17of cover plate10. Three segments17are shown as examples, the right segment17being parallel to the plane of cover plate10and the other two segments17having an angle to the plane of cover plate10that is different from zero. The reflection of the light rays at the interference layer16is shown in simplified form. The reflection at the interference layer16is explained in connection withFIG.12.FIG.17shows the light paths for three light beams, each of which hits the differently inclined segments17of the outer surface11of the cover plate10at the same angle to the normal of the plane of the cover plate10. The respective perpendicular to the segments17is shown as a dotted line. Due to the differently inclined segments17, the light rays are reflected in different ways. A first light beam1-1hits a segment17, crosses the cover plate2as refracted light beam1-2, is reflected as light beam1-3by the interference layer16(in the gloss angle), and emerges as refracted light beam1-4from the cover plate10towards the outer environment. The light beam1-4ultimately reflected by the cover plate10has a different angle to the normal to the plane of the cover plate10than the incident light beam1-1, so that there is no reflection at the gloss angle but scattering. In the same way, a second light beam2-1hits another segment17, crosses the cover plate2as refracted light beam2-2, is reflected as light beam2-3by the interference layer16, and emerges as refracted light beam2-4from the cover plate10towards the outer environment. The reflected light beam2-4emerges from the cover plate10approximately against the direction of incidence of the light beam2-1, which is also a scattering method and not a reflection in the gloss angle. A third light beam3-1hits another segment17, crosses the cover plate10as refracted light beam3-2, is reflected as light beam3-3by the interference layer16, and emerges as refracted light beam3-4from the cover plate10towards the outer environment. This segment17lies parallel to the plane of the cover plate10, so that the light beam2-4is reflected in the gloss angle. It is important to note that due to the refraction at the respective segment17and subsequent reflection at the interface with interference layer16and further refraction at the structured surface, those segments17which are inclined to the plane of the cover plate10, result in a strong overall reflection even outside the gloss angle (relative to the plane of the cover plate2), so that in combination with the interference layer16, a color effect of the reflected light is achieved even outside the gloss angle of the glass plane.FIG.17shows an example of the position of an observer B who is outside the gloss angle. Due to the relatively strongly (diffusely) scattering cover plate10with external structuring and an interference layer on the inside, there are usually suitable light paths for different viewing angles outside the gloss angle that have passed through the interference layer. This results in a color impression that is much less directional than in conventional modules without structured area15. FIG.18illustrates a measuring arrangement for determining the diffuse scattering of the flat body1according to the invention with a commercially available multi-angle colorimeter20(multi-angle color measurement). The structured area15, which is not shown in detail, extends over the complete cover plate10(e.g. glass). Here, a light beam is directed onto the outer surface11of the flat body1to be characterized at different angles of incidence and the scattered or reflected light is spectrally measured from different observation angles, for example 15° (related to gloss angle) For example, at an angle of observation of 45° (measured relative to the surface normal) and an angle of incidence of 45° (measured from the gloss angle), the incident steel is exactly perpendicular to the surface (45/45). At an observation angle of 15° and an angle of incidence of 45°, the direction of incidence 30° from the surface normal is on the same side as the direction of observation (15/45). The multi-angle colorimeter20is positioned relative to the surface normal at an observation angle of 45′ or 15°. As can be seen from the above description of the invention, the invention provides an improved cover plate, a flat body with the improved cover plate, as well as methods for its production, which have at least two very homogeneous, intensive colors, with little or no directional dependence. The surface of the flat body can be provided with at least two colors so that colored patterns and characters encoding information can be displayed against a differently colored background. Active and passive flat bodies can be produced cost-effectively in various shapes and sizes and can be used as integrated components of a building wall or a free-standing wall, especially as facade elements. Active and passive flat bodies can be combined as facade elements in an aesthetically pleasing way. Multicolored solar modules (coloring by interference layer(s), especially CIGS thin-film solar modules, can be advantageously be made available, whereby a homogeneous color effect of the facade can be achieved. With active flat bodies, the loss of efficiency is acceptable. For passive flat bodies, the semiconductor layer stack can be replaced by other, mostly cheaper materials and other elements such as junction box, edge sealing, contact strips and cables can be eliminated. The invention is particularly advantageous for the production of multicolored fitting pieces, which are particularly necessary for the transition to openings or the edges of buildings. Passive surface elements can provide largely the same color impression under different lighting conditions as solar modules. If non-rectangular facade elements are desired to complement solar modules, passive flat bodies can be produced much more cost-effectively than solar modules. The invention thus provides an advantageous improvement that enables the production of multicolored flat bodies that have a relatively low loss of efficiency as active flat bodies. In particular, the aesthetically pleasing use of active and passive flat bodies as facade elements is possible. | 42,755 |
11858846 | DETAILED DESCRIPTION In order to make the purposes, technical solutions and advantages of the present invention to be more clarity, the present invention will be further described in detail with reference to detailed embodiments, but not limited by the description. The measured parameters, measuring methods and instruments of the glass with high refractive index used for the fiber optic imaging element with medium-expansion of the present invention are as follows:(1) refractive index nD[the refractive index of glass at λ=589.3 nm];(2) the average coefficient of thermal expansion α30/300[10−7/° C.] at 30-300° C. Wherein the refractive index nDof glass is measured by a refractive index device; the coefficient of linear thermal expansion at 30-300° C. is measured by a horizontal dilatometer using the method specified in ISO 7991, and expressed by a coefficient of mean linear thermal expansion. Chemical compositions (wt. %) and glass performances of the embodiments are detailed listed in Table 1. TABLE 1chemical compositions (wt. %) and physical values ofthe glass samplescompositionembodiment 1embodiment 2embodiment 3embodiment 4embodiment 5SiO297785Al2O310005B2O32325252428CaO00003BaO128.41076La2O33432.8323430Nb2O54767.58Ta2O50.50.50.500.5Y2O30000.50ZnO48879TiO287654ZrO244566SnO20.50.260.510.5α30/30070.23467.91866.83071.09468.607[10−7/° C.]nD1.801.821.821.821.81 The raw materials used in the following embodiments and their requirements are as follows: Quartz sand (high purity, 150 μm oversize is less than 1%, 45 μm undersize is less than 30%, the content of Fe2O3is less than 0.01 wt. %), aluminum hydroxide (analytical purity, average particle size 50 μm), boric acid or boron anhydride (400 μm oversize is less than 10%, 63 μm undersize is less than 10%), calcium carbonate (analytical purity, average particle size 250 μm), barium carbonate (analytical purity, purity ≥99.0%), lanthanum trioxide (5N), niobium pentoxide (5N), tantalum pentoxide (5N), yttrium trioxide (5N), zinc oxide (analytical purity), titanium dioxide (chemical purity), zirconium oxide (analytical purity), stannic oxide (analytical purity). Referring toFIG.1, CTE in figures is Coefficient of Thermal Expansion, which test range is 30-300° C. The coefficient of thermal expansion of the comparative high expansion glass is 91.324×10−7/° C., and the coefficient of thermal expansion of embodiment 1 to embodiment 5 in the present invention respectively is 70.234×10−7/° C., 67.918×10−7/° C., 66.830×10−7/° C., 71.094×10−7/° C., 68.607×10−7/° C. The present invention will be further described below through the specific preparation method of embodiments: Embodiment 1 Firstly, raw materials are selected according to the glass composition of embodiment 1 in Table 1, and oxides of elements with valence state change in the glass raw materials such as Fe2O3are strictly controlled, and the content of Fe2O3in a finished product of glass is less than 100 PPm. The glass batch meets the chemical compositions of glass in Table 1, and then quartz sand, aluminum hydroxide, boric acid, calcium carbonate, barium carbonate, lanthanum oxide, niobium oxide, tantalum oxide, yttrium oxide, zinc oxide, titanium dioxide, zirconium oxide and stannic oxide are put into a platinum crucible and melted for 6 hours at 1400° C. In the glass melting process, the glass is stirred twice to melt evenly. After melting, the glass is cooled to 1320° C. and fining for 2 hours to obtain a molten glass. Thereafter, the molten glass is cast into a test specimen according to the specified requirements, then annealing is carried out and the annealing process is that preserving heat for 1 hour at 625° C., and cooling to 60° C. from 625° C. for 12 hours, and then cooling to room temperature along with the furnace. Its test performance is shown in Table 1, (1) a refractive index is 1.80; (2) a coefficient of mean linear thermal expansion at 30-300° C. is 70.234×10−7/° C. Embodiment 2 The actual composition of glass refers to embodiment 2 in Table 1, and uses the same requirements for raw material as embodiment 1. Quartz sand, aluminum hydroxide, boric anhydride, calcium carbonate, barium nitrate, lanthanum oxide, niobium oxide, tantalum oxide, yttrium oxide, zinc oxide, titanium dioxide, zirconium oxide and stannic oxide are put into a platinum crucible and melted for 8 hours at 1350° C. In the glass melting process, the glass is stirred once to melt evenly. After melting, the glass is cooled to 1300° C. and fining for 1 hour to obtain a molten glass. Thereafter, the molten glass is cast into a test sample according to the specified requirements, then annealing is carried out and the annealing process is that preserving heat for 1 hour at 650° C., and cooling to 60° C. from 650° C. for 12 hours, and then cooling to room temperature along with the furnace. The test conditions used are the same as embodiment 1, and the basic performances of samples are shown in Table 1. (1) a refractive index is 1.82; (2) an coefficient of mean linear thermal expansion at 30-300° C. is 67.918×10−7/° C. Embodiment 3 The actual composition of glass refers to embodiment 3 in Table 1, and uses the same raw material and requirements for raw material as embodiment 1. Raw materials are melted for 4 hours at 1450° C. In the glass melting process, the glass is stirred twice to melt evenly. After melting, the glass is cooled to 1340° C. and fining 2 hours to obtain a molten glass. Thereafter, the molten glass is cast into a test sample according to the specified requirements, then annealing is carried out and the annealing process is that preserving heat for 1 hour at 600° C., and cooling to 60° C. from 600° C. for 12 hours, and then cooling to room temperature along with the furnace. The test conditions used are the same as embodiment 1, and the basic performances of samples are shown in Table 1. (1) a refractive index is 1.82; (2) an coefficient of mean linear thermal expansion at 30-300° C. is 66.830×10−7/° C. Embodiment 4 The actual composition of glass refers to embodiment 4 in Table 1, uses the same raw material and requirements for raw material as embodiment 1 and adopts the same melting process system and test conditions as embodiment 1. The basic performances of samples are shown in Table 1. (1) a refractive index is 1.82; (2) a coefficient of mean linear thermal expansion at 30-300° C. is 71.094×10−7/° C. Embodiment 5 The actual composition of glass refers to embodiment 5 in Table 1, uses the same raw material and requirements for raw material as embodiment 1 and adopts the same melting process system and test conditions as embodiment 1. The basic performances of samples are shown in Table 1. (1) a refractive index is 1.81; (2) a coefficient of mean linear thermal expansion at 30-300° C. is 68.607×10−7/° C. From the data obtained in embodiments, it can be known that the glass with high refractive index for fiber optic imaging elements with medium-expansion of the present invention has the advantages of high refractive index and does not contain heavy metal oxides that are seriously harmful to the environment, and is suitable for fabricating fiber optic imaging elements. The fiber optic imaging element can be a fiber optical faceplate, a fiber optical image inverter, a fiber optical taper and a fiber optical bundle for image transmission, etc., wherein the core glass used is fabricated from the glass with high refractive index for fiber optic imaging elements with medium-expansion of the present invention. In addition, with the development trend of miniaturization of optical technology and photoelectronic technology, a glass with a high refractive index has an excellent chemical stability, a low coefficient of thermal expansion, and an excellent transmission can shorten the focal length of lens to achieve that shorten the size of the component or lens assembly. The glass with a high refractive index of the present invention can be used as an optical glass for this type of technology. The above descriptions are only exemplary embodiments of the present invention, and are not intended to limit the present invention. The protection scope of the present invention is claimed by the claims, and any modification, equivalent replacement, improvement, etc. made to the present invention by those skilled in the art within the spirit and protection scope of the present invention should be included in the protection scope of the present invention. | 8,503 |
11858847 | DETAILED DESCRIPTION OF THE DISCLOSED EMBODIMENTS Hyaloclastite is a hydrated tuff-like breccia typically rich in black volcanic glass, formed during volcanic eruptions under water, under ice or where subaerial flows reach the sea or other bodies of water. It has the appearance of angular fragments sized from approximately a millimeter to a few centimeters. Larger fragments can be found up to the size of pillow lava as well. Several minerals are found in hyaloclastite masses including, but not limited to, sideromelane, tachylite. palagonite, olivine, pyroxene, magnetite, quartz, hornblende, biotite, hypersthene, feldspathoids, plagioclase, calcite and others. Fragmentation can occur by both an explosive eruption process or by an essentially nonexplosive process associated with the spalling of pillow basalt rinds by thermal shock or chill shattering of molten lava. The water-quenched basalt glass is called sideromelane, a pure variety of glass that is transparent, and lacks the very small iron-oxide crystals found in the more common opaque variety of basalt glass called tachylite. In hyaloclastite, these glassy fragments are typically surrounded by a matrix of yellow-to-brown palagonite, a wax-like substance that forms from the hydration and alteration of the sideromelane and other minerals. Depending on the type of lava, the rate of cooling and the amount of lava fragmentation, the particle of the volcanic glass (sideromelane) can be mixed with other volcanic rocks or crystalline minerals, such as olivine, pyroxene, magnetite, quartz, plagioclase, calcite and others. Hyaloclastite is usually found within or adjacent subglacial volcanoes, such as tuyas, which is a type of distinctive, flat-topped, steep-sided volcano formed when lava erupts under or through a thick glacier or ice sheet. Hyaloclastite ridges are also called tindars and subglacial mounds are called tuyas or mobergs. They have been formed by subglacial volcanic eruptions during the last glacial period. A subglacial mound is a type of subglacial volcano. This type of volcano forms when lava erupts beneath a thick glacier or ice sheet. The magma forming these volcanoes was not hot enough to melt a vertical pipe through the overlying glacial ice, instead forming hyaloclastite and pillow lava deep beneath the glacial ice field. Once the glacier retreated, the subglacial volcano was revealed, with a unique shape as a result of its confinement within the glacial ice. Subglacial volcanoes are somewhat rare worldwide, being confined to regions that were formerly covered by continental ice sheets and also had active volcanism during the same period. Currently, volcanic eruptions under existing glaciers may create hyaloclastite as well. Hyaloclastite tuff-like breccia is a pyroclastic rock comprised of glassy juvenile clasts contained in a fine-grained matrix dominated by glassy shards. Hyaloclastite breccias are typically products of phreatomagmatic eruptions in particular associated with the eruption of magmas into bodies of water and form by fragmentation of chilled magma. They are often formed from basaltic magmas and are associated with pillow lavas and sheet flows. In addition, any other type of lava, such as intermediate, andesitic, dacitic and rhyolitic, can form hyaloclastite under similar rapid cooling or quenching conditions. In lava deltas, hyaloclastite forms the main constituent of foresets formed ahead of the expanding delta. The foresets fill in the seabed topography, eventually building up to sea level, allowing the subaerial flow to move forward until it reaches the sea again. At mid-ocean ridges, tectonic plates diverge, creating fissures on the ocean floor. Along these fissures underwater volcanoes erupt forming sea mounds that in some places can reach the surface of the water. As the lava erupts underwater, it can be rapidly quenched thereby creating hyaloclastite. This is an active process especially at hot spots around the world. These hot spots are an important cause of island formation. These islands are a prime sources of hyaloclastite formation. Volcanic lava eruptions in Hawaii that spill in the ocean are also rapidly quenched and fragmented thus producing hyaloclastite. The rapid cooling and quenching prevents or reduces lava crystallization thus hyaloclastite may have a significant amorphous make up. Basalt is an aphanitic (fine-grained) igneous rock with generally 43% to 53% silica (SiO2) containing essentially calcic plagioclase feldspar and pyroxene (usually Augite), with or without olivine. Intermediate basalt has generally between 53% to 57% silica (SiO2) content. Basalts can also contain quartz, hornblende, biotite, hypersthene (an orthopyroxene) and feldspathoids. Basalts are often porphyritic and can contain mantle xenoliths. Basalt is distinguished from pyroxene andesite by its more calcic plagioclase. There are two main chemical subtypes of basalt: tholeiites which are silica saturated to oversaturated and alkali basalts that are silica undersaturated. Tholeiitic basalt dominate the upper layers of oceanic crust and oceanic islands, alkali basalts are common on oceanic islands and in continental magmatism. Basalts can occur as both shallow hypabyssal intrusions or as lava flows. The average density basalt is approximately 3.0 gm/cm3. Andesite is an abundant igneous (volcanic) rock of intermediate composition, with aphanitic to porphyritic texture. In a general sense, it is an intermediate type between basalt and dacite, and ranges from 57% to 63% silicon dioxide (SiO2). The mineral assemblage is typically dominated by plagioclase plus pyroxene or hornblende. Magnetite, zircon, apatite, ilmenite, biotite, and garnet are common accessory minerals. Alkali feldspar may be present in minor amounts. Dacite is an igneous, volcanic rock with an aphanitic to porphyritic texture and is intermediate in composition between andesite and rhyolite and ranges from 63% to 69% silicon dioxide (SiO2). It consists mostly of plagioclase feldspar with biotite, hornblende, and pyroxene (augite and/or enstatite). It has quartz as rounded, corroded phenocrysts, or as an element of the ground-mass. The plagioclase ranges from oligoclase to andesine and labradorite. Sanidine occurs, although in small proportions, in some dacites, and when abundant gives rise to rocks that form transitions to the rhyolites. The groundmass of these rocks is composed of plagioclase and quartz. Rhyolite is an igneous (volcanic) rock of felsic (silica-rich) composition, typically greater than 69% SiO2. It may have a texture from glassy to aphanitic to porphyritic. The mineral assemblage is usually quartz, sanidine and plagioclase. Biotite and hornblende are common accessory minerals. Hyaloclastite can be classified based on the amount of silica content as: basaltic (less than 53% by weight SiO2), intermediate (approx. 53-57% by weight SiO2), or silicic such as andesitic (approximately 57-63% by weight SiO2), dacitic (approximately by weight 63-69% by weight SiO2), or rhyolitic (greater than 69% by weight SiO2). Basaltic hyaloclastite can be classified based on alkalinity level as tholeiitic, intermediate and alkaline. As used herein, the term “hyaloclastite” shall mean hyaloclastite from any and all sources; i.e., all hyaloclastites irrespective of the mineral source from which it is derived. Hyaloclastite deposits can be found in many places throughout the world including, but not limited to, Alaska, British Columbia, Hawaii, Iceland, throughout the world oceans on seamounts and on oceanic islands formed at magmatic arcs and tectonic plate rifts by volcanic activity, such as the mid-Atlantic ridge, and others. In one disclosed embodiment, the present invention comprises hyaloclastite in powder form. The particle size of the hyaloclastite powder is sufficiently small such that the hyaloclastite powder has pozzolanic properties. The hyaloclastite powder preferably has a volume-based mean particle size of less than or equal to approximately 40 μm, more preferably less than or equal to 20 μm, most preferably less than or equal to 15 μm, especially less than or equal to 10 μm, more especially less than or equal to 5 μm. The hyaloclastite powder preferably has a Blaine value of approximately 1,500 to approximately 10,000, more preferably approximately 3,500 to approximately 10,000, most preferably approximately 4,500 to approximately 10,000, especially approximately 6,000 to approximately 10,000. The hyaloclastite powder preferably has a Blaine value of greater than or equal to approximately 10,000. The foregoing ranges include all of the intermediate values. To achieve the desired particles size, the hyaloclastite rock can be ground using conventional rock grinding means including, but not limited to, a ball mill, a roll mill or a plate mill. A particle size classifier can be used in conjunction with the mill to achieve the desired particle size. Equipment for grinding and classifying hyaloclastite to the desired particle size is commercially available from, for example, F. L. Smidth, Bethlehem, PA; Metso, Helsinki, Finland and others. The ground hyaloclastite powder is then preferably classified by screening the powder with a 325 mesh screen or sieve. Preferably approximately 80% by volume of the hyaloclastite powder passes through a 325 mesh screen, more preferably approximately 85% by volume of the hyaloclastite powder passes through a 325 mesh screen, most preferably approximately 90% by volume of the hyaloclastite powder passes through a 325 mesh screen, especially approximately 95% by volume of the hyaloclastite powder passes through a 325 mesh screen and more especially approximately 100% by volume of the hyaloclastite powder passes through a 325 mesh screen. Preferably approximately 80% to approximately 100% by volume of the hyaloclastite powder passes through a 325 mesh screen, more preferably approximately 90% to approximately 100% by volume of the hyaloclastite powder passes through a 325 mesh screen, most preferably approximately 95% to approximately 100% by volume of the hyaloclastite powder passes through a 325 mesh screen, especially approximately 100% by volume of the hyaloclastite powder passes through a 325 mesh screen. The foregoing ranges include all of the intermediate values. Preferably a maximum of 34% by volume of the hyaloclastite powder is retained on the 325 mesh screen, more preferably a maximum of approximately 20% by volume of the hyaloclastite powder is retained on the 325 mesh screen, most preferably a maximum of approximately 10% by volume of the hyaloclastite powder is retained on the 325 mesh screen, especially a maximum of approximately 5% by volume of the hyaloclastite powder is retained on the 325 mesh screen, more especially approximately 0% by volume of the hyaloclastite powder is retained on the 325 mesh screen. The foregoing percentages include all of the intermediate values. In another disclosed embodiment, the hyaloclastite rock can be interground with hydraulic cement clinker. For example, hyaloclastite rock can be interground with portland cement clinker or slag cement clinker. That is hyaloclastite rock and portland cement clinker can be combined and ground at the same time with the same equipment. In one disclosed embodiment of the present invention, the hyaloclastite preferably has a chemical composition of approximately 43% to approximately 57% by weight SiO2, approximately 5% to approximately 20% by weight Al2O3, approximately 8% to approximately 15% by weight Fe2O3, approximately 5% to approximately 15% by weight CaO, approximately 5% to approximately 15% by weight MgO, less than or equal to approximately 3% by weight Na2O. In addition to the foregoing, other compounds can be present in small amounts, such as K2O, TiO2, P2O5, MnO, various metals, rare earth trace elements and other unidentified elements. When combined, these other compounds represent less than 10% by weight of the total chemical composition of the hyaloclastite mineral. In another disclosed embodiment, the hyaloclastite in accordance with the present invention preferably has a density or specific gravity of approximately 2.8 to approximately 3.1. Hyaloclastite in accordance with the present invention can be in crystalline or amorphous (glassy) form and is usually found as a combination of both in varying proportions. Preferably, the hyaloclastite in accordance with the present invention comprises approximately 0% to 99% by weight amorphous form, more preferably approximately 10% to approximately 80% by weight amorphous form, most preferably approximately 20% to approximately 60% by weight amorphous form, especially approximately 30% to approximately 50% by weight amorphous form. The crystalline portion of hyaloclastite preferably comprises approximately 3% to approximately 20% by weight olivine, approximately 5% to approximately 40% by weight clinopyroxene, approximately 5% to approximately 60% by weight plagioclase, and approximately 0% to approximately 10% (or less than 10%) by weight other minerals including, but not limited to, magnetite, UlvoSpinel, quartz, feldspar, pyrite, illite, hematite, chlorite, calcite, hornblende, biotite, hypersthene (an orthopyroxene), feldspathoids sulfides, metals, rare earth minerals, other unidentified minerals and combinations thereof. The foregoing ranges include all of the intermediate values. Hyaloclastite in accordance with the present invention can be used as a supplementary cementitious material in concrete or mortar mixes. Hyaloclastite in accordance with the present invention is not by itself a hydraulic cement, but is activated by CaOH (hydrate lime) produced by the hydration of hydraulic cements, such as portland cement, or by other minerals or compounds having reactive hydroxyl groups, such as CaO (quick lime). In addition hyaloclastite in accordance with the present invention when mixed with cement may improve the cement nucleation process thereby improving the cement hydration process. Hyaloclastite in finer particles generally yields shorter set times and accelerates hydration in blended cements. Finer particle size hyaloclastite increases the rate of hydration heat development and early-age compressive strength in portland cement. This acceleration may be attributable to the hyaloclastite particle size (nucleation sites), its crystalline make-up and/or chemical composition. Hyaloclastite in accordance with the present invention can be used in combination with any hydraulic cement, such as portland cement. Other hydraulic cements include, but are not limited to, blast granulated slag cement, calcium aluminate cement, belite cement (dicalcium silicate), phosphate cements and others. Also, hyaloclastite in accordance with the present invention by itself can be blended with lime to form a cementitious material. In one disclosed embodiment, blended cementitious material for cement or mortar preferably comprises approximately 10% to approximately 90% by weight hydraulic cement and approximately 10% to approximately 90% by weight hyaloclastite in accordance with the present invention, more preferably approximately 20% to approximately 80% by weight hydraulic cement and approximately 20% to approximately 80% by weight hyaloclastite in accordance with the present invention, most preferably approximately 30% to approximately 70% by weight hydraulic cement and approximately 30% to approximately 70% by weight hyaloclastite in accordance with the present invention, especially approximately 40% to approximately 60% by weight hydraulic cement and approximately 40% to approximately 60% by weight hyaloclastite in accordance with the present invention, more especially approximately 50% by weight hydraulic cement and approximately 50% by weight hyaloclastite in accordance with the present invention, and most especially approximately 70% by weight hydraulic cement and approximately 30% by weight hyaloclastite in accordance with the present invention. In another disclosed embodiment of the present invention, cementitious material for concrete or mortar preferably comprises approximately 50% to approximately 90% by weight hydraulic cement and approximately 10% to approximately 50% by weight hyaloclastite in accordance with the present invention. The foregoing ranges include all of the intermediate values. The present invention can be used with conventional concrete mixes. Specifically, a concrete mix in accordance with the present invention comprises cementitious material, aggregate and water sufficient to hydrate the cementitious material. The cementitious material comprises a hydraulic cement and hyaloclastite in accordance with the present invention. The amount of cementitious material used relative to the total weight of the concrete varies depending on the application and/or the strength of the concrete desired. Generally speaking, however, the cementitious material comprises approximately 6% to approximately 30% by weight of the total weight of the concrete, exclusive of the water, or 200 lbs/yd3(91 kg/m3) of cement to 1,200 lbs/yd3(710 kg/m3) of cement. In ultra high performance concrete, the cementitious material may exceed 25%-30% by weight of the total weight of the concrete. The water-to-cement ratio by weight is usually approximately 0.25 to approximately 0.7. Relatively low water-to-cement materials ratios by weight lead to higher strength but lower workability, while relatively high water-to-cement materials ratios by weight lead to lower strength, but better workability. For high performance concrete and ultra high performance concrete, lower water-to-cement ratios are used, such as approximately 0.20 to approximately 0.25. Aggregate usually comprises 70% to 80% by volume of the concrete. In ultra high performance concrete, the aggregate can be less than 70% of the concrete by volume. However, the relative amounts of cementitious material to aggregate to water are not a critical feature of the present invention; conventional amounts can be used. Nevertheless, sufficient cementitious material should be used to produce concrete with an ultimate compressive strength of at least 1,000 psi, preferably at least 2,000 psi, more preferably at least 3,000 psi, most preferably at least 4,000 psi, especially up to about 10,000 psi or more. In particular, ultra high performance concrete, concrete panels or concrete elements with compressive strengths of over 20,000 psi can be cast and cured using the present invention. The aggregate used in the concrete in accordance with the present invention is not critical and can be any aggregate typically used in concrete. The aggregate that is used in the concrete depends on the application and/or the strength of the concrete desired. Such aggregate includes, but is not limited to, fine aggregate, medium aggregate, coarse aggregate, sand, gravel, crushed stone, lightweight aggregate, recycled aggregate, such as from construction, demolition and excavation waste, and mixtures and combinations thereof. The reinforcement of the concrete in accordance with the present invention is not a critical aspect of the present invention, and, thus, any type of reinforcement required by design requirements can be used. Such types of concrete reinforcement include, but are not limited to, deformed steel bars, cables, post tensioned cables, pre-stressed cables, fibers, steel fibers, mineral fibers, synthetic fibers, carbon fibers, steel wire fibers, mesh, lath, and the like. The preferred cementitious material for use with the present invention comprises portland cement. The cementitious material preferably comprises a reduced amount of portland cement and an increased amount of supplementary cementitious materials; i.e., hyaloclastite in accordance with the present invention. This results in cementitious material and concrete that is more environmentally friendly. The portland cement can also be replaced, in whole or in part, by one or more pozzolanic materials. Portland cement is a hydraulic cement. Hydraulic cements harden because of a hydration process; i.e., a chemical reaction between the anhydrous cement powder and water. Thus, hydraulic cements can harden underwater or when constantly exposed to wet weather. The chemical reaction results in hydrates that are substantially water-insoluble and so are quite durable in water. Hydraulic cement is a material that can set and harden submerged in water by forming insoluble products in a hydration reaction. Other hydraulic cements useful in the present invention include, but are not limited to, calcium aluminate cement, belite cement (dicalcium silicate), phosphate cements and anhydrous gypsum. However, the preferred hydraulic cement is portland cement. In a disclosed embodiment of the present invention, concrete or mortar comprises a hydraulic cement, hyaloclastite in accordance with the present invention, aggregate and water. Preferably, the cementitious material used to form the concrete or mortar comprises portland cement and hyaloclastite powder, more preferably portland cement and hyaloclastite having a volume-based mean particle size of less than or equal to approximately 40 μm, most preferably portland cement and hyaloclastite having a volume average particle size of less than or equal to approximately 20 μm, especially less than or equal to 15 μm, more especially less than or equal to 10 μm, most especially less than or equal to 5 μm. In simple terms, the hyaloclastite is reduced to a fine powder. The foregoing ranges include all of the intermediate values. In another disclosed embodiment of the present invention, concrete including hyaloclastite in accordance with the present invention can include any other pozzolan in combination with hydraulic cement. The portland cement and hyaloclastite in accordance with the present invention can be combined physically or mechanically in any suitable manner and is not a critical feature of the present invention. For example, the portland cement and hyaloclastite in accordance with the present invention can be mixed together to form a uniform blend of dry cementitious material prior to combining with the aggregate and water. Or, the portland cement and hyaloclastite in accordance with the present invention can be added separately to a conventional concrete mixer, such as a transit mixer of a ready-mix concrete truck, at a batch plant. The water and aggregate can be added to the mixer before the cementitious material, however, it is preferable to add the cementitious material first, the water second, the aggregate third and any makeup water last. Chemical admixtures can also be used with the concrete in accordance with the present invention. Such chemical admixtures include, but are not limited to, accelerators, retarders, air entrainments, plasticizers, superplasticizers, coloring pigments, corrosion inhibitors, bonding agents and pumping aid. Mineral admixtures can also be used with the concrete in accordance with the present invention. Although mineral admixtures can be used with the concrete of the present invention, it is believed that mineral admixtures are not necessary. However, in some embodiments it may be desirable to include a water reducing admixture, such as a superplasticizer. Concrete can also be made from a combination of portland cement and pozzolanic material or from pozzolanic material alone. There are a number of pozzolans that historically have been used in concrete. A pozzolan is a siliceous or siliceous and aluminous material which, in itself, possesses little or no cementitious value but which will, in finely divided form and in the presence of water, react chemically with calcium hydroxide at ordinary temperatures to form compounds possessing cementitious properties (ASTM C618). The broad definition of a pozzolan imparts no bearing on the origin of the material, only on its capability of reacting with calcium hydroxide and water. The general definition of a pozzolan embraces a large number of materials, which vary widely in terms of origin, composition and properties The most commonly used pozzolans today are industrial by-products, such as slag cement (ground granulated blast furnace slag), fly ash, silica fume from silicon smelting, and natural pozzolans such as highly reactive metakaolin, and burned organic matter residues rich in silica, such as rice husk ash. Hyaloclastite in accordance with the present invention is a previously unknown natural pozzolan. It can be used as a substitute for any other pozzolan or in combination with any one or more pozzolans that are used in combination with any hydraulic cement used to make concrete or mortar. It is specifically contemplated as a part of the present invention that concrete formulations including hyaloclastite in accordance with the present invention can be used with concrete forms or systems that retain the heat of hydration to accelerate the curing of the concrete. Therefore, in another disclosed embodiment of the present invention, concrete in accordance with the present invention can be cured using concrete forms such as disclosed in U.S. Pat. Nos. 8,555,583; 8,756,890; 8,555,584; 8,532,815; 8,877,329; 9,458,637; 8,844,227 and 9,074,379 (the disclosures of which are all incorporated herein by reference); published patent application Publication Nos. 2014/0333010; 2014/0333004 and 2015/0069647 (the disclosures of which are all incorporated herein by reference) and U.S. patent application Ser. No. 15/418,937 filed Jan. 30, 2017 (the disclosure of which is incorporated herein by reference). The following examples are illustrative of selected embodiments of the present invention and are not intended to limit the scope of the invention. Example 1 The hyaloclastite in accordance with the present invention has the unexpected property of reduced water demand of the cementitious matrix. For example, the water demand of other pozzolans is higher. As an example, metakaolin's water demand is greater than portland cement when tested in accordance to ASTM C-618; i.e., water requirement as a percent of control is greater than 100. As shown in Table 1 below, pumice (a natural pozzolan) and comparable particle size to hyaloclastite in accordance with the resent invention had a water demand greater than portland cement. However, hyaloclastite in accordance with the present invention and having a mean particle size of 14 μm when tested in accordance with the ASTM C 311 and ASTM C-618 had a water requirement of 97% when compared with the portland cement control sample. The hyaloclastite in accordance with the present invention of mean particle size of 8 μm when tested in accordance with the ASTM C-618 had a water requirement of 96% when compared with the portland cement control sample. The hyaloclastite in accordance with the present invention having a mean particle size of 4 μm when tested in accordance with the ASTM C-618 had a water requirement of 97% when compared with the portland cement control sample. When tested in accordance to ASTM-618 the hyaloclastite had significantly lower water demand than pumice or portland cement. The water demand of each type is show in Table 1 below. TABLE 1ASTM C-618 Water requirement testresults compared to control sampleTotalWater(SiO2+RequirementSiO2Al2O3Fe2O3Al2O3+(Test H2O/Product type(%)(%)(%)Fe2O3)Control H2O)Pumice (14 μm,64.3015.177.8987.36103%d50)Hyaloclastite (1446.9912.1512.1371.2897%μm, d50)Pumice (8 μm, d50)63.5715.237.8286.62103%Hyaloclastite (8 μm,47.2012.4912.0471.7395%d50)Hyaloclastite (4 μm,47.2012.4912.0471.7397%d50) Example 2 Hyaloclastite in accordance with the present invention has the unexpected property of significantly reducing ASR in concrete. Test specimens were prepared in accordance with the procedures described in ASTM C441 as modified by ASTM C311. Three control mortar bars were each prepared from a control mix and three test mortar bars were each prepared from a test mix using the modified proportions specified by ASTM C311. The mix proportions are listed in Table 2 below. TABLE 2Mix ProportionsControl MixTest MixCemex Cement, g4000Lehigh Cement, g0300Hyaloclastite (8 μm, d50), g0100Graded Pyrex Glass, g900900Water, ml226213Flow (100-115%)115102 As required by ASTM C311, the cement for the control mixture had an alkali content less than 0.60% (as equivalent Na2O) and the cement used in the test mixture had an alkali content greater than that of the cement used in the control mixture. Cemex cement with an equivalent Na2O of 0.30% was used for the control mixtures and Lehigh cement with an equivalent Na2O of 0.61% was used for the test mixture. A sufficient amount of water was used to produce a flow of 100% to 115%. The specimens were cured in a moist room for 24 hours and then stored in a moist container as specified in ASTM C227-10 Standard Test Method for Potential Alkali Reactivity of Cement-Aggregate Combinations (Mortar-Bar Method) at 38° C.±2° C. for 14 days. Results of the testing are reported in Table 3 below. TABLE 3ASR Test ResultsLength (inches)LengthInitial14 DaysChange (%)Control 10.04630.04870.022Control 20.05280.05460.016Control 30.05420.04390.018Average0.019Longview 10.04640.0463−0.003Longview 20.04560.0452−0.006Longview 30.04430.0439−0.006Reference0.04360.0438—Average−0.005Reduction of Mortar Expansion as % of Control126.3% When tested in accordance to the ASTM C441-11, the test bars showed a reduction of Mortar Bar Expansion of 126.3% when compared to the control bar. Typical Fly Ash Mortar Bar Expansion reduction when tested in accordance with ASTM C441-11 is approximately 60%-75%. Thus, hyaloclastite in accordance with the present invention reduces ASR much better than fly ash. Example 3 Hyaloclastite in accordance with the present invention has the unexpected property of improved strength development. Test specimens were prepared in accordance with the procedures described in ASTM C311 and tested in accordance with ASTM C618. Control mortar samples were each prepared from a control mix and mortar samples of pumice of 14 μm and 8 μm average mean particle size and hyaloclastite of 14 μm, 8 μm and 4 μm average mean particle size in accordance with the present invention. These mortar cubes samples were each prepared from a test mix using the modified proportions specified by ASTM C311 and tested in accordance with ASTM C618. Sufficient samples we made and testing was conducted at 1, 3, 7, 14, 28 and 56 days. In order to pass ASTM C618, a natural pozzolan must have a minimum of 75% strength gain at 7 and 28 days when compared to the portland cement sample. As shown below, hyaloclastite in accordance with the present invention performed better than pumice at each of these intervals. Surprisingly, while pumice at 8 μm mean particle size developed lower compressive strength than pumice at 14 μm mean particle size; whereas, hyaloclastite at 8 μm mean particle size developed higher compressive strength than hyaloclastite at 14 μm mean particle size. Over time hyaloclastite in accordance with the present invention had similar or better compressive strength test results than the portland cement control samples. Results are of these tests are shown in Table 4 and 5 below. TABLE 4ASTM C-618 Mortar Cube Testing resultsCompression PSIControlControlControlPumicePumiceHyaloclastiteHyaloclastiteHyaloclastiteTest#1#2#3(14 μm, d50)(8 μm, d50)(14 μm, d50)(8 μm, d50)(4 μm, d50)1Day2850298021702450251026203Day4840461033003620371041607Day468051503750336039604240506014Day55205630443041304770576028Day564063505180461052805530703056Day641060605540557057006670 TABLE 5Percentage strength gain (test sample/control sample)SAI %PumicePumice(14 μm,(8 μm,HyaloclastiteHyaloclastiteHyaloclastiteTestd50)d50)(14 μm, d50)(8 μm, d50)(4 μm, d50)1Day768284883Day687980907Day807285919814Day80738510228Day9282949811156Day869294110 The foregoing tests demonstrate that hyaloclastite in accordance with the present invention unexpectedly produces greater compressive strength gain than pumice (a natural pozzolan) and the portland cement control samples. Example 4 The specific gravity of portland cement is 3.1. The specific gravity of pozzolans varies from 2.05 to 2.65. Table 6 below shows the specific gravity for portland cement, hyaloclastite, pumice, dacite, rhyolite, fly ash, matakaolin and nano silica. TABLE 6Specific Gravity comparisonProduct typeSpecific GravityPortland Cement3.10Hyaloclastite2.8-3.0Pumice2.3-2.6Dacite2.6-2.7Rhyolite2.7-2.8Fly Ash2.03-2.6Metakaolin2.5-2.6Nanosilioca2.20 When pozzolans are used to replace portland cement, the ratio of replacement takes into consideration specific gravity. Since all pozzolans have a lower specific gravity than portland cement, the pozzolan's replacement weight must be adjusted according to the difference in the density. Accordingly, known pozzolan replacement ratios are often greater than 1 and sometimes as high as 1.3. Hyaloclastite in accordance with the present invention has a specific gravity of 2.90-3.0. Therefore, the replacement ratio of hyaloclastite in accordance with the present invention for portland cement can be one-to-one, thereby saving material and costs. Example 5 The particle size of hyaloclastite in accordance with the present invention was analyzed using a MICROTRAC-X100 light scattering particles size measuring equipment. The particles were measure in isopropyl alcohol, had a reflective index of 1.38, a load factor of 0.0824 and a transmission of 0.87. Table 7 below shows a summary of the particles size analysis for a hyaloclastite sample wherein 85% by volume of the particles passed through a 325 mesh screen. TABLE 7PropertyValuemv15.10mn1.180ma4.651cs1.290sd12.62 In Table 7 above, the abbreviation “my” means “mean diameter in microns of the “volume distribution” represents the center of gravity of the distribution. Mie or modified Mie calculations are used to calculate the distribution. Implementation of the equation used to calculate MV will show it to be weighted (strongly influenced) by a change in the volume amount of large particles in the distribution. It is one type of average particle size or central tendency”. The abbreviation “mn” means “mean diameter, in microns, of the “number distribution” is calculated using the volume distribution data and is weighted to the smaller particles in the distribution. This type of average is related to population or counting of particles”. The abbreviation “ma” means “mean diameter, in microns, of the “area distribution” is calculated from the volume distribution. This area mean is a type average that is less weighted (also less sensitive) than the MV to changes in the amount of coarse particles in the distribution. It represents information on the distribution of surface area of the particles of the distribution”. The abbreviation “cs” means “calculated surface—Provided in units of M2/cc, the value provides an indication of the specific surface area. The CS computation assumes smooth, solid, spherical particles. It may be converted to classical units for SSA of M2/g by dividing the value by the density of the particles. It should not be interchanged with BET or other adsorption methods of surface area measurement since CS does not take into effect porosity of particles, adsorption specificity or topographical characteristics of particles”. The abbreviation “cs” means “Standard Deviation in microns, also known as the Graphic Standard Deviation (Gg), is one measure of the width of the distribution. It is not an indication of variability for multiple measurements. Equation to calculate is: (84%−16%)/2”. In Table 8 below, the particle size distribution is shown in terms of percentile. TABLE 8PercentileValue10%1.73520%3.04730%4.63840%6.70750%9.39360%13.1170%17.9280%24.2790%35.3195%47.68 Table 9 below, the particle size distribution is shown in terms of particle size. TABLE 9Size (microns)% Pass704.0-104.7100.0095.9699.7488.0099.3680.7098.9974.0098.5867.8698.1062.2397.5452.3396.0657.0696.8747.9895.0844.0093.9240.3592.5537.0090.9633.9389.1331.1187.0728.5384.7926.1682.3123.9979.6522.0076.8520.1773.9718.5071.0716.9668.1815.5665.3514.2762.6013.0859.9212.0057.3011.0054.7110.0952.139.25049.558.48246.967.77844.377.13341.806.54136.835.99836.835.50034.455.04432.154.62529.934.24127.763.88925.653.56623.583.27021.582.99919.662.75017.832.52216.122.31214.542.12113.081.94511.711.78310.411.6359.151.4997.911.3756.691.2615.491.1564.361.0603.330.9722.440.8921.720.8181.150.7500.730.6880.410.6300.160.578-0.1330.00 Example 6 The particle size of hyaloclastite in accordance with the present invention was analyzed using a MICROTRAC-X100 light scattering particles size measuring equipment. The particles were measure in isopropyl alcohol, had a reflective index of 1.38, a load factor of 0.0884 and a transmission of 0.86. Table 10 below shows a summary of the particles size analysis for a hyaloclastite sample wherein 95% by volume of the particles passed through a 325 mesh screen. TABLE 10PropertyValuemv8.736mn1.488ma4.386cs1.368sd6.136 In Table 11 below, the particle size distribution is shown in terms of percentile. TABLE 11PercentileValue10%1.95320%2.96230%3.98740%5.27050%6.83060%8.68270%10.7480%13.4490%17.7495%22.21 Table 12 below, the particle size distribution is shown in terms of particle size. TABLE 12Size (microns)% Pass704.0-52.33100.0047.9899.8744.0099.6840.3599.4637.0099.2033.9398.8631.1198.4328.5397.8726.1697.1223.9996.1322.0094.8520.1793.2118.5091.1616.9688.6615.5685.7514.2782.4613.0878.8612.0075.0511.0071.1110.0967.129.25063.158.48259.257.77855.457.13351.786.54148.255.99844.865.50041.585.04438.394.62535.274.24132.183.88929.133.56626.113.27023.182.99920.392.75017.802.52215.462.31213.382.12111.551.9459.931.7838.481.6357.151.4995.911.3754.761.2613.691.1562.731.0601.920.9721.260.8920.770.8180.410.7500.150.688-0.1330.00 It should be understood, of course, that the foregoing relates only to certain disclosed embodiments of the present invention and that numerous modifications or alterations may be made therein without departing from the spirit and scope of the invention as set forth in the appended claims. | 38,324 |
11858848 | DETAILED DESCRIPTION OF EMBODIMENTS The disclosure will be described in further detail below in conjunction with specific embodiments, but embodiments of the disclosure are not limited to these. A ye'elimite mineral may be prepared as that: powders of calcium carbonate (CaCO3), aluminum oxide (Al2O3) and calcium sulfate (CSH2) are mixed according to a molar ratio of CaCO3:Al2O3:CSH2=3:3:1 to obtain a powder mixture, a powder of ye'elimite of 5 wt % of the powder mixture then is added into the powder mixture as crystalline seeds so that a resulting mixture is obtained; next, the resulting mixture is sequentially mixed evenly, compacted and calcinated by raising a temperature to 1350° C. within 2 h and then keeping/maintaining the temperature of 1350° C. for 2 h; and afterwards, the calcinated mixture is taken out and cooled to a room temperature within 1 minute (min), and then grinded until all passing through 200 mesh sieve. An anhydrite may be prepared as that: keeping a raw anhydrite at 200° C. for 2 h for calcining in a high-temperature furnace. Dosages of ingredients of a regulating cementitious material in various embodiments are as follows: Embodiment 1 A regulating cementitious material for promoting rapid hydration of Portland cement may be composed of ingredients in parts by weight as follows:ye'elimite, 67.02 parts;anhydrite, 29.83 parts;lithium nitrite, 2.91 parts;ethylene glycol monoisopropanolamine, 0.14 parts;triethanolamine acetate, 0.05 parts; andpolyglycerol, 0.05 parts.Moreover, the ingredients in total are 100 parts by weight. Embodiment 2 A regulating cementitious material for promoting the rapid hydration of Portland cement may be composed of ingredients in parts by weight as follows:ye'elimite, 45.70 parts;anhydrite, 50.92 parts;lithium nitrite, 2.91 parts;ethylene glycol monoisopropanolamine, 0.29 parts;triethanolamine acetate, 0.09 parts; andpolyglycerol, 0.09 parts.Moreover, the ingredients in total are 100 parts by weight. Embodiment 3 A regulating cementitious material for promoting the rapid hydration of Portland cement may be composed of ingredients by weight as follows:ye'elimite, 34.06 parts;anhydrite, 60.82 parts;lithium nitrite, 4.75 parts;ethylene glycol monoisopropanolamine, 0.19 parts;triethanolamine acetate, 0.09 parts; andpolyglycerol, 0.09 parts.Moreover, the ingredients in total are 100 parts by weight. Embodiment 4 A regulating cementitious material for promoting the rapid hydration of Portland cement may be composed of ingredients by weight as follows:ye'elimite, 27.49 parts;anhydrite, 67.30 parts;lithium nitrite, 4.74 parts;ethylene glycol monoisopropanolamine, 0.29 parts;triethanolamine acetate, 0.09 parts; andpolyglycerol, 0.09 parts.Moreover, the ingredients in total are 100 parts by weight. In an application in promoting hydration of Portland cement, an addition amount of the regulating cementitious material may be 10 wt % of the Portland cement. According to the dosages of raw materials (i.e., ingredients), dry powders of raw materials in each of the above illustrated embodiments 1-4 are evenly mixed and placed in a cement mortar mixing pot/vessel. 1 part by weight of the regulating cementitious material and 3 parts by weight of Chinese ISO standard sand are taken, cement mortars in form of a 40 mm×40 mm×160 mm prism specimen prepared by a group of plastic cementitious sands made as per a water-cement ratio of 0.5 are placed in water and maintained to a specified age at 20° C., and then a strength test is carried out on a universal testing machine. The test shall be carried out in accordance with a testing method specified in GB/T17671-1999 (Method of testing cements-Determination of strength (ISO method)). The dry powders of raw materials are evenly mixed according to predetermined dosages in each of the above illustrated embodiments 1-4 to obtain a dry powder mixture and then placed in a cement paste mixing pot/vessel, the water-cement ratio is determined to be 0.35, the dry powder mixture is stirred in a form of slow stirring (rotational speed of 140 revolutions per minute (r/min)) for 2 min first, then is stopped for 15 seconds (s), and afterwards is stirred in a form of quick/fast stirring (rotational speed of 280 r/min) for 2 min, 20 mm×20 mm×20 mm cement paste blocks are then formed in a six-piece mold and placed in water and maintained to a specified age at 20° C., and thereafter, a strength test is performed on a universal testing machine. TABLE 1test results of flexural strengths of cement mortarsBlankEmbodi-Embodi-Embodi-Embodi-Flexuralcontrolmentmentmentmentstrengthsgroup12341 d3.644.734.314.155.123 d4.955.795.645.987.327 d7.218.628.149.2310.15 TABLE 2test results of compressive strengths of cement mortarsBlankEmbodi-Embodi-Embodi-Embodi-Compressivecontrolmentmentmentmentstrengthsgroup12341 d9.3713.3712.1412.8713.953 d22.1527.4725.4126.1334.217 d32.9445.6743.1742.4850.51 TABLE 3test results of compressive strengths of cement pastesBlankEmbodi-Embodi-Embodi-Embodi-Compressivecontrolmentmentmentmentstrengthsgroup12341 d12.3721.3719.1420.8724.953 d35.1543.4741.4146.1349.217 d55.9468.6763.1763.4873.51 | 5,169 |
11858849 | DETAILED DESCRIPTION Structural assembly boards comprising magnesium oxide cement may be provided with improved properties, such as improved flexure strength and reduced corrosivity, by the formation of crystal structures such as 5MgO·MgCl2·8H2O (Phase-5 crystal structures). Increasing the amount of MgO converted into Phase-5 crystal structures, from an initial cement mixture, may improve the properties of a structural assembly board made from MgO cement. In contrast, MgO cement is typically made from 80-85% pure MgO, MgCl2, and water, see e.g. U.S. Pat. No. 7,998,547B2, which may result in weaker structural properties in comparison to the present invention. Maximizing Phase-5 crystal structure in a structural assembly board made from MgO cement may be achieved using high purity magnesium oxide with multiple particle sizes. The use of high-purity MgO with multiple particles sizes may improve the properties of the structural assembly board in comparison of existing MgO boards, for example, by increasing the strength of the board, minimizing corrosivity of the board by reducing free chloride ions, and reducing manufacturing time by reducing the number of steps required to make the structural assembly board. In an embodiment, a composition to make a structural assembly board comprises magnesium oxide having purity of 94-98 wt %, magnesium chloride (MgCl2), and water. In this disclosure, purity of MgO should be understood as the content of MgO in the magnesium oxide source material, e.g. a 94-98 wt % purity of MgO will have 94-98 wt % MgO with the remainder comprising oxides of at least one of calcium, iron, aluminium, and/or silicon. In a further embodiment, the purity of the magnesium oxide may be greater than 96.5 wt % MgO. The magnesium oxide has at least two different range of particles sizes, for example, MgO(30) and MgO(40) from Baymag™. MgO(30) may have a particle distribution where 90 vol % is less than 65 μm. MgO(40) may have a particle distribution where 90 vol % is less than about 36 μm. In an embodiment, the MgO will comprise a first particle size of about 30 m2/g and a second particle size of about 70 m2/g. During the reaction between MgO, MgCl2and water, the desirable product of the reaction is a Phase-5 Crystal Structure; however, a competing reaction may convert MgO and water into magnesium hydroxide which may cause cured cement to become brittle. Smaller MgO particles, e.g. 30 m2/g, are more reactive than larger MgO particles, yet if reacted alone with MgCl2and water will promote formation of magnesium hydroxide. Larger MgO particles, e.g. 70 m2/g, if reacted alone with MgCl2and water, are less reactive than a small particle and tend to favour Phase-5 Crystal structure formation; however, the center of the particle may become non-reactive. A combination of small and larger particle sizes may promote a reaction rate that favours the formation of Phase-5 Crystal Structure. Typical mixtures of large to small particles are 3:1 by weight and demonstrate substantial Phase-5 crystal growth. Traditional MgO cements, and more particularly boards made from the cement, have a propensity for chloride migration in humid (e.g. >90% humidity) or flood conditions due to the porosity of the boards and their inherent water unstable MgO:MgCl2structures. Unbound chloride ions have the ability to permeate the porous structure of the MgO concrete board and corrode lumber and steel. Accordingly, the usage of traditional MgO cement board is generally limited to use with stainless steel fasteners. The problem associated with free chloride ions may be addressed by binding those ions to prevent their migration. In an embodiment, the MgCl2is magnesium chloride hexahydrate. In another embodiment, the molar ratio of MgO:MgCl2:H2O of the composition to make a structural assembly board is 5-9:1:10-20. In a further embodiment, the molar ratio of MgO:MgCl2:H2O is about 5.5:1:12.5. In combination with high purity MgO (e.g. 94-98 wt %), a molar ratio of 5-9:1:10-20 MgO:MgCl2:H2O may allow greater than 80% MgO in the composition to form Phase-5 Crystal Structure in the resulting cement. By binding chloride ions in the Phase-5 Crystal Structure, the amount of corrosivity causing free chloride ions is reduced in MgO structural assembly boards in comparison to boards made from MgO having lower Phase-5 Crystal Structure content. Free chloride ion migration may also be reduced by enhancing water resistance of a structural assembly board. In an embodiment, the composition for making a structural assembly board includes at least one of carboxylic functionalized amphiphilic molecules, phosphonic functionalized amphiphilic molecules, and/or polymers may be added to a composition according to the present invention. Incorporation of carboxylic or phosphonic functionalized amphiphilic small molecules or polymers in the composition to make a structural board has shown an enhancement in water resistance in the resulting board. It is postulated that the acidic anchoring group bond covalently to the metal oxychloride nanoporous structure and create a hydrophobic coating. In a further embodiment, the composition includes at least one of NaH2PO4, KH2PO4, H3PO4, and/or sodium silicate to promote water resistance of the cement formed from the composition. In another embodiment, cellulosic fibers with polyol functionality may be added to the composition to make a structural assembly board. Cellulosic fibers with polyol functionality have also demonstrated enhanced water resistance. In a further embodiment, a structural assembly board may be coated with a thin superhydrophobic film to make the board impermeable to water. Traditional MgO cement boards are generally reinforced by reinforcing mesh, e.g. fiberglass mesh, to provide a supporting structure for the cement board so that it does not fracture when flexed. In an embodiment of the present invention, flexural strength of an MgO structural assembly board may be improved by adding reinforcing fiber to the composition for making a structural assembly board. In an further embodiment, the fiber may be at least one of basalt, polypropylene, hemp, and/or flax. In another embodiment, aggregate, for example fly ash (type F) and/or perlite, may be added to lower the density of the composition and increase flexural strength of a structural assembly board made from the composition. Two particle sizes of perlite have been investigated as part of the composition for making a structural assembly board. In an embodiment, the two sizes of perlite may be added as 10-15% wt of the composition for making a structural assembly board. For example, the particle size may be 0.5 mm-2 mm, and the density of perlite may be Perlite C (coarse) and Perlite F (fine). Alternative perlite particle sizes and densities may be used in the composition. In another embodiment, the composition for making a structural assembly board may further comprise a defoamer, e.g. the commercial defoamer KFO105, to destabilize foam created from the composition which promote reactivity of MgO and homogeneous mixing of the composition. In another embodiment, the composition for making a structural assembly board may further comprise pigment of any colour. Exemplary compositions for use in making a structural assembly board are shown in Examples 1-5. Each of the exemplary compositions also contained either NaH2PO4or H3PO4at <3 wt % of total MgO weight, and one of carboxylic or phosphonic functionalized amphiphilic small molecules or polymers at <5 wt % of total MgO content. Example 1 (ID #9) ComponentMass (kg)Mol Ratio (MgO:MgCl2:H2O)MgO (30/40)2.5-3.05.5MgCl2•6H2O2.3-2.71.0H2O1.2-1.612.3KFO1050.07Flax0.2-0.6Pigment0.02Fly Ash0.8-1.2 Example 2 (ID #10) ComponentMass (kg)Mol Ratio (MgO:MgCl2:H2O)MgO (30/40)2.5-2.95.4MgCl2•6H2O2.3-2.71.0H2O1.2-1.612.3KFO1050.07Flax0.2-0.6Pigment0.02Fly Ash0.8-1.2 Example 3 (ID #17) ComponentMass (kg)Mol Ratio (MgO:MgCl2:H2O)MgO (30/40)2.5-2.95.4MgCl2•6H2O2.3-2.71.0H2O1.2-1.612.3KFO1050.07Perlite F0.5-0.9Flax0.2-0.4Pigment0.02Fly Ash0.3-0.6 Example 4 (ID #18) ComponentMass (kg)Mol Ratio (MgO:MgCl2:H2O)MgO (30/40)2.0-2.35.5MgCl2•6H2O1.8-2.21.0H2O1.1-1.413.3KFO1050.07Perlite C0.1-0.3Perlite F0.3-0.5Flax0.3-0.5Fly Ash0.3-0.5 Example 5 (ID #27) ComponentMass (kg)Mol Ratio (MgO:MgCl2:H2O)MgO (30/40)1.8-2.25.61MgCl2•6H2O1.6-2.01.00H2O1.0-1.313.21KFO1050.07Perlite C0.1-0.2Perlite F0.5-0.7Flax0.1-0.2Fly Ash0.7-0.9Polypropylene Fiber0.01 Controlling formation of Phase-5 Crystal Structure when making a structural assembly board is important to provide the board with improved properties, e.g. flexural strength. With reference to the method flow chart ofFIG.1, some embodiments may provide for a method of manufacturing a structural assembly board. At102, a brine solution may be produced by dissolving magnesium chloride, e.g. magnesium chloride hexahydrate (MgCl2.6H2O), in a warmed solution of water (e.g. ˜40° C.). In an embodiment, a total ratio of 1:12-13 MgCl2:H2O may be maintained in the brine solution. The brine solution may then be cooled (e.g. to −14-24° C.) and checked for absolute clarity before addition of remaining components. At104, high purity MgO having a purity of 94-98 wt % MgO is endothermically dissolved in the brine solution to form a cement mixture. In an embodiment, the purity of MgO is greater than or equal to 96.5 wt % MgO. The magnesium oxide may have at least two different particles sizes, for example, a first particle size having a surface areas equal to 30 m2/g and a second particle size having a surface area equal to 70 m2/g. The mixture of the two particle sizes imbues an ability to control the reaction rate of the initial crystallization of the cement. Smaller particles react more quickly than larger particles, however, the use of small particles alone can cause rapid curing, formation of magnesium hydroxide, and weakening issues in the cement product if not controlled precisely. Larger particles are less reactive and tend to convert MgO into stronger crystalline structures; however, the center of the particle may become non-reactive leaving gaps in said crystalline structures. A mixture of at least two particle sizes may optimize Phase-5 crystal formation. In an embodiment, aggregate and/or reinforcing fibers, may be added to augment the strength of the concrete. The aggregate (e.g. perlite and fly ash) and/or reinforcing fibers (e.g. basalt, polypropylene, hemp and/or flax) may be added by monitoring the temperature of cement mixture to determine when aggregate and reinforcing fibers is added. The endothermic dissolution of MgO into the brine solution is preferably accomplished at low temperature, e.g. 14° C., to avoid the formation of the higher activation energy product Mg(OH)2. The aggregate and reinforcing fibers serve to augment the strength of structural assembly board such that the board will may not require supplementary structural support (e.g. fiberglass mesh). Accordingly, in an embodiment, a structural assembly board may be free of supplementary structural support such as fiberglass mesh. At106, the cement mixture is mixed to provide a homogenous mixture. In an embodiment, a high shear or low shear mixing process provides a workable homogeneous after approximately 15 minute of mixing time. In an embodiment, mixing should not exceed 1.5 hours to avoid crystallization in turbulent conditions. At108, the cement mixture is cured. In an embodiment, the cement mixture is moulded and then vibrated to remove trapped air before curing. In another embodiment, curing may occur under high humidity (50-90%) and temperature (30-50° C.) conditions to improve strength of the cement. The board may then be demoulded after 24 hours, however when temperature is increase above 50° C. the board may be demoulded faster than 24 hours. In another embodiment, a cured board may then be put in a less humid environment (e.g. less than 50% humidity) to dry and then be cut to specification. In an embodiment, a defoamer, e.g. KFO105, and/or pigment, may be added to the brine solution or cement mixture. According to some embodiments, a structural assembly board may be made from a composition for use in making a structural assembly board described above. The structural assembly board may have a Phase-5 crystal structure composition comprising more than 80% of the MgO in the composition. In another embodiment, the Phase 5 crystal structure composition of the board comprises greater than 90% of the MgO in the composition. Structural properties of MgO concrete (e.g. flexural strength) increase over the time as long as the concrete is not exposed to harsh environments. However, MgO concrete made according to embodiments of the above method may be cured to a commercially acceptable flexural strength within 7 days. Further, as shown inFIG.2, the flexural strength of commercially available MgO board, which has been cured for at least 1 year, is compared to the structural assembly boards produced from the compositions of Examples 1-4, over a measured period of curing time in air at room temperature. As shown inFIG.2, the structural assembly board made from the composition of Examples 1-4, exceed the flexural strength of MgO board after at least 30 days. Screw withdrawal tests (ASTM D1037) shown in Table 1, also illustrate that structural assembly boards made according to the invention may yield a product that stronger than commercially available MgO board in certain situations. TABLE 1Selected top performance metrics from prototype boards.CuringWeightScrewFlexuralTime(4x8 ft ×WithdrawalStrength(days)½ inch)(lbf)(psi)MgO board>365863081267ID#9721154501970ID#186933541220 Although the embodiments have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed, that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps As can be understood, the detailed embodiments described above and illustrated are intended to be examples only. The invention is defined by the appended claims. The claims are not intended to include, and should not be interpreted to include, means-plus- or step-plus-function limitations, unless such a limitation is explicitly recited in a given claim using the phrase(s) “means for” or “step for,” respectively. | 15,090 |
11858850 | DETAILED DESCRIPTION OF PREFERRED EMBODIMENT According to the high-strength zirconia-alumina composite ceramic substrate applied to semiconductor devices and its manufacturing method thereof the present invention, the produced zirconia-alumina composite ceramic substrate is made of alumina (Al2O3), zirconia (ZrO2) and pre-synthesized sintering additives (MCS). As shown inFIG.1, the manufacturing process of the high-strength zirconia-alumina composite ceramic substrate applied to semiconductor devices and its manufacturing method thereof the present invention includes: Ball milling step100: Using alumina with a powder particle size (D50) of 0.70 to 3.0 μm, zirconia with a powder particle size (D50) of 0.20 to 0.80 μm, and pre-synthesized sintering additives of staring powder with a powder particle size of (D50) 0.30˜1.5 μm, is mixed with organic solvents by ball milling to achieve dispersion uniformly at room temperature; Slurry preparing step200: Preparing an alumina-based slurry by mixing alumina with addition of 1 to 15 wt. % zirconia and 0.01 to 5.0 wt. % a sintering promotion additives; Degassing step300: Degassing and defoaming the mixed slurry until the viscosity of the slurry reaches the pre-set range value of 8000˜30000 cps; Green tape forming step400: Forming a green tape roll with a thickness of 0.12 to 1.10 mm by tape casting the mixed slurry with a viscosity of 8000 to 30000 cps; Punching step500: Punching the zirconia-aluminum composite green tape roll into sheets of pre-set size; Calculation step600: The outside diameter of 227×168 mm of the green sheet is obtained by pre-testing the sintering shrinkage rate to calculate the size of the punched green sheet; Sintering step700: The green sheets of 227×168 mm size are fired at a temperature of 1560-1660° C. in a conventional continuous tunnel furnace to obtain the zirconia-alumina composite ceramic substrate having the size of 7.5 inches×5.5 inches and the thickness of 0.1-0.9 mm, preferably of 0.32 mm. According to the high-strength zirconia-alumina composite ceramic substrate applied to semiconductor devices and its manufacturing method thereof the present invention, the obtained zirconia-alumina composite ceramic substrate includes a matrix phase formed by the micron alumina particles and the secondary phase formed the submicron zirconia particles dispersed on the matrix phase, and a sintering additive synthesized in advance by calcination. The matrix phase of alumina particles serves as the main phase, and the dispersed zirconia particles in the matrix are tetragonal zirconia crystals containing yttrium trioxide (Y2O3) as a stabilizer. In the manufacturing process, the pre-synthesized additive is composed of calcium oxide, silicon dioxide and magnesium oxide in a certain proportion (for example, calcium oxide is 0.8˜8.8 wt. %, silicon dioxide is 56.7˜61.7 wt %, and magnesium oxide is 32.5˜37.5 wt %), is used as feedstock. The starting materials are mixed by bead mill and dried, and then the precursor is fired at a temperature of 850˜1250° C. to produce a silicon-magnesium-calcium oxide compound to ensure the less amount of 0.1 wt. % or more doping zirconia-alumina composite particles being surrounded with the certain proportion of silicon-magnesium-calcium oxides. Therefore, the function of pre-synthesized additive is noted to be beneficial for lowering sintering temperature for zirconia-alumina composite ceramics and enhancing the microstructural morphology uniformly. According to the high-strength zirconia-alumina composite ceramic substrate applied to semiconductor devices and its manufacturing method thereof in the present invention, in the process for manufacturing the zirconia-alumina composite ceramic substrate, the self-prepared additive (MCS) can also be synthesized by combining calcium oxide, silica and magnesium oxide in a certain proportion by bead milling using zirconia beads as a mixing media. After mixing and drying, the powder mixture was obtained by calcining in furnace. According to the high-strength zirconia-alumina composite ceramic substrate applied to a semiconductor devices and its manufacturing method thereof the present invention, the organic chemical binder comprises the solvent-based polyvinyl butyral (PVB), ether ester as the plasticizer, and an appropriate amount of surfactant as the dispersant. MCS sinteringAluminaZirconiapromotion additives(wt. %)(wt. %)(wt. %)Example 192.7570.25Example 291.258.50.25Example 389.75100.25Example 489.75100Example 588.5101.5 Three-pointHigh temperatureApparentBendingThermalsurface leakagedensitystrengthconductivitycurrent(gcm-3)(wt. %)(W/mK)(nA)Example 14.04463328.00.170Example 24.06464928.10.169Example 34.12566126.70.113 According to the high-strength zirconia-alumina composite ceramic substrate applied to semiconductor devices of the present invention, the less amount of silicon magnesium calcium sintering additives is uniformly dispersed among alumina particles by means of the pre-synthesized procedure. It is noted that the silicon-magnesium-calcium compound is helpful for lowering the sintering temperature to avoid abnormal grain growth of alumina, resulting a decrease in strength. Besides, alumina grain boundaries are surrounded by the excessive glass phases, thus giving a lower thermal conductivity. Therefore, it should be pointed out that the produced zirconia-alumina composite ceramic substrate with adequate amount of sintering additives and temperature shall have the following properties:1. Excellent three-point bending strength>600 MPa mechanical properties.2. Thermal conductivity>26 W/mK.3. Insulation resistance>1014Ω·cm.4. Low surface leakage current (150° C.)<200 nA. In summary, according to the high-strength zirconia-alumina composite ceramic substrate applied to semiconductor devices and its manufacturing method thereof the present invention, the characteristics of the zirconia-alumina composite ceramic substrate produced by the method are obviously superior than the traditional alumina ceramic substrate. The novel substrate is successfully satisfied with achieving the desired reliability for the post-substrate process operation and the required stability for the terminal devices. Therefore, the novel substrate along with its manufacturing method meet the conditions of the approvable patent. The above description illustrates the preferred embodiment of the present invention. Any future alternative inventions as well as their effects deemed to be resulted from modifications of the above described invention should not be considered as new inventions, and thus the alternatives should belong to the present invention. | 6,696 |
11858851 | EMBODIMENTS FOR CARRYING OUT THE INVENTION <Complex> Hereinafter, the complex according to one embodiment of the present disclosure will be described in detail. The complex of the present embodiment contains a β-eucryptite (LiAlSiO4) crystal phase and a lithium tantalate (LiTaO3) crystal phase. β-eucryptite exhibits negative thermal expansion behavior, and lithium tantalate exhibits positive thermal expansion behavior. Since the complex contains the crystal phases of β-eucryptite and lithium tantalate that exhibit such thermal expansion behaviors, it is possible to exhibit low thermal expansion properties. In addition, the complex having the above-mentioned configuration may contain 90% by volume or more, or further 99% by volume or more of the total of the β-eucryptite crystal phase and the lithium tantalate crystal phase. In the complex, β-eucryptite and lithium tantalate each maintain their pre-complex, crystal states, and when made complex, another product (crystal phase or glass phase) other than the crystal phases of β-eucryptite and lithium tantalate is not substantially generated, and therefore, there is no effect on the thermal expansion behavior by another product, and the thermal expansion behavior of the entire complex can be accurately controlled. Therefore, the complex of the present embodiment can exhibit low thermal expansion properties over a wide temperature range. The complex may contain other compositions that do not react with β-eucryptite or lithium tantalate. The complex can also exhibit high rigidity due to the lithium tantalate crystal phase. In addition, it can be said that the complex of the present embodiment does not contain a crystal phase or a glass phase other than the β-eucryptite crystal phase and the lithium tantalate crystal phase. The respective crystal phases of β-eucryptite and lithium tantalate can be confirmed by, for example, X-ray Diffraction (hereinafter, referred to as “XRD” in some cases). It can also be confirmed by XRD that the complex does not contain a crystal phase or a glass phase other than the β-eucryptite crystal phase and the lithium tantalate crystal phase. As a raw material to be made complex with β-eucryptite, other raw materials showing positive thermal expansion behavior can be considered, but when the raw material is made complex, a by-product of a crystal phase or a glass phase other than the raw material is generated. For example, when β-eucryptite is made complex with alumina or zirconia to prepare a low thermal expansion complex, the mass ratio of the β-eucryptite and such raw material is about 1:1 or it is necessary to further increase the amount of such raw material. The bulk density of such a complex greatly exceeds 3 g/cm3. In addition, it is difficult to produce such a complex having stable characteristics because the amount and state of production of by-products may vary due to variations in the manufacturing process and the like. Low thermal expansion properties mean that the thermal expansion is close to zero and deformation due to temperature change is small. The temperature range in which the complex can exhibit low thermal expansion properties is, for example, from 0 to 50° C. In the temperature range of 0 to 50° C., the coefficient of (linear) thermal expansion calculated for each 1° C. may be within 0±1 ppm/K. When such a configuration is satisfied, the complex can exhibit low thermal expansion properties over a wide temperature range. The coefficient of thermal expansion is, for example, a value measured in accordance with JIS R 1618:1994. The coefficient of (linear) thermal expansion calculated for each 1° C. in the temperature range of 0 to 50° C. means that a coefficient of (linear) thermal expansion at 0 to 1° C., a coefficient of (linear) thermal expansion at 1 to 2° C., . . . and a coefficient of (linear) thermal expansion at 49 to 50° C. have been calculated. Hereinafter, the unit of the coefficient of thermal expansion is expressed as ppm/K or ppb/K, and 1 ppm/K is 1×10−6/K and 1 ppb/K is 1×10−9/K. The low thermal expansion material containing cordierite as a main component exhibits negative thermal expansion behavior below a certain temperature and positive thermal expansion behavior at a temperature higher than that temperature. In other words, the coefficient of thermal expansion can be brought close to 0 only in a very narrow temperature range. In some documents, it may be stated that the coefficient of thermal expansion in the predetermined temperature range can be reduced, but only the coefficient of thermal expansion calculated from the difference between the two temperatures of the minimum temperature and the maximum temperature in the predetermined temperature range is small. Therefore, it is unlikely that the coefficient of thermal expansion calculated for each 1° C. in the predetermined temperature range is small. In particular, it seems unlikely that, in the temperature range of 0 to 50° C., the coefficient of (linear) thermal expansion calculated for each 1° C. is set within 0±1 ppm/K, and further within 0±0.5 ppm/K. The complex may have a bulk density of 3 g/cm3or less. The complex may further have a bulk density of 2.55 g/cm3or less. When such a configuration is satisfied, the weight of the complex can be reduced. The lower limit of the bulk density may be 2.34 g/cm3. The bulk density is, for example, a value measured in accordance with JIS R 1634-1998. A typical low thermal expansion glass has a bulk density of about 2.53 g/cm3. A complex having a bulk density of 3 g/cm3can be prepared, for example, from a raw material having a mass ratio of lithium tantalate to β-eucryptite of 28.6 to 71.4. Such a complex contains 12% by volume of lithium tantalate and 88% by volume of β-eucryptite, and exhibits low thermal expansion properties with a coefficient of (linear) thermal expansion of 30 ppm/K. It is desirable that the members used for optical components are lightweight. In particular, members mounted on objects launched from the ground into space, such as artificial satellites, are desired to be lightweight, instead of limiting the mass that can be launched and reducing the launch cost. Therefore, a material having a low material density and high rigidity can be reduced in weight. A large configuration proportion of β-eucryptite is preferable because it enables a reduction in density. Further, a complex having a bulk density of 2.55 g/cm3can be prepared, for example, from a raw material having a mass ratio of lithium tantalate to β-eucryptite of 28.6 to 71.4. Such a complex contains 12% by volume of lithium tantalate and 88% by volume of β-eucryptite, and exhibits low thermal expansion properties with a coefficient of (linear) thermal expansion of 30 ppm/K. A complex containing 10% by volume of lithium tantalate and 90% by volume of β-eucryptite exhibits low thermal expansion properties with a coefficient of (linear) thermal expansion of 30 ppm/K. The coefficient of (linear) thermal expansion at 22° C. can be reduced to about 50 ppm/K, and the bulk density can be reduced to about 2.43 g/cm3. The Young's modulus of the complex may be 100 GPa or more. When such a configuration is satisfied, the rigidity of the complex is increased. The Young's modulus is improved by dispersing fine particles of lithium tantalate, which has a higher hardness than β-eucryptite, in a sintered body. In the absence of lithium tantalate, a glass phase is formed at the grain boundary and the Young's modulus decreases. The upper limit of the Young's modulus may be 123 GPa or 120 GPa. The Young's modulus is, for example, a value measured using a nanoindenter method. A typical low thermal expansion glass has a Young's modulus of about 90 GPa. The complex may have a specific rigidity of, for example, 33 or more. The complex may further have a specific rigidity of 39 or more. When such a configuration is satisfied, the rigidity of the complex is increased. The upper limit of the specific rigidity may be 51. The specific rigidity is, for example, a value calculated from the formula: Young's modulus/bulk density. A typical low thermal expansion glass has a specific rigidity of about 36. The complex may have a thermal conductivity of, for example, 2 W/mK or more. When such a configuration is satisfied, the thermal conductivity of the complex is increased, so that it is suitable as a fixing member for applications requiring heat dissipation property, such as the primary mirror of an astronomical telescope. The upper limit of the thermal conductivity may be 3.5 W/mK. The thermal conductivity is, for example, a value measured in accordance with JIS R 1611:2010. A typical low thermal expansion glass has a thermal conductivity of about 1.5 W/mK. The average particle size of the lithium tantalate crystal phase may be larger than the average particle size of the β-eucryptite crystal phase. When such a configuration is satisfied, the bending strength of the complex can be improved. The lithium tantalate crystal phase may have an average particle size of 4 μm or less, or 3 μm or less. The lower limit of the average particle size of the lithium tantalate crystal phase may be 0.7 μm or 1 μm. The particle size is related to the bending strength of the complex, and a small particle size has the effect of improving the bending strength. Therefore, it is preferable that the particle size of the crystal phase is small. For the same reason, the β-eucryptite crystal phase may have an average particle size of 5 μm or less, or 2 μm or less. The lower limit of the average particle size of the β-eucryptite crystal phase may be 0.7 μm or 1 μm. The average particle size is a value obtained by observing a cross section of the complex using, for example, a scanning electron microscope (hereinafter, referred to as “SEM” in some cases). The average particle size of a crystal phase having the β-eucryptite crystal phase and the lithium tantalate crystal phase combined may be 2 μm or less. The lower limit of the average particle size of the crystal phase may be 1 μm. The particle size is related to the bending strength of the complex, and a small particle size has the effect of improving the bending strength. Therefore, it is preferable that the particle size of the crystal phase is small. The percent by volume of the β-eucryptite crystal phase may be larger than the percent by volume of the lithium tantalate crystal phase. When such a configuration is satisfied, the proportion of β-eucryptite, which is lighter than lithium tantalate, is relatively large, so that the weight of the complex can be reduced. The volume ratio (volume proportion) of the β-eucryptite crystal phase to the lithium tantalate crystal phase may be from 90:10 to 99:1 or from 90:10 to 99.5:0.5. The volume ratio (percent by volume) is a value obtained by observing a cross section of the complex using, for example, SEM. When the volume ratio is as described above, the value of the coefficient of thermal expansion of the complex can be brought close to 0. Specifically, the coefficient of (linear) thermal expansion at 22° C. can be in the range of −500 ppb/K to 1000 ppb/K. Furthermore, by setting the above-mentioned volume ratio to 95:5 to 99:1, the coefficient of (linear) thermal expansion at 22° C. can be set within the range of −50 ppb/K to 50 ppb/K. The complex may have a relative magnetic permeability of 1.001 or less, or 1 or less. When such a configuration is satisfied, the complex becomes substantially non-magnetic, so that it is suitable as a member for applications requiring non-magnetism. The lower limit of the relative magnetic permeability may be 0.999. The relative magnetic permeability is a value measured using, for example, a vibrating sample magnetometer. The preferred range of the relative magnetic permeability is within 1±0.001. The complex is desired to be non-magnetic for application to, for example, members that may move in strong magnetic fields (e.g., components of artificial satellites) and members used in devices that use electron beams. In such cases, the relative magnetic permeability is required to be 1.001 or less. It has been found that the effect on the electron beam is significantly adversely affected when the relative magnetic permeability exceeds 1.001, and therefore, the relative magnetic permeability is desired to be 1.001 or less. The relative magnetic permeability is smaller than 1 in the case of a substance having diamagnetism, and is calculated to be smaller than 1. It has been found that β-eucryptite has a relative magnetic permeability of about 0.9999. When lithium tantalate to be made complex has an appropriate relative magnetic permeability, the relative magnetic permeability of the complex can fall within the above range. As a result of evaluation, typical commercially available lithium tantalate has a relative magnetic permeability of 1.2, and when the lithium tantalate is made into a complex, the complex may have a relative magnetic permeability of 1.001 or more, which is not preferable as members that may operate in strong magnetic fields and as members in devices that use electron beams. In a case where a test such as high-speed rotation (8000 Hz) in a magnetic field of 9.4 Tesla has been conducted, a behavior of a sample becoming eccentric in the container has been confirmed in the above-mentioned lithium tantalate powder, and a strong effect on the magnetic field has been confirmed. On the other hand, for example, lithium tantalate powder prepared by performing a heating/melting reaction treatment using lithium carbonate and tantalum pentoxide, having a purity of 99.9% or more, has a relative magnetic permeability of 1.001 or less, and even if the lithium tantalate powder is made into a complex with β-eucryptite at the above-mentioned ratio, the complex can have a relative magnetic permeability of 1.001 or less. It has been found that such lithium tantalate powder does not show eccentricity even when rotated at high speed (8000 Hz) in the above-mentioned magnetic field of 9.4 Tesla, and is not affected by the magnetic field. It has further been found that when complex of a lithium tantalate crystal phase and a β-eucryptite crystal phase at a ratio (volume ratio) of 0.12:0.88 is prepared using lithium tantalate having a relative magnetic permeability of 1.009, the complex has a relative magnetic permeability of 1.001. The complex may have a bending strength of, for example, 70 MPa or more, 110 MPa or more, or 150 MPa or more. When such a configuration is satisfied, the rigidity of the complex is high. The upper limit of the bending strength may be 170 MPa. The bending strength is, for example, a value measured in accordance with JIS R 1601:2008. The water absorption rate of the complex may be, for example, 0.1% or less. When such a configuration is satisfied, the complex can be densified. The water absorption rate is, for example, a value measured using the Archimedes method. The complex may be for optical members. Specific examples thereof include, for example, a fixed member such as a primary mirror of an astronomical telescope or a mirror mounted on an artificial satellite. The application of the complex is not limited to the optical member. <Method for Producing Complex> Next, a method for producing a complex according to the embodiment for the present disclosure will be described. In the present embodiment, first, crystals of β-eucryptite and lithium tantalate are mixed to obtain a mixture. At this time, in the obtained complex, the crystals may be mixed at a ratio such that the crystal phases of β-eucryptite and lithium tantalate each have a mass ratio of 70:30 to 99:1. As β-eucryptite (LiAlSiO4), a commercially available powder may be used, or lithium carbonate, Al2O3, and SiO2may be mixed at a predetermined ratio and heat-synthesized. The mixture is then sintered to give a complex. The sintering conditions may be set as follows, for example. The sintering temperature may be from 1050° C. to 1150° C. When the sintering temperature is set to 1150° C. or lower, the particle size can be controlled and densified. The keep time may be from 1 to 10 hours. <Lithium Tantalate> Next, lithium tantalate according to an embodiment of the present disclosure will be described. The lithium tantalate of the present embodiment has a relative magnetic permeability of 1.009 or less. Such lithium tantalate is suitable as a raw material for the above-mentioned complex. The lithium tantalate of the present embodiment may be used when the relative magnetic permeability of the complex is 1.001 or less. The lower limit of the relative magnetic permeability may be 0.993. Further, the lithium tantalate having the above-mentioned relative magnetic permeability can be used for other applications. For example, single-crystal lithium tantalate having the above-mentioned relative magnetic permeability can be used in a surface acoustic wave device. Such a surface acoustic wave device can reduce variations in characteristics in a magnetic field. Further, as such lithium tantalate, one having a relative magnetic permeability of 1.1 or less can be used. The lower limit of the relative magnetic permeability of such lithium tantalate may be 0.9. <Method for Producing Lithium Tantalate> Next, a method for producing lithium tantalate according to the embodiment of the present disclosure will be described. First, lithium carbonate and tantalum pentoxide, having a purity of 99.9% by mass or more, are used to perform dry mixing and pulverization, and then heated and melted at 1000° C. or higher in a crucible to synthesize lithium tantalate. Then, the lithium tantalate is subjected to heat treatment in coexistence with potassium hydrogen carbonate (KHCO3) or a mixture of potassium hydrogen carbonate and at least one powder of transition metal elements such as Ti, Fe, Al, Ni, and Zn in a temperature range equal to or lower than the Curie temperature of lithium tantalate from 550° C. under a nitrogen atmosphere to thereby obtain the lithium tantalate of the present embodiment. The transition metal element to be combined with KHCO3is not particularly limited, but Ti and Fe are preferable, and Ti and Fe may be used. The potassium hydrogen carbonate and the transition metal element are mixed, for example, in a ratio such that the amount of the potassium hydrogen carbonate is from 5 to 15 parts by mass with respect to 100 parts by mass of the lithium tantalate, and the amount of the transition metal element is from 1 to 10 parts by mass with respect to 100 parts by mass of the potassium hydrogen carbonate. The conventional lithium tantalate without the above-mentioned treatment has a relative magnetic permeability of 1.2, and it is considered that this relative magnetic permeability is expressed by the presence of lithium pores. In the lithium tantalate of the present embodiment to be subjected to the above-mentioned treatment, the lithium pores are reduced by forming a K solid solution in the lithium pores existing in the conventional lithium tantalate, and the relative magnetic permeability is reduced to 1.1 or less, and further 1.009 or less. Next, a complex according to another embodiment of the present disclosure will be described in detail. The complex according to another embodiment contains a β-eucryptite (LiAlSiO4) crystal phase and a lithium tantalate (LiTaO3) crystal phase, and the lithium tantalate crystal phase contains calcium (Ca). When calcium is contained in the lithium tantalate crystal phase, the range in which the coefficient of thermal expansion of the complex varies with temperature change can be narrowed. As a result, the value of the coefficient of thermal expansion can also be brought close to 0 (zero). As the reason for this, the following reasons can be presumed. A comparison of β-eucryptite and lithium tantalate on the effect of the coefficient of thermal expansion of the complex on the temperature dependence (the range in which the coefficient of thermal expansion varies with temperature changes from 15° C. to 40° C.) shows that the effect of lithium tantalate is greater than that of β-eucryptite. Therefore, when the temperature dependence of the coefficient of thermal expansion of lithium tantalate is reduced, the temperature dependence of the coefficient of thermal expansion of the complex can also be reduced. When calcium is contained in the lithium tantalate crystal phase, the temperature dependence of the coefficient of thermal expansion of lithium tantalate can be reduced due to the substitution of lithium in the lithium tantalate with calcium. Therefore, when calcium is contained in the lithium tantalate crystal phase, the temperature dependence of the coefficient of thermal expansion of lithium tantalate can be reduced, and accordingly, the temperature dependence of the coefficient of thermal expansion of the complex can also be reduced. As a result, the range in which the coefficient of thermal expansion of the complex varies with temperature change can be narrowed, and the value of the coefficient of thermal expansion can also be brought close to 0. Combined with these effects, the complex can exhibit low thermal expansion characteristics over a wide temperature range. The complex can also exhibit high rigidity due to the lithium tantalate crystal phase. When the lithium tantalate is represented by the composition formula (Li1-xCax/2)TaO3, a relationship of 0<x≤0.2 may be satisfied. In the composition formula, x indicates the amount of calcium substituted. As x increases from 0 to 0.1, the temperature dependence of the coefficient of thermal expansion (from 15° C. to 40° C.) can be reduced. Moreover, the temperature dependence tends to slightly increase when x increases from 0.1 to 0.2, but becomes smaller than that when x is 0. By setting x to 0.05 or more, the temperature dependence of the coefficient of thermal expansion can be reduced. The composition of lithium tantalate represented by the composition formula described above can be measured, for example, by ICP (Inductively Coupled Plasma) emission spectroscopy. Calcium up to about x=0.1 is dissolved in the lithium tantalate crystal phase. Lithium tantalate at x=0 to 0.1 is composed substantially only of the lithium tantalate crystal phase. Lithium tantalate with x greater than 0.1 is presumed to be composed of a lithium tantalate crystal phase with about x=0.1 and excess calcium component. Therefore, the lithium tantalate of the present embodiment may contain excess calcium component, and it can be said that the lithium tantalate crystal phase of the present embodiment does not contain excess calcium component. The excess calcium component is considered to exist outside the crystal phase, but is not directly observed. In the complex according to another embodiment, 2θ of a diffraction peak of a (006) plane in the lithium tantalate crystal phase may be 39.25° or higher. The diffraction peak of the (006) plane is shifted to the higher angle side due to the calcium substitution. This indicates that the c-axis lattice constant is contracted by the calcium solid solution. In the above-mentioned composition formula, a relationship of 2θ≥39.25° corresponds to a relationship of x≥0.05. Further, 2θ=39.18° corresponds to x=0. Therefore, the value of 2θ indicates the content of calcium in the lithium tantalate crystal phase. 2θ may be 39.33° or less. 2θ is, for example, a value obtained by measuring by XRD. In the complex according to another embodiment, the change width of the coefficient of (linear) thermal expansion calculated for each 1° C. in the temperature range of 15° C. to 40° C. may be 50 ppb/K or less. Further, in the temperature range of 0° C. to 50° C., the change width of the coefficient of (linear) thermal expansion calculated for each 1° C. may be 100 ppb/K or less. The coefficient of (linear) thermal expansion at 22° C. may be from −500 ppb/K to 1000 ppb/K. The coefficient of (linear) thermal expansion is a value measured in accordance with JIS R 1618:1994, for example. The change width of the coefficient of thermal expansion calculated for each 1° C. in the temperature range of 15° C. to 40° C. is a value obtained by calculating a coefficient of thermal expansion of 15° C. to 16° C., a coefficient of thermal expansion of 16° C. to 17° C., . . . , and a coefficient of thermal expansion of 39° C. to 40° C., selecting the maximum value and the minimum value from the calculated coefficients of thermal expansion, and applying them to the formula: maximum value-minimum value. This point is the same as in the change width of the coefficient of thermal expansion calculated for each 1° C. in the temperature range of 0° C. to 50° C. <Method for Producing Complex> Next, a method for producing a complex according to another embodiment of the present disclosure will be described. First, a β-eucryptite crystal and a lithium tantalate crystal, which are raw materials, are prepared. As the β-eucryptite crystal, in the same manner as above, a commercially available powder may be used, or one in which lithium carbonate, Al2O3, and SiO2are mixed at a predetermined ratio and heat-synthesized may be used. As the lithium tantalate crystal, one in which lithium is substituted with calcium is used. As such lithium tantalate crystal, for example, one in which calcium carbonate is mixed with lithium carbonate and tantalum pentoxide at a predetermined ratio and heat-synthesized may be used. This point will be described in detail in the method for producing lithium tantalate, which will be described later. Next, the crystals of β-eucryptite and lithium tantalate are mixed to give a mixture. At this time, in the obtained complex, the crystals may be mixed at a ratio such that the crystal phases of β-eucryptite and lithium tantalate each have a mass ratio of 70:30 to 99:1. Then, the above-mentioned mixture is sintered to give a complex. The sintering conditions may be set as follows, for example. The sintering temperature may be from 1050° C. to 1250° C., or may be from 1050° C. to 1150° C. The keep time may be from 1 to 10 hours. <Lithium Tantalate> Next, lithium tantalate according to another embodiment of the present disclosure will be described. When the lithium tantalate according to another embodiment is represented by the composition formula (Li1-xCax/2)TaO3, a relationship of 0<x≤0.2 is satisfied. Such lithium tantalate is suitable as a raw material for the above-mentioned complex. When single-crystal lithium tantalate is used, the lithium tantalate may satisfy a relationship of 0<x≤0.1, which does not form the excess calcium component described above. Lithium tantalate may have a relative magnetic permeability of 1.009 or less. Such lithium tantalate is suitable as a raw material when the relative magnetic permeability of the complex is 1.001 or less. The lower limit of the relative magnetic permeability may be 0.993. Further, the lithium tantalate represented by the above-mentioned composition formula can be used for other applications. For example, single-crystal lithium tantalate represented by the above-mentioned composition formula can be used in a surface acoustic wave device. Such a surface acoustic wave device can reduce variations in characteristics in a magnetic field. Further, as such lithium tantalate, one having a relative magnetic permeability of 1.1 or less can be used. The lower limit of the relative magnetic permeability of such lithium tantalate may be 0.9. <Method for Producing Lithium Tantalate> Next, a method for producing lithium tantalate according to another embodiment of the present disclosure will be described. For example, when lithium carbonate, tantalum pentoxide, and calcium carbonate, having a purity of 99.9% by mass or more, are used to perform dry mixing and pulverization, and then heated and melted at 1000° C. or higher in a crucible, lithium tantalate represented by the above-mentioned composition formula can be synthesized. The ratio of the calcium carbonate may be set so as to satisfy a relationship of 0<x≤0.2 in the above-mentioned composition formula. Specifically, the amount of the calcium carbonate may be 1 mol or less with respect to 4 mol of the lithium carbonate. The obtained lithium tantalate may be subjected to heat treatment in coexistence with potassium hydrogen carbonate (KHCO3) or a mixture of potassium hydrogen carbonate and at least one powder of transition metal elements such as Ti, Fe, Al, Ni, and Zn in a temperature range equal to or lower than the Curie temperature of lithium tantalate from 550° C. under a nitrogen atmosphere. The heat treatment time may be set to 1 to 10 hours. The transition metal element to be combined with KHCO3is not particularly limited, but Ti and Fe are preferable, and Ti and Fe may be used. The amount of the potassium hydrogen carbonate and the transition metal element may be set, for example, such that the amount of the potassium hydrogen carbonate is from 5 to 15 parts by mass with respect to 100 parts by mass of the lithium tantalate, and the amount of the transition metal element is from 1 to 10 parts by mass with respect to 100 parts by mass of the potassium hydrogen carbonate. The lithium tantalate without the above-mentioned heat treatment has a relative magnetic permeability of 1.2, and it is considered that this relative magnetic permeability is expressed by the presence of lithium pores. In the lithium tantalate to be subjected to the above-mentioned heat treatment, the lithium pores are reduced by forming a K solid solution in the lithium pores existing in the lithium tantalate, and the relative magnetic permeability is reduced to 1.1 or less, and further 1.009 or less. Hereinafter, the present disclosure will be described in detail with reference to examples, but the present disclosure is not limited to the following examples. EXAMPLES [Samples 1 and 2] <Preparation of Complex> A crystal of lithium tantalate having a relative magnetic permeability of 1.00001 was prepared. Specifically, first, lithium carbonate and tantalum pentoxide, having a purity of 99.9% by mass or more, were used to perform dry mixing and pulverization, and then heated and melted at 1670° C. in an iridium crucible to synthesize lithium tantalate. Then, the lithium tantalate was pulverized to obtain a crystal powder of lithium tantalate having an average particle size (D50) of 1.5 μm. Then, the obtained lithium tantalate was subjected to heat treatment in coexistence with a mixture of potassium hydrogen carbonate and a powder of Ti and Fe as transition metal elements at 550° C. for 3 hours in a nitrogen atmosphere to thereby obtain lithium tantalate having a relative magnetic permeability of 1.00001. The potassium hydrogen carbonate and the transition metal element were mixed in a ratio such that the amount of the potassium hydrogen carbonate was 10 parts by mass with respect to 100 parts by mass of the lithium tantalate, and the amount of the transition metal element was 5 parts by mass with respect to 100 parts by mass of the potassium hydrogen carbonate. A complex was prepared using the crystal of lithium tantalate obtained as described above. Specifically, crystals of β-eucryptite having an average particle size (D50) of 0.9 μm and lithium tantalate were mixed to give a mixture. At this time, in the obtained complex, the crystals were mixed at a ratio such that the crystal phases of β-eucryptite and lithium tantalate each had the mass ratio shown in Table 1. Then, the mixture was sintered to give complexes of samples 1 and 2 shown in Table 1. The sintering conditions are as follows. Such sintering conditions cause grain growth in the crystals of β-eucryptite and lithium tantalate to have the average particle size to be shown later. Sintering temperature: 1150° C. Keep time: 3 hours The obtained complex was measured by XRD. The XRD measurement conditions are as follows. Analyzer: “X'Pert PRO-MRD” manufactured by PANalytical Bulb: CuKα Slit width: 0.5° Measurement range: 2θ=10 to 80° From the measurement results by XRD, the crystal phases of β-eucryptite and lithium tantalate were confirmed in the obtained complex. It was also confirmed that the complex did not contain a crystal phase or a glass phase other than the β-eucryptite crystal phase and the lithium tantalate crystal phase. The fact that no crystal phase other than the above-mentioned two crystal phases is contained means that when the diffraction peak having a peak intensity of more than 3 times the background intensity of XRD is set as a dominant peak, there is no peak except those of lithium tantalate and β-eucryptite. In addition, in the presence of an amorphous phase such as glass, a halo peak is confirmed near 2θ=20° in XRD. The fact that no glass phase other than the above-mentioned two crystal phases is contained means that there is no halo peak having a peak intensity of more than 3 times the background intensity as described above. <Evaluation> For samples 1 and 2, the volume proportion (percent by volume) of the β-eucryptite crystal phase to the lithium tantalate crystal phase, average particle size of each of the crystal phases of β-eucryptite and lithium tantalate, bulk density, Young's modulus, specific rigidity, thermal conductivity, relative magnetic permeability, and coefficient of thermal expansion were measured. The measurement method is shown below, the measurement results of the coefficient of thermal expansion are shown inFIG.1, and the other measurement results are shown in Table 1. In the following measurements, the cross section of the complex was mirror-finished by polishing with a 0.5 μm diamond paste. (Volume Proportion) The cross section of the complex was mirror-finished, and the cross section was observed with a reflected electron image at a magnification of 250 times using SEM. At this time, lithium tantalate and β-eucryptite were observed with different contrasts, so that both were distinguishable from each other. Then, the cross-sectional observation photograph was subjected to image analysis to determine their areas with respect to the area of the analyzing range, each of which was taken as a percent by volume. (Average Particle Size) The cross section of the complex was mirror-finished and then observed with a reflected electron image, and the average particle size was determined by image analysis of the observed image. (Bulk Density) Measured in accordance with JIS R 1634-1998. (Young's Modulus) The cross section of the mirror-finished complex was measured at 10 points at an indentation depth of 2000 nm by continuous rigid body measurement (CSM) using a Nano Indenter XP manufactured by MTS Systems Corporation, and the average value thereof was defined as Young's modulus. (Specific Rigidity) The specific rigidity was calculated by applying the measurement results of bulk density and Young's modulus to the formula: Young's modulus/bulk density. (Thermal Conductivity) Measured in accordance with JIS R 1611:2010. (Relative Magnetic Permeability) Sample size: 9 mm×9 mm×1.5 mm Analyzer: Vibrating sample magnetometer “VSM-5” manufactured by Toei Industry Co., Ltd. Measurement temperature: Room temperature (22° C.) Magnetic field application direction: parallel to the surface Magnetization range: 0.005 emu Magnetic field range: 10 kOe Magnetic field sweep: 1.4 kOe/min Time constant: 0.3 sec (Coefficient of Thermal Expansion) Measured in accordance with JIS R 1618:1994. For comparison, the coefficients of thermal expansion of β-eucryptite as sample 3 and lithium tantalate as sample 4 were also measured. TABLE 1Volume ratioAverage particleMixing ratio(% by volume)size (μm)(mass ratio)LithiumB-eucryptiteLithiumβ-Lithiumβ-eucryptitetantalateβ-eucryptitetantalateeucryptitetantalatecrystal phasecrystal phasecrystal phasecrystal phaseSample 193797.52.542Sample 286.313.795.05.042BulkYoung'sThermalRelativedensitymodulusSpecificconductivitymagnetic(g/cm3)(GPa)rigidity(W/mK)permeabilitySample 12.371185030.9999899Sample 22.381185030.9999895 [Sample Nos. 1 to 43] <Preparation of Complex> A complex different from samples 1 to 4 was prepared. When represented by the composition formula (Li1-xCax/2)TaO3, crystals of lithium tantalate in which x had the values shown in Table 2 were prepared. Specifically, first, lithium carbonate, tantalum pentoxide, and calcium carbonate, having a purity of 99.9% by mass or more, were used to perform dry mixing and pulverization, and then heated and melted at 1670° C. in an iridium crucible to synthesize lithium tantalate. Then, the lithium tantalate was pulverized to obtain a crystal powder of lithium tantalate having an average particle size (D50) of 1.5 μm. The ratio of calcium carbonate was set so that x would be the values shown in Table 2. x in Table 2 is a value measured on the obtained crystal powder of lithium tantalate by ICP emission spectroscopy. The obtained lithium tantalate was subjected to heat treatment in coexistence with a mixture of potassium hydrogen carbonate and a powder of Ti and Fe as transition metal elements at 550° C. for 3 hours in a nitrogen atmosphere to thereby obtain lithium tantalate having a relative magnetic permeability of 1.00001. The potassium hydrogen carbonate and the transition metal element were mixed in a ratio such that the amount of the potassium hydrogen carbonate was 10 parts by mass with respect to 100 parts by mass of the lithium tantalate, and the amount of the transition metal element was 5 parts by mass with respect to 100 parts by mass of the potassium hydrogen carbonate. A complex was prepared using the crystal of lithium tantalate obtained as described above. Specifically, crystals of β-eucryptite having an average particle size (D50) of 0.9 μm and lithium tantalate were mixed to give a mixture. At this time, in the obtained complex, the crystals were mixed at a ratio such that the crystal phases of β-eucryptite and lithium tantalate each had the percent by volume shown in Table 2. Specifically, each crystal was mixed at the mixing ratio (mass ratio) shown in Table 2. Then, the mixture was sintered to give complexes of Sample Nos. 1 to 43 shown in Table 2. The sintering conditions are as follows. Such sintering conditions caused grain growth in the crystals of β-eucryptite and lithium tantalate to the average particle size to be shown later. Here, a sample in which the same amount of glass (borosilicate glass) instead of lithium tantalate in Sample No. 7 shown in Table 2 was added, had a Young's modulus of 90 GPa and a specific rigidity of 36. Sintering temperature: 1150° C. Keep time: 3 hours The obtained complex was measured by XRD. The XRD measurement conditions are as follows. Analyzer: “X'Pert PRO-MRD” manufactured by PANalytical Bulb: CuKα Slit width: 0.5° Measurement range: 2θ=10 to 80° From the measurement results by XRD, the crystal phases of β-eucryptite and lithium tantalate were confirmed in the obtained complex. It was also confirmed that the complex did not contain a crystal phase or a glass phase other than the β-eucryptite crystal phase and the lithium tantalate crystal phase. The fact that no crystal phase other than the above-mentioned two crystal phases is contained means that when the diffraction peak having a peak intensity of more than 3 times the background intensity of XRD is set as a dominant peak, there is no peak except those of lithium tantalate and β-eucryptite. In addition, in the presence of an amorphous phase such as glass, a halo peak is confirmed near 2θ=20° in XRD. The fact that no glass phase other than the above-mentioned two crystal phases is contained means that there is no halo peak having a peak intensity of more than 3 times the background intensity as described above. <Evaluation> The following (1) to (10) were evaluated for Sample Nos. 1 to 43. (1) Volume proportion of β-eucryptite crystal phase to lithium tantalate crystal phase (2) 2θ of diffraction peak of (006) plane in lithium tantalate crystal phase (3) Average particle size of crystal phase (4) Change width of coefficient of thermal expansion calculated for each 1° C. in evaluation temperature range (5) Coefficient of thermal expansion at 22° C. (6) Bulk density (7) Young's modulus (8) Specific rigidity (9) Thermal conductivity (10) Relative magnetic permeability The measurement methods are shown below, and the measurement results except (3) are shown in Table 2. In the following measurements, the cross section of the complex was mirror-finished by polishing with a diamond paste having an average particle size of 0.5 μm. (1) Volume Proportion of β-Eucryptite Crystal Phase to Lithium Tantalate Crystal Phase The cross section of the complex was mirror-finished, and the cross section was observed with a reflected electron image at a magnification of 250 times using SEM. At this time, lithium tantalate and β-eucryptite were observed with different contrasts, so that both were distinguishable from each other. Then, the cross-sectional observation photograph was subjected to image analysis to determine their areas with respect to the area of the analyzing range, each of which was taken as a percent by volume. Since the above-mentioned excess calcium component is in a very small amount (0.1% by volume or less), the total value of the β-eucryptite crystal phase and the lithium tantalate crystal phase is indicated as 100% by volume in Table 2. (2) 2θ of Diffraction Peak of (006) Plane in Lithium Tantalate Crystal Phase Determined from the above-mentioned measurement results by XRD. (3) Average Particle Size of Crystal Phase The cross section of the complex was mirror-finished and then observed with a reflected electron image, and the average particle size of each of the crystal phases of β-eucryptite and lithium tantalate was determined by image analysis of the observed image. In addition, the average particle size of the whole crystal phase was determined without distinguishing between those crystal phases. In each of the samples, the β-eucryptite crystal phase had an average particle size of 2 μm, the lithium tantalate crystal phase had an average particle size of 4 μm, and the combined crystal phase had an average particle size of 2 μm. (4) Change Width of Coefficient of Thermal Expansion Calculated for Each 1° C. in Evaluation Temperature Range The coefficient of thermal expansion for each 1° C. from 0° C. to 50° C. was measured in accordance with JIS R 1618:1994. Then, the maximum and minimum values of the coefficient of thermal expansion in each of the evaluation temperature ranges of 15° C. to 40° C. and 0° C. to 50° C. were applied to the formula: maximum value-minimum value, and the change width of the coefficient of thermal expansion was calculated. In addition, the change in the coefficient of thermal expansion with respect to temperature was described. A monotonous increase means that the coefficient of thermal expansion increases as the temperature increases in the target temperature range. And, a monotonous decrease is vice versa. When the temperature dependence of the coefficient of thermal expansion is low, the opposite behavior may be exhibited in a narrow temperature range due to factors such as measurement error. (5) Coefficient of Thermal Expansion at 22° C. The coefficient of thermal expansion at 21.5 to 22.5° C. was measured in accordance with JIS R 1618:1994. (6) Bulk Density Measured in accordance with JIS R 1634:1998. (7) Young's Modulus The cross section of the mirror-finished complex was measured at 10 points at an indentation depth of 2000 nm by continuous rigid body measurement (CSM) using a Nano Indenter XP manufactured by MTS Systems Corporation, and the average value thereof was defined as Young's modulus. (8) Specific Rigidity The specific rigidity was calculated by applying the measurement results of bulk density and Young's modulus to the formula: Young's modulus/bulk density. (9) Thermal Conductivity Measured in accordance with JIS R 1611:2010. (10) Relative Magnetic Permeability Sample size: 9 mm×9 mm×1.5 mm Analyzer: Vibrating sample magnetometer “VSM-5” manufactured by Toei Industry Co., Ltd. Measurement temperature: Room temperature (22° C.) Magnetic field application direction: parallel to the surface Magnetization range: 0.005 emu Magnetic field range: 10 kOe Magnetic field sweep: 1.4 kOe/min Time constant: 0.3 sec TABLE 2Complex(006)surfaceMixingofLithiumβ-Volume ratioLithiumCoefficienttantalateeucryptite(% by volume)tantalateofMixingMixingLithiumβ-crystalthermalrationrationtantalateeucryptitephaseChange with coefficent of thermal expansion inexpansionBulkYoung'sThermalRelativeSample(mass(masscrystalcrystal20evaluation temperature range (ppb/K)(ppb/K)densitymodulusSpecificconductivitymagneticNos.Xratio)ratio)phasephase(deg.)15° C.~40° C.0° C.~50° C.22° C.(g/cm3)(GPa)rigidity(W/mK)permeability1039719939.18400Monotonous increase420Monotonous increase−502.391184930.99998992069429839.18398Monotonous increase419Monotonous increase−262.391184930.9999900307932.597.539.18401Monotonous increase421Monotonous increase102.371185030.99998884099139739.18399Monotonous increase420Monotonous increase302.381215130.999990050148659539.18402Monotonous increase422Monotonous increase492.381215130.9999890602674109039.18505Monotonous increase513Monotonous increase9942.391225130.999991370.052980.589.539.2550Monotonous increase91Monotonous increase−4212.391184930.999990080.0539719939.2550Monotonous increase80Monotonous increase−482.391184930.999987890.0569429839.2549Monotonous increase81Monotonous increase−232.391205030.9999890100.057932.597.539.2548Monotonous increase79Monotonous increase82.401205030.9999890110.0599139739.2549Monotonous increase81Monotonous increase252.411205030.9999910120.05148659539.2548Monotonous increase80Monotonous increase472.421215030.9999809130.052674109039.2548Monotonous increase81Monotonous increase9892.451225030.9999898140.082980.599.539.3046Monotonous increase59Monotonous increase−4172.391184930.9999880150.0839719939.3045Monotonous increase51Monotonous increase−452.391184930.9999900160.0869429839.3043Monotonous increase49Monotonous increase−202.391184930.9999899170.087932.597.539.3044Monotonous increase50Monotonous increase72.411205030.9999898180.0899139738.3045Monotonous increase48Monotonous increase202.411215030.9999897190.08148659539.3044Monotonous increase52Monotonous increase392.421215030.9999879200.082674109039.3044Monotonous increase52Monotonous increase9922.451225030.9999910210.12980.599.539.3311Monotonous increase is22Monotonous increase is−4222.391184930.9999888changed to monotonouschanged to monotonousdecrease at room temperaturedecrease at room temperature220.139719939.3311Monotonous increase is20Monotonous increase is−482.391184930.9999899changed to monotonouschanged to monotonousdecrease at room temperaturedecrease at room temperature230.169429839.339Monotonous increase is21Monotonous increase is−212.401195030.9999877changed to monotonouschanged to monotonousdecrease at room temperaturedecrease at room temperature240.17932.597.539.337Monotonous increase is19Monotonous increase is22.411205030.9999990changed to monotonouschanged to monotonousdecrease at room temperaturedecrease at room temperature250.199139739.3310Monotonous increase is24Monotonous increase is172.411205030.9999799changed to monotonouschanged to monotonousdecrease at room temperaturedecrease at room temperature260.1148659539.3312Monotonous increase is22Monotonous increase is202.421215030.9999904changed to monotonouschanged to monotonousdecrease at room temperaturedecrease at room temperature270.12674109039.3312Monotonous increase is22Monotonous increase is9952.451225030.9999899changed to monotonouschanged to monotonousdecrease at room temperaturedecrease at room temperature280.152980.599.539.3349Monotonous increase72Monotonous increase−4252.391174930.9999901290.1539719939.3349Monotonous increase77Monotonous increase−502.391184930.9999889300.1569429839.3350Monotonous increase76Monotonous increase−232.401184930.9999798310.157932.597.539.3348Monotonous increase78Monotonous increase92.411194930.9999887320.1599139739.3348Monotonous increase75Monotonous increase302.421184930.9999699330.15148659539.3350Monotonous increase79Monotonous increase492.431214930.9999888340.152674109039.3350Monotonous increase80Monotonous increase9912.451234930.9999896350.22980.599.539.3350Monotonous increase99Monotonous increase−4302.391184930.9999902360.239719939.3349Monotonous increase98Monotonous increase−492.401184930.9999899370.269429839.3349Monotonous increase99Monotonous increase−252.411194930.9999895380.27932.597.539.3349Monotonous increase97Monotonous increase102.421205030.9999899390.299139739.3349Monotonous increase99Monotonous increase322.421205030.9999798400.2148659539.3350Monotonous increase99Monotonous increase482.431225030.9999809410.22674109039.3350Monotonous increase99Monotonous increase9942.451235030.9999960420.051981118939.3361Monotonous increase101Monotonous increase−4382.391195030.999987430.050.699.40.399.739.3362Monotonous increase103Monotonous increase9932.451225030.999967 [Sample Nos. 44 and 45] <Preparation of Complex> First, when represented by the composition formula (Li1-xCax/2)TaO3, crystals of lithium tantalate in which x had the values shown in Table 3 were prepared in the same manner as in Sample Nos. 1 to 43. Next, in the same manner as in Sample Nos. 1 to 43, except that the mixing ratio (mass ratio) was set to the ratio shown in Table 3, the crystals of β-eucryptite and lithium tantalate were mixed to give a mixture. Then, in the same manner as in Sample Nos. 1 to 43, except that the sintering temperature was set to the conditions shown in Table 3, the mixture was sintered, and complexes of Samples Nos. 44 and 45 shown in Table 3 were obtained. The obtained complex was measured by XRD in the same manner as in Sample Nos. 1 to 43. As a result, the crystal phases of β-eucryptite and lithium tantalate were confirmed in the obtained complex. It was also confirmed that the complex did not contain a crystal phase or a glass phase other than the β-eucryptite crystal phase and the lithium tantalate crystal phase. <Evaluation> The following (1), (3), (11) and (12) were evaluated for Sample Nos. 44 and 45. (1) Volume proportion of β-eucryptite crystal phase to lithium tantalate crystal phase (3) Average particle size of crystal phase (11) Bending strength (12) Water absorption rate The measurement methods of (1) and (3) are the same as those for Sample Nos. 1 to 43. The measurement methods of (11) and (12) are shown below, and the measurement results are shown in Table 3. For comparison, (11) and (12) were also evaluated for Sample Nos. 10 and 38. The results are also shown in Table 3. (11) Bending Strength Measured in accordance with JIS 1601. (12) Water Absorption Rate Measured by the Archimedes method. TABLE 3MixingComplesβ-Volume ratioLithium tantalateeucryptite(% by volume)Average particle size (μm)MixingMixingLithiumβ-Lithiumβ-WaterratiorationtantalateeucryptiteSinteringtantalateeucryptiteBendingabsorptionSample(mass(masscrystalcrystaltemperaturecrystalcrystalAs astrengthrateNos.xratio)ratio)phasephase(° C.)phasephaseWhole(MPa)(%)100.057932.597.511504221600.04440.057932.597.5125041111730.02380.27932.597.511504221630.03450.27932.597.5125041212700.02 | 51,659 |
11858852 | DETAILED DESCRIPTION Certain embodiments described herein relate generally to the field of processing igneous anorthosite rock to form 3D printable material. The systems and methods enable the construction of structures using raw, in-situ natural resources without the need for additives to adjust or modify the viscosity of the molten material prior to extrusion or printing. Additionally, the printable material described herein differs from traditional cementitious ink in that the printable material derived from igneous anorthosite rock that is readily available in certain locations. The present application is directed toward the in-situ use of aluminosilicate materials in 3D printing. Extrusion involves creating a viscous fluid that is pumped through a nozzle to print beads of material in layers that harden after deposition. Extrusion of concrete is the predominant approach to 3D printing for construction, although foams and other polymers have also been used. In contrast, the presently disclosed 3D printable material is derived from igneous anorthosite rock that is readily available in certain locations or areas. In one embodiment, the igneous anorthosite rock predominantly comprises plagioclase feldspar. FIG.1illustrates an exemplary rock processing system100for preparing printable material derived from an aluminosilicate material such as igneous anorthosite rock. The rock processing system100includes a hopper102secured to a feeding tube104that directs material into an electric reactor assembly106. An auger108directs the material through the feeding tube104, and the material is extruded from the furnace assembly106through a high temperature nozzle assembly110. The hopper102, the feeding tube104, the auger108, and the nozzle assembly110can be any commercially available products. The electric reactor assembly106may operate through electric induction means, multiple electric resistive-based designs, or any other suitable design. FIG.2outlines an exemplary method200for developing the printable material using the rock processing system100. In a first step202, an aluminosilicate powder material is fed into the hopper102and moves through the feeding tube104by means of the auger108into the electric reactor assembly106. In one embodiment, the aluminosilicate powder is derived from igneous anorthosite rock. The natural aluminosilicate predominantly consists of Labradorite, a feldspar mineral. The powder may be passed through a sieve to remove larger pieces before entering the hopper. The aluminosilicate material is heated to a melting temperature in the reactor assembly106in step204during which the material melts from a solid to a molten state. The aluminosilicate powder is heated gradually to a temperature between approximately 1,100° C. and approximately 1,750° C., preferably at least approximately 1,150° C., to form a molten aluminosilicate material. In other embodiments, the aluminosilicate material may be derived from another rock source and the temperature range is adjusted to the melting temperature of the rock source. In a preferred embodiment, no additives are used to adjust or modify the viscosity of the liquid state before the molten mixture reaches the nozzle110. In step206, the molten aluminosilicate material is maintained at the melting temperature within the reactor assembly106for a period of time in order to allow for phase changes and to reach the viscosity needed for extrusion. In one embodiment, maintaining the temperature for between about at least one minute and up to about 45 minutes, preferably at least approximately 45 minutes, allows the molten aluminosilicate material to form crystalline and amorphous phases and reach a suitable viscosity. In other embodiments, the temperature may be maintained for more than 45 minutes. When the aluminosilicate material is derived from another rock source, the duration of time at which the molten material is held at its melting temperature may vary to reach the desired crystalline structure and viscosity. In step108, the molten aluminosilicate material is extruded through the high temperature nozzle assembly110, and the printed aluminosilicate material hardens after about 15 minutes under normal conditions. In one embodiment, the molten material cools to the hardened state at a rate of about 300 degrees Celsius for the first two minutes and then the cooling rate decreases. The initial set time is around 30 seconds. The hardening step may take longer or shorter, depending on the conditions of the environment under which the printable material is extruded. FIG.3provides the phases of the crystalline structure of a hardened sample of aluminosilicate material after it was melted at 1,300° C. The 3D printable material contains about 11.5% amorphous phase (having no clear structure). The crystalline phase includes of 76.1% of albite/anorthosite feldspar, 10.1% dolomite, and 2.4% calcite. The strength of the hardened material is provided by the crystalline phase, primarily the feldspar. In one embodiment, the crystalline structure of a hardened sample of aluminosilicate material includes between about 50 and 90% albite/anorthosite feldspar. Density of the cooled material was measured using a pycnometer. One set of samples provided densities ranging between about 1.916 g/cm3to about 2.3 g/cm3. Referring toFIG.4, the hardened sample demonstrates a compressive strength of 20,222 psi after about 7.5 minutes. In a preferred embodiment, hardened aluminosilicate material has a compressive strength between about 5,000 psi to about 30,000 psi due to the generation of crystalline phases during the period of time that the material is held at its melting temperature. Specifically, the albite/anorthosite feldspar generated during this period and the calcite contribute to the increased strength. The porosity of a hardened sample of the printed material was determined using mercury intrusion porosimetry. As shown inFIG.5, the hardened sample has a porosity of 14.84% with a threshold pore diameter of 1.04 μm and a critical pore diameter of 0.27 μm. In a preferred embodiment, the hardened aluminosilicate material has a porosity between about 10% and about 20%. Threshold pore diameters are defined as the largest pore diameter at which significant intruded mercury pore volume is detected were calculated to be the pore size at the first inflection point. These dimensions are comparable to a normal concrete system. The enhanced strength can therefore be attributed to the formation of the albite/anorthosite feldspar generated during the period at which the material is held at its melting temperature. In some embodiments, the rock processing system100for developing 3D printable material from aluminosilicate material is mounted within a robotic motion platform. In other embodiments, the rock processing system100is incorporated into a large scale gantry used by the construction system to place the high temperature nozzle assembly110of the rock processing system100at the appropriate x, y and z axis positions. Other gantry designs, rolling towers, robotic arms on mobile bases, and other systems may also be used to deposit the 3D printable material described herein. An exemplary construction system10is shown inFIG.6. In this embodiment, the construction system effectuates the construction of a wall structure by passing the rock processing system100above a surface and extruding molten material from the nozzle of the rock processing system100. As the rock processing system100moves in three possible orthogonal axes, as well as angles therebetween, the nozzle emits extruded molten material onto the upper surface of the wall structure as it is being formed. The wall structure is formed layer-by-layer by laying down an elongated bead of printable material beginning with the first layer on ground or a pre-existing foundation. As each layer of elongated beads are laid down onto the foundation or onto a previous layer, a plurality of stacked elongated beads of extruded building material additively, and three dimensions, form a building structure. The printing assembly may shut off flow of extruded material in order to switch printable inks and/or nozzles printing printable inks. Referring toFIG.6, the construction system10generally includes a pair of rail assemblies20, a gantry50movably disposed on rail assemblies20, and the rock processing system100movably disposed on gantry50. The construction system10is configured to form a structure5(such as for example a personal dwelling) via additive manufacturing, specifically 3D printing, on a foundation4. In particular, construction system10(via rail assemblies20and gantry50) is configured to controllably move or actuate printing assembly150relative to the foundation4along each of a plurality of orthogonal movement axes or directions12,14,16such that the rock processing system100may controllably deposit an extrudable building material in a plurality of vertically stacked layers5ato form structure5on a preexisting foundation4. The gantry can be moved on wheels to the appropriate position, and then stabilized on jacks that raise the vertical supports and wheels off ground. The gantry may be moved in the x direction, the printing assembly may be moved in the y direction, as well as vertically up and down in the z direction. As used in this specification, including the claims, the term “and/or” is a conjunction that is either inclusive or exclusive. Accordingly, the term “and/or” either signifies the presence of two or more things in a group or signifies that one selection may be made from a group of alternatives. Without further elaboration, it is believed that one skilled in the art can use the preceding description to utilize the claimed inventions to their fullest extent. The examples and embodiments disclosed herein are to be construed as merely illustrative and not a limitation of the scope of the present disclosure in any way. It will be apparent to those having skill in the art that changes may be made to the details of the above-described embodiments without departing from the underlying principles discussed. In other words, various modifications and improvements of the embodiments specifically disclosed in the description above are within the scope of the appended claims. For example, any suitable combination of features of the various embodiments described is contemplated. | 10,446 |
11858853 | DETAILED DESCRIPTION OF THE EMBODIMENTS Embodiments of the present disclosure will now be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all of the embodiments of the disclosure are shown. As used herein, the words “a” and “an” and the like carry the meaning of “one or more”. Additionally, within the description of this disclosure, where a numerical limit or range is stated, the endpoints are included unless stated otherwise. Also, all values and subranges within a numerical limit or range are specifically included as if explicitly written out. As used herein, the terms “optional” or “optionally” means that the subsequently described event(s) can or cannot occur or the subsequently described component(s) may or may not be present (e.g. 0 wt. %). The phrase “substantially free”, unless otherwise specified, describes an amount of a particular component (e.g., a metal oxide), that when present, is present in an amount of less than about 1 wt. %, preferably less than about 0.5 wt. %, more preferably less than about 0.1 wt. %, even more preferably less than about 0.05 wt. %, relative to a total weight of the composition being discussed, and also includes situations where the composition is completely free of the particular component (i.e., 0% wt.). The term “comprising” is considered an open-ended term synonymous with terms such as including, containing or having and is used herein to describe aspects of the invention which may include additional components, functionality and/or structure. Terms such as “consisting essentially of” are used to identify aspects of the invention which exclude particular components that are not explicitly recited in the claim but would otherwise have a material effect on the basic and novel properties of the polycrystalline Y3Ba5Cu8Oyor the methods for making said material. The term “consisting of” describes aspects of the invention in which only those features explicitly recited in the claims are included and thus other components not explicitly or inherently included in the claim are excluded. A weight percent of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included. For example if a particular element or component in a composition is said to have 8 wt. %, it is understood that this percentage is in relation to a total compositional percentage of 100%. The terms “milled” vs. “unmilled” are used herein to differentiate products produced using the inventive ball mill-based methods (“milled”) vs. those produced by non-ball mill-based methods (i.e., hand milling/hand grinding with a mortar and pestle). Methods Besides the different molecular formula and thus atomic percentages of Y, Ba and Cu, polycrystalline Y3Ba5Cu8Oy(“Y-358”) differs from other YBCO family members such as YBa2Cu3Od(“Y-123”) in that it possesses five CuO2planes and three CuO chains, and has distinct characteristics and properties. In the nominal chemical formula of Y3Ba5Cu8Oy, y is the oxygen content that v in most cases between 17 and 19, most preferably 18. Y-358 refers to a polycrystalline material composed of oxides of yttrium, barium, and copper in a 3:5:8 molar ratio, where the purity of oxides of yttrium, barium, and copper is greater than 99 wt. %, preferably greater than 99.5 wt. %, preferably greater than 99.9 wt. %, most preferably 99.99 wt. %. In preferred embodiments, no metals are present (which can be in the form of elemental metals, metal oxides, or metal salts) other than yttrium, barium, and copper. For example, the polycrystalline Y-358 is preferably substantially free of or completely free of elements, oxides and/or salts of bismuth, tungsten, promethium, silver, and the like. In some embodiments, only the polycrystalline Y-358 superconducting material is present, and the Y-358 is not composited or coated with other non-metal materials such as graphene to make the superconducting material. Furthermore, when referencing the Y-358 product produced by the methods described herein, it is to be assumed that the produced polycrystalline material contains at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95% of the Y-358 phase as determined by X-ray diffraction, and is free of or is substantially free of other polycrystalline phases, e.g., YBa2Cu3Oy(Y-123), Y2BaCuOy(Y-211), Y7Ba11Cu18Oy(Y-7-11-18), YBa2Cu4Oy (Y-124), Y2Ba4Cu7Oy (Y-247), and the like, unless specifically stated otherwise. Perhaps due to the fundamental chemical differences between Y-358 and other YBCO family members (e.g., Y-123), it disclosed herein that the techniques and process parameters effective for producing Y-358 with advantageous superconducting properties differ from techniques and process parameters suitable for forming Y-123 [see A. Hamrita, Y. Slimani, M. K. Ben Salem, E. Hannachi, L. Bessais, F. Ben Azzouz, M. Ben Salem, Ceramics International, 40 (2014) 1461-1470—incorporated herein by reference in its entirety]. The inventive method for producing polycrystalline Y-358 are disclosed below. Starting Material Mixture Yttrium (III) oxide, a barium (II) salt, and copper(II) oxide are preferably used as starting materials. The barium (II) salt may be a barium oxocarbon anion or carboxylate e.g., barium carbonate (BaCO3), barium cyclohexanebutyrate, barium 2-ethylhexanoate, barium octoate; a barium alkoxide e.g., barium methoxide, barium ethoxide, barium isopropoxide; a barium halide e.g., barium bromide, barium chloride, barium fluoride, barium iodide; barium chromate; barium hydroxide; barium phosphate; barium metaphosphate; and the like, including mixtures thereof. In preferred embodiments, the barium (II) salt is barium carbonate (BaCO3). It is preferred that powders of the yttrium (III) oxide (Y2O3), barium (II) carbonate (BaCO3), and copper (II) oxide (CuO) are used, and that the powders are mixed in an atomic percentage to provide a nominal composition of Y:3/Ba:5/Cu:8. While it is possible to introduce other materials, compounds, additives, etc. at this stage, the mixed powder preferably consists of or consists essentially of only the yttrium, barium, and copper starting materials (i.e., respective oxides and/or salts thereof), and thus it is preferred that no other materials, compounds, additives, etc. are present which would materially affect the ability of the mixture to be pelletized, mechanically alloyed, and sintered as discussed hereinafter to form the polycrystalline Y-358. For example, the mixed powder is preferably free of potassium carbonate. Furthermore, while not always the case, it is preferred that only a single source of each of yttrium, barium, and copper is employed in the methods herein, i.e., the only source of yttrium used to make the polycrystalline Y-358 is yttrium (III) oxide, the only source of copper used to make the polycrystalline Y-358 is copper (II) oxide, and there is only one source of barium (i.e., one barium (II) salt e.g., BaCO3) used to make the polycrystalline Y-358. Other sources of yttrium (e.g., yttrium carbonate, yttrium chloride, yttrium nitrate, yttrium trifluoroacetate, yttrium acetate, yttrium acetoacetonate, etc.), other sources of copper (copper carbonate, copper chloride, copper nitrate, copper trifluoroacetate, copper acetate, copper acetoacetonate, copper bromide, copper hydroxide, etc.), and other sources of barium (e.g., barium oxide), are preferably not employed as starting materials in the disclosed inventive methods. The powders of yttrium (III) oxide (Y2O3), barium (II) salt carbonate (e.g. BaCO3), and copper (II) oxide (CuO) are mixed in accordance to the chemical formula Y:3/Ba:5/Cu:8 using an agate mortar and pestle. Pressing/Pelletizing After mixing, the mixed powders may be advantageously shaped by processes such as uniaxial pressing, isostatic pressing, molding, compacting, extrusion, injection, or any other pelletizing technique known to those of ordinary skill in the art, to produce a pelletized mixture. Preferably, the mixed powders are uniaxially pressed/pelletized, meaning the compaction of powder into a rigid mold by applying pressure in a single axial direction through a rigid die or piston. The mixed powder may be pelletized using hot uniaxial pressing (i.e., uniaxial pressing under the application of heat), for example under a temperature of 800 to 1,500° C. as described in U.S. Pat. No. 8,168,092B2. In most preferred embodiments, the mixed powders are uniaxially cold pressed, preferably at a temperature of less than 40° C., preferably less than 35° C., preferably 20 to 30° C. The mixed powders may be pelletized under a wide range of applied pressures, for example 5 to 700 MPa, preferably 10 to 600 MPa, preferably 20 to 300 MPa, preferably 30 to 100 MPa, preferably 40 to 60 MPa. The shape of the produced pellets is not particularly limiting, and can be adjusted by appropriate selection of the mold, die, and/or piston employed during the pelletizing processes, so long as a uniform density is achieved in the pelletized mixture. A uniform density is desirable as it may aid even distribution of heat during the subsequent calcination process. If a uniform density is not provided by uniaxial pressing, then the pelletized mixture may optionally be isostatically pressed until the desired density uniformity is achieved. Calcination The method involves calcining the pelletized mixture. In some embodiments, the calcination step is performed in a furnace using, for example, a pre-set temperature program or using other variable temperature systems known by those of ordinary skill in the art. In some embodiments, the pelletized mixture is calcined at 700 to 1,000° C., preferably 800 to 975° C., preferably 850 to 950° C., more preferably 875 to 925° C., more preferably 900° C. to produce a calcined mixture. In some embodiments, the pelletized mixture is calcined for 8 to 16 hours, preferably 10 to 14 hours, preferably about 12 hours. The pelletized mixture may be calcined using an isothermal procedure or a non-isothermal procedure. When a non-isothermal procedure is utilized, the temperature may be ramped using various ramp rates, for example 0.1 to 10° C./min, preferably 0.3 to 8° C./min, preferably 0.5 to 7° C./min, preferably 0.8 to 6° C./min, preferably 1 to 5° C./min, including ramp rates outside of these ranges. To ensure adequate removal of the barium salt anion (e.g., carbonate anion in BaCO3), the calcined mixture may be optionally subjected to an intermediate grinding stage, for example with a mortar and pestle or a mechanical grinding machine, and then re-subjected to further calcination under similar or different conditions to those described above. For example, the calcination process may involve 1) a first calcination at 850 to 950° C. for 10 to 14 hours, 2) intermediate grinding, followed by 3) a second calcination at 900 to 1,150° C. for 20 to 24 hours. Various other modifications, such as changes of gaseous atmosphere, may also be practiced so long as suitable conversion of the barium salt to barium oxide is adequately achieved. Most preferably, the pelletized mixtures are subjected to two calcinations processes, for 12 hours at 900° C. with ramp rate of 5° C./min, each with intermediate grinding for the aim of producing an oxide precursor without residue of any carbonates. The obtained precursors were divided into two parts; the first part was grounded by hand using an agate pestle in the agate mortar. The second part was ball milled. Ball Milling After producing calcined mixtures without residue of any carbonates, the calcined mixtures are then ball milled to produce ball milled samples. A high energy ball mill is preferably used, for example, a standard ball mill, a planetary mill, a vibration mill, an attritor—stirring ball mill, a pin mill, or a rolling mill may be employed. In some embodiments, the calcined mixture is ball milled with a planetary ball mill. Planetary ball mills are typically used for grinding sample material down to very small sizes. A planetary ball mill includes at least one grinding vial which is arranged eccentrically on a so-called sun wheel. The direction of movement of the sun wheel is opposite to that of the grinding vials. The grinding balls in the grinding vials are subjected to superimposed rotational movements, the so-called Coriolis forces. The difference in speeds between the balls and vials produces an interaction between frictional and impact forces, which releases high dynamic energies. Besides the typical mixing result of ball milling, the interplay between these forces in planetary ball milling produces the high and very effective degree of size reduction, and this high degree of fineness can be accomplished using short milling times. An example planetary ball mill useful in the disclosed method is a Retsch PM 200F type planetary ball mill, Haan Germany. The vials and balls used for the ball milling may be one or more of agate (cryptocrystalline silica), corundum (Al2O3), zirconium oxide (ZrO2), stainless steel (Fe, Cr, Ni), tempered steel (Fe, Cr), and tungsten carbide (WC). In preferred embodiments, the balls are made of stainless steel (e.g., SS 316), for example, 6 mm SS316 ball bearings may be employed. In some embodiments, the calcined mixture is ball milled with stainless steel vials and balls. In some embodiments, ball milling is performed in air (or a generally oxygen-containing atmosphere, e.g., which includes any atmosphere that contains at least 20%, preferably at least 40%, preferably at least 60%, preferably at least 80%, preferably at least 90%, preferably at least 95%, preferably at least 99%, or about 100% oxygen by volume). To avoid or reduce contamination, the ball milling may be carried out under an inert atmosphere such as under nitrogen or argon, preferably argon. In some embodiments, the weight of the calcined mixture (g) per volume (1,000 cm3) of vials used in the ball milling is 50-150 g/1,000 cm3, preferably 75-130 g/1,000 cm3, preferably 90-110 g/1,000 cm3. As used in the present disclosure, “controlled ball billing” or ball milling under “controlled” conditions refers to a ball milling process that maintains a consistent, stable, and highly reproducible milling event by avoiding overly energetic milling parameters that can cause over-milling and over-heating of the ball system leading to unwanted morphology changes and diminishment of superconducting properties. The phrase controlled ball milling is not to be confused with low energy ball milling methods, as high energy ball milling (e.g., planetary ball milling) techniques may be employed herein under particular parameters. Parameters used herein for “controlled” ball milling are now described below. The ball to powder ratio (BPR) represents the weight ratio of the milling balls to the calcined mixture charge. The ball to powder ratio used herein may range from 1:1 to 4:1, preferably 3:2 to 7:2, preferably 2:1 to 3:1, most preferably 5:2. The calcined mixture may be ball milled at a rotational speed of 200 to 600 rpm, preferably 250 to 550 rpm, preferably 300 to 500 rpm, preferably 350 to 450 rpm, most preferably 400 rpm. The milling time may also influence the product morphology and superconducting properties of the produced polycrystalline Y-358 material. Suitable milling times that may be practiced herein range from 2 to 8 hours, preferably 2.5 to 6 hours, preferably 3 to 5 hours, preferably 3.5 to 4.5 hours, most preferably about 4 hours. For controlled ball milling, it is also preferred to maintain a relatively low and consistent temperature within the ball mill throughout the milling operation, for example, a milling temperature of less than 150° C., preferably less than 100° C., preferably less than 80° C., preferably less than 60° C., preferably less than 40° C., for example 20 to 35° C. The milling temperature herein is an average temperature within the mill, which can be measured by direct calorimetric measurements of the milling balls or vials, and not a measurement of maximum local temperatures generated transiently during impact between the powder and/or colliding milling tools. While the calcined mixture may in certain circumstances be ball milled continuously over the entire milling time (e.g., 4 hours), such continuous operation may inadvertently cause elevated temperatures or temperature spikes (uncontrolled milling temperatures) that may negatively impact the final product. Therefore, in preferred embodiments, the calcined mixture is ball milled non-continuously over the selected milling time. Such non-continuous operation typically entails ball milling in increments of 10 to 60 minutes, preferably 15 to 50 minutes, preferably 20 to 40 minutes, preferably 25 to 30 minutes, separated by periods of inactivity (“cooling off periods”) ranging from 1 to 15 minutes, preferably 5 to 10 minutes, to control and maintain a more consistent maximum milling temperature over the entire ball milling operation. For example, a non-continuous ball milling operation may include cycles of ball milling for 25 minutes, cooling off for 5 minutes, then restarting the cycle again until a total milling time of 4 hours is reached (i.e., the milling time is the sum of all active milling periods and all cooling off periods). On the other hand, uncontrolled ball milling, i.e., overly energetic ball milling, generally involves application of a BPR, a rotational speed, a milling time, and/or a milling temperature that fall outside of the above described controlled ball milling ranges. For example, a method that employs a BPR of 5:1 or more, a rotational speed of 700 rpm or more, a milling time of 10 hours or more, a milling temperature of 200° C. or more, or any combination of two or more of these parameters would be considered herein as “uncontrolled” ball milling. In preferred embodiments, the calcined mixture which is subjected to ball milling consists of or consists essentially of yttrium, barium, and copper oxides, and a process control agent is not employed in order to avoid contamination during said ball milling process. Process control agents that are typically excluded herein, include, but are not limited to, organic acids or salts thereof (e.g., stearic acid, oxalic acid, benzoic acid, sodium stearate), polymers (e.g., polyvinyl alcohol, cellulose polymers such as sodium carboxymethyl cellulose, polyethylene glycol), alcohols (e.g., methanol, ethanol, isobutyl alcohol), aluminum-containing compounds (e.g., aluminum tri-sec-butylate, aluminum chloride), alkanes (e.g., hexane), potassium carbonate, as well as any other process control agent known by those of ordinary skill in the art. Surprisingly, it has been found that methods utilizing a controlled ball milling step afford polycrystalline Y-358 materials with superior superconducting properties, while the use of uncontrolled ball milling may negatively impact the superconducting properties of the polycrystalline Y-358 material compared to unmilled samples. Therefore, as will become clear, methods utilizing controlled ball milling>other milling techniques (e.g., hand grinding/milling)>uncontrolled ball milling, in terms of making polycrystalline Y-358 material with desirable superconducting properties. While not bound by theory, this may be due to the morphology produced using controlled ball milling. Sintering After milling, the produced hand grinded and ball milled samples may then be sintered, which is the process of compacting and forming a solid mass of material by heat or pressure without melting it to the point of liquefaction. In some embodiments, the ball milled sample is sintered at 800 to 1100° C., preferably 850 to 1050° C., preferably 900 to 1000° C., most preferably at 950° C. In preferred embodiments, the ball milled sample is sintered in an oxygen environment, which includes any environment that contains at least 20%, preferably at least 40%, preferably at least 60%, preferably at least 80%, preferably at least 90%, preferably at least 95%, preferably at least 99%, or about 100% oxygen by volume. In some embodiments, the ball milled sample is sintered for up to 72 hours, preferably 6 to 72 hours, preferably 12 to 60 hours, most preferably for 48 hours. Sintering may also optionally be performed above atmospheric pressure, for example at a pressure of 200 to 900 MPa, preferably 500 to 800 MPa, preferably 700 to 775 MPa, most preferably about 750 MPa. After sintering and optionally cooling to room temperature, the polycrystalline Y-358 material is formed. Product Morphology The polycrystalline Y3Ba5Cu8Oymaterial produced from the methods disclosed herein is in the form of a matrix of elongated grains/crystals which are separated by grain boundaries. The elongated crystals may have a variety of shapes, including cylindrical and cuboid shapes. In some embodiments, the elongated crystals have an average length of 1 to 20 μm, preferably 1 to 15 μm, most preferably 2 to 10 μm and an average width of 0.5 to 3 μm, preferably 1 to 2.5 μm, most preferably 1 to 2 μm. These elongated crystals may have an ordered or aligned orientation, whereby at least 60%, at least 70%, at least 80%, at least 90% of all elongated grains/crystals are arranged or oriented in the same or substantially the same direction as determined by SEM microscopy. In preferred embodiments, the matrix of the elongated grains/crystals are randomly oriented, that is, the elongated crystals are generally not aligned or oriented in the same direction along their longitudinal axis (seeFIGS.2B and3B). The polycrystalline Y3Ba5Cu8Oymaterial produced from the methods disclosed herein also include spherical nanoparticles of Yttrium deficient Y3Ba5Cu8Oydisposed on the elongated crystals. The spherical nanoparticles typically have an average diameter of 5 to 20 nm, preferably 6 to 15 nm, preferably 7 to 12 nm, preferably 9 to 11 nm, or about 10 nm. “Dispersity” is a measure of the homogeneity/heterogeneity of sizes of particles in a mixture. The coefficient of variation (CV), also known as relative standard deviation (RSD) is a standardized measure of dispersion of a probability distribution. It is expressed as a percentage and may be defined as the ratio of the standard deviation (σ) to the mean (μ, or its absolute value |μ|), and it may be used to show the extent of variability in relation to the mean of a population. In a preferred embodiment, the spherical nanoparticles produced by the methods of the present disclosure have a narrow size dispersion, i.e., are monodisperse, with a coefficient of variation of less than 30%, preferably less than 25%, preferably less than 20%, preferably less than 15%, preferably less than 12%, preferably less than 10%, preferably less than 8%, preferably less than 5%, preferably less than 3%, with the coefficient of variation being defined in this context as the ratio of the standard deviation to the mean diameter of the spherical nanoparticles. Sphericity is a measure of how closely the shape approaches that of a mathematically perfect sphere, and is defined as the ratio of the surface area of a perfect sphere of the same volume to the surface area of the spherical nanoparticles (with unity being a perfect sphere). Preferably, the spherical nanoparticles have an average sphericity of at least 0.7, preferably at least 0.8, preferably at least 0.9, preferably at least 0.95. In some embodiments, the spherical nanoparticles are classified based on roundness, and are categorized herein as being sub-rounded, rounded, or well-rounded, preferably well-rounded, using visual inspection similar to characterization used in the Shepard and Young comparison chart (FIG.4B). In some embodiments, the spherical nanoparticles (microstructure) may be present on the elongated crystals in the form of agglomerates, wherein a plurality of spherical nanoparticles agglomerate, and thus share interconnected outer boundaries, to form a distinct agglomerated macrostructure. In preferred embodiments, the agglomerates have a flower-like morphology, such flower-like morphology being characterized by the presence of individual spherical nanoparticles arranged radially in a petal-like manner surrounding centrally located spherical nanoparticles, the centrally located spherical nanoparticles being analogous to the ovary of a flower (FIG.4B). In some embodiments, the flower-like agglomerates have an average particle size of 30 to 60 nm, preferably 35 to 55 nm, preferably 40 to 50 nm, preferably about 45 nm. The average particle size of agglomerates is measured according to an average of the largest particle dimensions of the agglomerates, that is, the largest possible agglomerate particle dimension is measured and averaged. In some embodiments, the agglomerates having the flower-like morphology are uniformly dispersed on the elongated crystals, that is, the spherical nanoparticles are clustered into agglomerates, and those agglomerates are spread evenly/uniformly over the matrix of elongated crystals (e.g.,FIGS.3B-3D,4A and4B). Such flower-like agglomerates are different from the coral-like agglomerates (about 100 nm in size), previously observed in Y-123 materials [A. Hamrita, Y. Slimani, M. K. Ben Salem, E. Hannachi, L. Bessais, F. Ben Azzouz, M. Ben Salem Ceramics International, 40 (2014) 1461-1470—incorporated herein by reference in its entirety]. Contrary to ball milling-based methods, the use of other forms of milling/grinding (e.g., hand grinding with a mortar and pestle) forms only elongated crystals of Y3Ba5Cu8Oy, with no observable spherical nanoparticles (FIG.3A). Furthermore, it has been found that the amount of spherical nanoparticles formed increases with increasing intensity/energy of ball milling (as can be seen inFIGS.3B-3D). Product Properties The methods of the present disclosure produce Y-358 materials with superior superconducting properties, which can be clearly seen by comparing the products produced by the inventive methods to those made using milling techniques other than ball milling. This may be due to the morphology produced with the controlled ball milling procedures disclosed herein, that is, the amount of spherical nanoparticles present on the elongated crystals. One measurement for determining the quantity of spherical nanoparticles formed is residual resistivity, ρ0, which measures resistivity arising from impurity and imperfection scattering. Therefore, in the present disclosure, the residual resistivity may be correlated to the quantity of spherical nanoparticles, with higher residual resistivity values indicating a higher content of spherical nanoparticles. In preferred embodiments, the Y-358 materials provided herein have a residual resistivity of 0.3 to 0.55 mΩ·cm, preferably 0.33 to 0.5 mΩ·cm, preferably 0.36 to 0.48 mΩ·cm, most preferably 0.4 to 0.44 mΩ·cm. Such residual resistivity values are indicative of Y-358 materials having an advantageous content of spherical nanoparticles, while Po values above or below these ranges may be associated with polycrystalline Y-358 materials having inferior superconducting properties due to too many or too little (including none) spherical nanoparticles. In some embodiments, the Y-358 materials provided herein have an advantageous intrinsic superconducting parameters, for example a lower critical magnetic field, Bc1(0), of 5 to 10 T, preferably 5.5 to 8 T, preferably 6.0 to 7.5 T, most preferably 7 to 7.25 T, and an upper critical magnetic field, Bc2(0), of 500 to 650 T, preferably 550 to 650 T, preferably 570 to 600 T, most preferably 580 to 585 T. On the other hand, methods instead involving hand grinding or uncontrolled ball milling have a Bc1(0) of 4.41 T and 2.51 T, respectively, and a Bc2(0) of 274 T and 109.6 T, respectively. Critical current density is one measure of a materials ability to act as a superconductor, which is the point at which the vector sum of current densities is high enough to quench the superconducting state and the material transitions back to a normal state. In some embodiments, the polycrystalline Y3Ba5Cu8Oyproduced by the methods herein has an estimated critical current density at temperature 0 K, Jc(0), of 290 to 400×103A·cm−2, preferably 300 to 370×103A·cm−2, preferably 310 to 350×103A·cm−2, most preferably 320 to 330×103A·cm−2. Such a critical current density compares favorably to unmilled-based methods (e.g., Jc(0) of 148.8×103A·cm−2) and methods employing uncontrolled ball milling techniques (e.g., Jc(0) of 60.17×103A·cm−2). Flux pinning force density, Fp (T·A/m2) is measurement of sensitivity to magnetic field and flux pinning properties, with higher values indicating enhanced flux pinning and less sensitivity to magnetic fields. The products provided by the inventive methods have a superior flux pinning force density, Fp, compared to both hand ground samples and samples which have subject to over-milling (i.e., uncontrolled ball milling), under all applied magnetic fields up to 800 mT (FIG.10A). Furthermore, ball milling Y-358 under controlled conditions greatly increases Fp(e.g., more than a 2×106T·A/m2increase at 1 T), compared to unmilled Y-358, while there is less observed difference in Fpvalues between other yttrium-containing polycrystalline materials (e.g., Y-123) which have been subject to controlled ball milling and hand grinding (an increase of only about 0.5×106T·A/m2at 1 T,FIG.10B). This is unexpected, and demonstrates that the inventive method does not enhance the superconducting properties of all yttrium-containing polycrystalline materials equally or to a similar extent. Normalized transport critical current density, JctN, where JctN=Jct(B)/Jct(0), is another measure of sensitivity to magnetic field and flux pinning properties, with higher values indicating enhanced flux pinning and less sensitivity to magnetic field. Methods disclosed herein utilizing a controlled ball milling step produce polycrystalline Y3Ba5Cu8Oymaterials having a JctNof 0.039 to 0.045, preferably 0.040 to 0.044, preferably 0.041 to 0.043, most preferably about 0.042 under an applied transverse magnetic field μ0H of 100 mT at 77K. It can be appreciated that controlled ball milling enhances the JctNvalue of polycrystalline Y-358 materials compared to unmilled products, while over-milling (i.e., uncontrolled ball milling) weakens the normalized transport critical current density property of the material (FIGS.7A-7B). Furthermore, the inventive method results in a clear improvement in JctNwhen applied to Y-358 materials compared to unmilled variants, whereas there is no appreciable observed difference in JctNvalues between ball milled and hand ground samples of other yttrium-containing polycrystalline materials, e.g., Y-123 (FIG.7C). This is unexpected, and once again demonstrates that the inventive method is suitable for enhancing the superconducting properties of Y-358, while other YBCO materials do not necessarily show a similar improvement. In some embodiments, the polycrystalline Y-358 product has an offset superconducting transition temperature, Tco, of 91.0 to 92.4, preferably 91.4 to 92.2, preferably 91.8 to 92.0 K. The superconducting Y3Ba5Cu8Oymaterials produced in the present disclosure can be manufactured into rods, films, wires, tapes, coatings, coils, bulk materials, and the like, for various applications, such as in magnetic resonance imaging, particle accelerators, magnetic levitation, electric motors, bulk magnetic materials, electrical or computer components, power cables, power transmissions, transfer cable generators, frictionless bearings, Josephson junctions, and the like. Having generally described this disclosure, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting unless otherwise specified. The examples below are intended to further illustrate methods of preparing and characterizing the polycrystalline Y3Ba5Cu8Oymaterials and they are not intended to limit the scope of the claims. EXAMPLES Experimental Products of Y-358 were elaborated by solid state reaction by using two different milling methods, hand grinding in a mortar and ball milling in a planetary crusher. In accordance to the chemical formula of Y:3/Ba:5/Cu:8, the starting powders of Y2O3, BaCO3, and CuO were mixed in an agate mortar by hand grinding using an agate pestle. The mixture was pressed uniaxially into pellets under an applied pressure of 100 MPa and thereafter subjected to two calcinations processes for 12 h at 900° C. each with intermediate grinding for the sake of producing an oxide precursor without residue of any carbonates. The obtained precursor was divided into two parts; the first part was grounded by hand per an agate pestle in the agate mortar. The second part was milled using Retsch PM 200F type planetary ball milling technique with stainless steel balls and vial for 4 hours with various processing parameters. The number of balls, the ball to powder weight ratio and the speed rotation were varied. The process of milling was paused every 25 min for 5 min in favor of cooling the system down and reverse rotation. The precursors powders were then pelletized under an applied pressure of 750 MPa and heated in an oxygen atmosphere for 48 h at 950° C. The samples elaborated through sintering of planetary ball-milled precursor powder are named as S1, S2 and S3. For hand grinded precursor, the sintered sample is named S0. The notation and experimental variables for all elaborated products are summarized in Table 1. TABLE 1Notation and experimental conditions of ball milling parameters.Sample notationProcessing ball-milling parametersS0S1S2S3Number of balls—334Ball-to-powder weight ratio—5:25:25:1Rotation speed—400600600 Product Properties XRD and SEM Characterizations XRD data (FIG.1) confirms the formation of a mainly Y-358 single phase with a small quantity of secondary phases identified with (*) and (+) in spectrum. FIGS.2A-2Dshowed that the average grain size is smaller for ball milled samples compared to hand grinded one meaning that the planetary high energy ball milling technique has a significant impact on the microstructure of sintered samples. The different samples are formed by elongated crystals that have an average length of 2 to 10 μm and an average width of 1 to 2 μm. The images ofFIGS.3B-3D, taken under higher magnification, showed bright nanometer scale entities with almost regular form dispersed on the matrix relating to the milled samples. Such nano-entities are not visible in hand grinded sample (FIG.3A). The density of these nano-entities is raised on increasing the weigh ball-powder proportion and the speed rotation. A closer look at much higher magnification (FIG.4A) shows a spherical shape nano-entities with a size of about 10 nm dispersed finely and relatively uniformly within the matrix. These nano-entities stick together forming flower-like agglomerates (FIG.4B). The clumping of fine grains incorporated in the superconductor will lead to more disorder in the crystal lattice that expect to amplify the vortices pinning centers and consequently improve the transport properties of the synthesized products. Characterization of Superconducting Properties The methods of the present disclosure produce Y-358 materials with superconducting properties. Varying the number of balls, the rotation speed and the ball-to-powder weight ratio cause considerable disturbance of the microstructure in samples induced either by interfaces, heterogeneities or created defects. These differences manifest into differences in various superconducting parameters (FIG.5Aand Table 2). TABLE 2Characteristic parameters of different sintered samples.Characteristic parametersSampleTcoT*TcΔTρnρonotation(K)(K)(K)(K)(mΩ · cm)(mΩ · cm)S092.68118.2293.240.840.980.29S191.85140.3192.991.490.710.41S291.71148.5292.881.510.790.53S391.17161.8892.872.101.280.98 The increase in the residual resistivity, ρ0, can be explained by the larger number of defects and heterogeneities induced by planetary high energy ball milling technique. Therefore, in the present disclosure, the residual resistivity may be correlated to the quantity of spherical nanoparticles, with higher residual resistivity values indicating a higher content of spherical nanoparticles. The milled samples exhibit higher residual resistivity compared to the hand grinded one. The residual resistivity increases with increasing the various processing parameters such as the number of balls, speed rotation and the number of ball—powder. The hand grinded sample (S0) exhibits a single transition to the superconducting state, however, the milled ones exhibit a double superconducting transition (FIG.5B). This can be confirmed by plotting dρ/dT versus temperature or Δσ−2versus temperature (FIG.6A-6D). For example, the presence of one maximum in plots of dρ/dT versus temperature for the S0 unmilled sample indicates the occurrence of a single transition to the superconducting state (FIG.6A), however the observation of two maximums for milled samples indicates the presence of a double superconducting transition (FIG.6B-6D). It is assumed that the double transition, which is not observed in the case of hand grinded sample, seems to arise from the nano-entities generated by the planetary high energy ball milling technique. Normalized transport critical current density, JctN, where JctN=Jct(B)/Jct(0), is a measure of sensitivity to magnetic field and flux pinning properties, with higher values indicating enhanced flux pinning and less sensitivity to magnetic field. It can be appreciated that controlled ball milling enhances the JctNvalue of polycrystalline Y-358 materials compared to hand grinded products. The optimized ball milled sample (S1) exhibits less sensitivity to magnetic field and JctNvalues are higher throughout the considered whole range of magnetic field when compared to those of hand grinded (S0) and other ball milled (S2 and S3) samples (FIG.7A). The optimized ball milled polycrystalline Y3Ba5Cu8Oymaterial has a JctNof 0.042 under an applied transverse magnetic field μ0H of 100 mT at 77K, which is higher compared to that for hand grinded samples where JctNis around 0.026 (FIG.7B). The nano-entities induced by the use of appropriate and well-controlled ball milling parameters could act as efficient pinning sources resulting in a global improvement of flux pinning properties. In comparison to hand grinded and ball milled Y-123, the hand grinded and ball milled Y-358 samples exhibit higher values of critical current density proving better intrinsic superconducting properties in Y-358 compounds (FIG.7C). The Y-358 samples exhibit less sensitivity to magnetic field and JctNvalues are higher throughout the considered whole range of magnetic field when compared to those of other yttrium-containing polycrystalline materials, e.g., Y-123 (FIG.7C). The obtained result reveals that the optimized ball milled Y-358 product displays the better flux pinning characteristics. This is unexpected, and once again demonstrates that the inventive method is suitable for enhancing the superconducting properties of Y-358, while other YBCO materials do not necessarily show a similar improvement. All samples exhibit an improvement of Jct(T) in the whole temperature range between close to Tcoand down to T=20K. Jct(T) values of milled samples are drastically better in the existence of external magnetic fields compared to unmilled ones. This result confirms once again the beneficial effect of well-dispersed nano-entities induced by planetary HEBM technique in the enrichment of the flux pinning properties. The performances of milled Y-358 product are better over the entire temperature range (FIGS.8A-8C). The hand grinded Y-358 product displays noticeably higher magnetization critical current density, Jcm(H), values in comparison to the hand grinded Y-123, at least in part due to better intra-granular characteristics in Y-358 (FIG.9A). Jcmis improved significantly in the ball milled Y-358 sample compared to ball milled Y-123 at both 0 and 1 Tesla (FIG.9B). The high energy ball milling technique leads to a larger improvement of magnetization critical current density for the Y-358 compound compared to the Y-123 ball milled variant. In some embodiments, the optimized ball milled polycrystalline Y3Ba5Cu8Oyhas a magnetization critical current density Jcmof 14×103A·cm−2and 550 A·cm−2at 0 Tesla and 1 Tesla, respectively. However, the optimized ball milled polycrystalline YBa2Cu3Odhas lower Jcmwith values around 7.0×103A·cm−2and 200 A·cm−2at 0 Tesla and 1 Tesla, respectively. The S1 milled sample exhibits less sensitivity to magnetic field and flux pinning force density Fpvalues are higher throughout the considered whole range of magnetic field when compared to those of S0, S2 and S3 materials (FIG.10A). That is to say, the flux pinning in S1 milled sample has been enhanced compared to the other products. The nano-entities induced by the use of appropriate and well-controlled ball milling parameters could act as efficient pinning sources resulting in a global improvement of flux pinning properties. The milled Y-358 exhibits a distinctly higher flux pinning force density Fpand the planetary high energy ball milling technique once again strengthens the flux pinning properties of this product in comparison to that of Y-123, which shows a much smaller observed difference between milled and unmilled Y-123 materials (FIG.10B). TABLE 3Conductivity exponents and cross-over temperatures values for differentsintered samples.SampleTSWF-1DT1D-2DT2D-3DTGnotationλSWFλ1Dλ2Dλ3Dλcr(K)(K)(K)(K)S02.971.511.040.470.34122.92109.8102.9294.79S12.941.460.960.480.30149.18129.04111.997.88S22.951.530.960.470.21160.16137.52115.898.38S32.951.540.960.470.22173.31145.84119.8499.06 TABLE 4Physical parameters associated with fluctuation-induced conductivity (FIC).Jc(0)Sampleξc(0)dsBc(0)Bc1(0)Bc2(0)(×103notationNG× 10−2(Å)(Å)(Å2)J(Tesla)(Tesla)(Tesla)A · cm−2)S01.6310.9687.121008.870.063224.104.41274.17148.80S16.317.5032.53195.620.212643.327.24584.39329.57S24.849.4435.98254.490.275332.756.04368.47237.17S36.6717.3265.68815.730.278112.182.51109.6460.17 The excess conductivity investigation of Y3Ba5Cu8Oysuperconductors prepared by various parameters of planetary High Energy Ball Milling technique were examined (FIGS.11A-11D,FIGS.12A-12B, and Tables 3 and 4). InFIGS.11A-11D, the abbreviations C.R., M.F.R. and S.W.F. stand for critical region, mean-field region and short-wave fluctuation region, respectively. The lower critical magnetic field (Bc1(0)), upper critical magnetic field (Bc2(0)) and critical current density at T=0K (Jc(0)) are improved for S1 and S2 ball milled samples compared to S0 unmilled (hand grinded) sample. It is noticeable that the enhancement of these parameters reaches the highest values for S1. The structure of multi-layers and the existence of greater number of insulating layers interpolated between the planes CuO2playing as efficient intrinsic pinning centers and the generated nano-entities by high energy ball milling technique may conduce together to much better intrinsic pinning capabilities in Y-358. The nano-entities induced by the use of appropriate and well-controlled ball milling parameters in Y-358 sample could act as additional and efficient pinning sources resulting in a global improvement of flux pinning properties. Thus, the foregoing discussion discloses and describes merely exemplary embodiments of the present disclosure. As will be understood by those skilled in the art, the present disclosure may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. Accordingly, the disclosure of the present invention is intended to be illustrative, but not limiting of the scope of the disclosure, as well as other claims. The disclosure, including any readily discernible variants of the teachings herein, defines, in part, the scope of the foregoing claim terminology such that no inventive subject matter is dedicated to the public. | 44,396 |
11858854 | DETAILED DESCRIPTION Reference will now be made in detail to exemplary embodiments which are illustrated in the accompanying drawings. Whenever possible, the same reference numerals will be used throughout the drawings to refer to the same or like parts. The components in the drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the exemplary embodiments. It should be understood that the present application is not limited to the details or methodology set forth in the description or illustrated in the figures. It should also be understood that the terminology is for the purpose of description only and should not be regarded as limiting. Additionally, any examples set forth in this specification are illustrative, but not limiting, and merely set forth some of the many possible embodiments of the claimed invention. Other suitable modifications and adaptations of the variety of conditions and parameters normally encountered in the field, and which would be apparent to those skilled in the art, are within the spirit and scope of the disclosure. Definitions “Major phase,” “first phase,” or like terms or phrases refer to a physical presence of a lithium garnet in greater than 50% by weight, by volume, by mols, or like measures in the composition. “Minor phase,” “second phase,” or like terms or phrases refer to a physical presence of a lithium dendrite growth inhibitor (i.e., grain boundary bonding enhancer) in less than 50% by weight, by volume, by mols, or like measures in the composition. “SA,” “second additive,” “second phase additive,” “second phase additive oxide,” “phase additive oxide,” “additive oxide,” “additive,” or like terms refer to an additive oxide that produces a minor phase or second minor phase within the major phase when included in the disclosed compositions. “LLZO” or like terms refer to compounds comprising lithium, lanthanum, zirconium, and oxygen elements. For example, lithium-garnet electrolyte comprises at least one of: (i) Li7-3aLa3Zr2LaO12, with L=Al, Ga or Fe and 0<a<0.33; (ii) Li7La3-bZr2MbO12, with M=Bi or Y and 0<b<1; (iii) Li7-cLa3(Zr2-c,Nc)O12, with N=In, Si, Ge, Sn, V, W, Te, Nb, or Ta and 0<c<1, or a combination thereof. “Include,” “includes,” or like terms means encompassing but not limited to, that is, inclusive and not exclusive. As utilized herein, the terms “approximately,” “about,” “substantially”, and similar terms are intended to have a broad meaning in harmony with the common and accepted usage by those of ordinary skill in the art to which the subject matter of this disclosure pertains. It should be understood by those of skill in the art who review this disclosure that these terms are intended to allow a description of certain features described and claimed without restricting the scope of these features to the precise numerical ranges provided. Accordingly, these terms should be interpreted as indicating that insubstantial or inconsequential modifications or alterations of the subject matter described and claimed are considered to be within the scope of the invention as recited in the appended claims. For example, in modifying the quantity of an ingredient in a composition, concentrations, volumes, process temperature, process time, yields, flow rates, pressures, viscosities, and like values, and ranges thereof, or a dimension of a component, and like values, and ranges thereof, employed in describing the embodiments of the disclosure, “about” or similar terms refer to variations in the numerical quantity that can occur, for example: through typical measuring and handling procedures used for preparing materials, compositions, composites, concentrates, component parts, articles of manufacture, or use formulations; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of starting materials or ingredients used to carry out the methods; and like considerations. The term “about” (or similar terms) also encompasses amounts that differ due to aging of a composition or formulation with a particular initial concentration or mixture and amounts that differ due to mixing or processing a composition or formulation with a particular initial concentration or mixture. As utilized herein, “optional,” “optionally,” or the like are intended to mean that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event or circumstance occurs and instances where it does not occur. The indefinite article “a” or “an” and its corresponding definite article “the” as used herein means at least one, or one or more, unless specified otherwise. References herein to the positions of elements (e.g., “top,” “bottom,” “above,” “below,” etc.) are merely used to describe the orientation of various elements in the FIGURES. It should be noted that the orientation of various elements may differ according to other exemplary embodiments, and that such variations are intended to be encompassed by the present disclosure. Abbreviations, which are well known to one of ordinary skill in the art, may be used (e.g., “h” or “hrs” for hour or hours, “g” or “gm” for gram(s), “mL” for milliliters, and “rt” for room temperature, “nm” for nanometers, and like abbreviations). Specific and preferred values disclosed for components, ingredients, additives, dimensions, conditions, times, and like aspects, and ranges thereof, are for illustration only; they do not exclude other defined values or other values within defined ranges. The compositions, articles, and methods of the disclosure can include any value or any combination of the values, specific values, more specific values, and preferred values described herein, including explicit or implicit intermediate values and ranges. With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. The various singular/plural permutations may be expressly set forth herein for the sake of clarity. As explained above, solid-state lithium batteries based on Li-garnet electrolyte (LLZO) often suffer from insufficient contact between the Li anode and garnet electrolyte, which often leads to the battery experiencing a low critical current density (CCD) and eventual short circuiting. Conventional approaches to address these issues have included: (A) H3PO4acid treatments for removing impurities while forming a protective interlayer of Li3PO4to increase CCD of the electrolyte to 0.8 mA·cm−2and (B) modifying the electrolyte-anode interface with SnO2and MoS2to form Sn, Mo, and related alloy interlayers. However, it was found that for these proposals, as the battery circulates, the interlayers gradually become exhausted and result in eventual battery failure. Moreover, these interlayers do not increase the resistance of the electrolyte itself against lithium dendrite growth. Composite ceramic electrolytes are effective in improving bonding at the major phase grain boundary, thereby improving CCD by minimizing lithium dendrite growth. Critical current density (CCD) refers to the maximum current density that LLZO electrolyte can tolerate before lithium dendrite penetration occurs in the electrolyte, which affects the dendrite suppression capability of the electrolyte. By adding additives during the LLZO sintering process, the additive or its decomposition product aggregates at the grain boundary to enhance grain boundary bonding and block lithium dendrite growth. Current efforts at studying additives have included (i) LiOH·H2O in LLZO to form a minor phase of Li2CO3and LiOH or (ii) adding Li3PO4to LLZO precursor and allowing Li3PO4to remain as the minor phase at the grain boundaries by controlling sintering conditions or (iii) adding LiAlO2-coated LLZO particles to obtain a Li-garnet composite ceramic electrolyte. However, none of (i) to (iii), can achieve a desired CCD to meet the requirements of practical applications. Disclosed herein is a Li-garnet composite ceramic electrolyte prepared by adding a lithium-rich additive (e.g., LixTiO(x+4)/2(0.66≤x≤4), “LTO”), into LLZO with optional elemental doping (e.g., at least one of In, Si, Ge, Sn, V, W, Te, Nb, Ta, Al, Ga, Fe, Bi, Y, etc.), during LLZO ceramic sintering, according to some embodiments. In some embodiments, while variations of LTO include Li2TiO3, Li4Ti5O12, Li2Ti3O7, and Li4TiO4, the sintering atmosphere is mainly Li2TiO3and Li4TiO4. Li2Ti3O7and Li4Ti5O12as a second phase may gather at the LLZO grain boundary. Elemental dopants may be used to stabilize LLZO into a cubic phase with at least one of In, Si, Ge, Sn, V, W, Te, Nb, Ta, Al, Ga, Fe, Bi, Y, etc. The composite ceramic comprises a major LLZO phase and a minor LTO second phase. The addition of lithium-rich additive during sintering reduces sintering temperature of LLZO and creates a lithium atmosphere for LLZO sintering, which simplifies the sintering process and reduces its cost. The lithium-rich additives and their decomposition products are distributed at the LLZO grain boundary, which enhances bonding at the LLZO grain boundary and blocks formation of lithium dendrite growth. The CCD of the Li-garnet composite described herein is at least 1.5 mA·cm−2. Methods for Preparation of Li-Garnet Composite Ceramic Electrolyte First Mixing Step In the first mixing step, a stoichiometric amount of inorganic materials is mixed together, in the formula of garnet oxides and, for example, milled into fine powder. The inorganic materials can be, for example, a lithium compound and at least one transition metal compound (e.g., La-based, Zr-based, etc.). In some embodiments, the inorganic materials compounds may also comprise at least one of Al, Ga, Fe, Bi, Y, In, Si, Ge, Sn, V, W, Te, Nb, Ta, Mg, or combinations thereof in the chemical formula. In some embodiments, it may be desirable to include an excess of a lithium source material in the starting inorganic batch materials to compensate for the loss of lithium during the high temperature of from 1000° C. to 1300° C. (e.g., 1100° C. to 1200° C.) sintering step. The first mixing step can be a dry milling process, or a wet milling process with an appropriate liquid that does not dissolve the inorganic materials. The mixing time, such as from several minutes to several hours, can be adjusted, for example, according to the scale or extent of the observed mixing performance (e.g., 1 min to 48 hrs, or 30 mins to 36 hrs, or 1 hr to 24 hrs (e.g., 12 hrs), or any value or range disclosed therein). The milling can be achieved by, for example, a planetary mill, an attritor, or like mixing or milling apparatus. Calcining Step In the calcining step, the mixture of inorganic material, after the first mixing step, is calcined at a predetermined temperature, for example, at from 800° C. to 1200° C. (e.g., 950° C.), including intermediate values and ranges, to react and form the target Li-garnet. The predetermined temperature depends on the type of the Li-garnet. The calcination time, for example, varies from 1 hr to 48 hrs (e.g., 2 hrs to 36 hrs, or 3 hrs to 24 hrs, or 4 hrs to 12 hrs (e.g., 6 hrs), or any value or range disclosed therein), and also may depend upon on the relative reaction rates of the selected inorganic starting or source batch materials. In some embodiments, a pre-mix of inorganic batch materials can be milled and then calcinated or calcined, as needed, in a first step. Second Mixing Step The calcined Li-garnet mixture and minor or second phase additives are mixed together and ground to form a mixture of a homogeneous composition (e.g., as determined by the LTO distribution in green ceramic pellets or bars). LTO minor phase was prepared in similar manner as described in the First Mixing (milling for 30 mins to 36 hrs, e.g., 24 hrs) and Calcining (e.g., for 12 hrs to 24 hrs) steps. The second mixing step can include, for example, one or more of: a wet-milling, a dry-milling, or a combination thereof. During milling of the mixture, one can optionally heat the mixture at a low temperature of, for example, from 60° C. to 100° C. (e.g., 70° C.) to remove adsorbed moisture or solvents. Compacting Step The homogeneous second mixture composition was pulverized simultaneously during the second mixing step. After drying at temperatures ranging from 60° C. to 100° C. (e.g., 70° C.) for a time ranging from 6 hrs to 24 hrs (e.g., 12 hrs), the second mixture composition was compacted by passing through a 200-grit sieve to form a green pellet. The green pellet may be formed as arbitrary shapes by any suitable method, for example, cold isotropic pressing, hot isotropic pressing, hot pressing, uniaxial pressing, or by like means and instrumentalities. The green pellet may have at least one dimension ranging from 1 mm to 30 mm (e.g., ˜20 mm). The green pellet is then sintered at a temperature greater than the temperature of the calcining step, as described below. Sintering Step During the sintering step, the green pellet was placed in a crucible with a lid (e.g., Pt, ZrO2, Al2O3and MgO crucible). The sintering temperature was, for example, from 1000 to 1300° C., including intermediate values and ranges, with a temperature ramping rate (pre-sintering) and cooling rate (post-sintering) ranging from 0.5° C./min to 10° C./min (e.g., 5° C./min). EXAMPLES Example 1—Li-Garnet (LLZO) Electrolyte Preparation Precursor powder LiOH·H2O (AR, 2% excess), La2O3(99.99%, calcined at 900° C. for 12 hours), ZrO2(AR), and Ta2O5(99.99%) were weighed and mixed according to the stoichiometric ratio of Li6.5La3Zr1.5Ta0.5O12. Wet ball milling was conducted for 12 hours via yttrium-stabilized zirconia (YSZ) balls as the grinding medium at a speed of 250 rpm using isopropanol as the solvent. The dried mixture powder was calcined in an alumina crucible at 950° C. for 6 hours to obtain pure cubic Li-garnet electrolyte powder. In some embodiments, the solid electrolyte is a Li-garnet ceramic electrolyte LLZO with a chemical formula of one or more of Li7-3aLa3Zr2LaO12(L=Al, Ga or Fe; 0<a<0.33), Li7La3-bZr2MbO12(M=Bi or Y; 0<b<1), and Li7-cLa3(Zr2-c,Nc)O12(N=In, Si, Ge, Sn, V, W, Te, Nb, Ta; 0<c<1). Example 2—Preparation of Li-Garnet Composite Ceramic Electrolyte (LLZO-LTO) The LLZO powder of Example 1 and LTO powder (Li2TiO3, Alfa) were weighed in a predetermined ratio and wet-milled at 250 rpm for 12 hours using the same techniques described above. The obtained mixture was dried at 70° C. for 12 hours and then passed through a 200-grit sieve. A green pellet (1.25 grams) with a diameter of 18 mm was formed by uniaxial pressing at a pressure of 140 MPa. Thereafter, the green body was placed in an Al2O3, MgO or Pt crucible and sintered at 1190° C. for 30 minutes to obtain LLZO-LTO. Temperature ramping rate and cooling rate pre- and post-sintering, respectively, was conducted at 5° C./min. The mother powder was not used in the sintering process in this experiment. LixTiO(x+4)/2, includes, but is not limited to: Li2TiO3, Li4Ti5O12, Li2Ti3O7, Li4TiO4. Optionally, mother powder (Li6.5La3Zr1.5Nb0.5O12) may also be used to compensate Li-garnet (LLZO) electrolyte samples' lithium loss during sintering. The synthesis process for the mother powder is similar to that for preparing LLZO as described herein (e.g., Example 1), except with excessive lithium content in the precursor powder (e.g., 15%). While sintering to prepare LLZO, the green pellet may optionally be covered by a mother powder to prevent loss of volatile components (Li2O) and avoid the presence of a lithium-deficient phase (La2Zr2O7). At the same time, the presence of a Li2O atmosphere promotes densification of LLZO. Example 3—Preparation of Coin Cell LLZO-LTO electrolyte pellets prepared in Example 2 were polished first with 400-grit and second with 1200-grit SiC sandpaper, followed by Au-sputtering thereon for 5 minutes. After transferring to an argon-filled glove box, the cell was assembled by positioning lithium metal foil at a center portion of a first LLZO-LTO sample surface and heating it to 250-300° C. on a hot plate. Because of the heating, molten lithium spreads across the first surface of the pellet. Thereafter, the sample was rotated, followed by the same lithium metal positioning and heating steps to a second LLZO-LTO sample surface. The Li/LLZO-LTO/Li symmetrical battery was finally sealed in a CR2032 coin cell. Example 4—Characterization Techniques Morphology and Phase Analysis Scanning electron microscopy (SEM) images were obtained by a scanning electron microscope (Hitachi, S-3400N). Element mapping images were characterized by an energy dispersive spectrometer (EDS) affiliated with the HITACHI SEM. X-ray powder diffraction (XRD) patterns were obtained by x-ray powder diffraction (Rigaku, Ultima IV, nickel-filtered Cu—Kα radiation, λ=1.542 Å) in the 2θ range of 10-80° at room temperature. Density of the ceramic samples was measured by the Archimedes method with ethanol as the immersion medium. Electrochemical Impedance Spectroscopy (EIS) EIS was measured by AC impedance analysis (Autolab, Model PGSTAT302 N) with a frequency range of 0.1 Hz to 1 MHz. Electrochemical Performance All Li symmetric cells and the full battery were tested on a LAND CT2001A battery test system (Wuhan, China). The Li/LLZO-LTO/Li symmetrical battery prepared in Example 3 was subjected to a rate cycling test at an initial current density of 0.1 mA·cm−2, followed by increments of 0.1 mA·cm−2to determine the critical current density (CCD) of LLZO-LTO. Charge and discharge durations were set to 30 minutes. All battery tests were performed at 25° C. Example 5—Sample Preparation and Characterization Sample 1 Li-garnet electrolyte (LLZO) and lithium-titanium composite oxide (Li2TiO3, LTO) were weighed at a mass ratio of 100:2 (40 g of LLZO, 0.8 g of LTO in 120 g isopropyl alcohol). Wet ball milling was conducted for 12 hours by using yttrium-stabilized zirconia (YSZ) beads as a grinding medium at a speed of 250 rpm. Particle size distribution (D90) ranged between 1.2 μm and 1.7 μm. The obtained mixture was dried at 70° C. for 12 hours and then passed through a 200-grit sieve. A green pellet (1.25 grams) with a diameter of 18 mm was formed by uniaxial pressing at a pressure of 140 MPa. Thereafter, the green body was placed in a Pt crucible and sintered at 1190° C. for 30 minutes, the temperature ramping rate (pre-sintering) and cooling rate (post-sintering) both being 5° C./min. Sample 2 Preparation was the same as in Sample 1, except the Li-garnet electrolyte LLZO and lithium-titanium composite oxide LTO were ball milled at a mass ratio of 100:4. Sample 3 Preparation was the same as in Sample 1, except the Li-garnet electrolyte LLZO and lithium-titanium composite oxide LTO were ball milled at a mass ratio of 100:6. Sample 4 Preparation was the same as in Sample 1, except the Li-garnet electrolyte LLZO and lithium-titanium composite oxide LTO were ball milled at a mass ratio of 100:8. Comparative Sample 1 Li-garnet electrolyte (LLZO) powder was wet ball milled for 12 hours by using yttrium-stabilized zirconia (YSZ) beads as a grinding medium at a speed of 250 rpm. Particle size distribution (D90) ranged between 1.2 μm and 1.7 μm. The obtained mixture was dried at 70° C. for 12 hours and then passed through a 200-grit sieve. A green pellet (1.25 grams) with a diameter of 18 mm was formed by uniaxial pressing at a pressure of 140 MPa. Thereafter, the green body was placed in a MgO crucible and sintered at 1190° C. for 30 minutes, with 0.4 g mother powder per pellet (Li6.5La3Zr1.5Nb0.5O12; Li excess 15%) during LLZO sintering. Comparative Sample 2 Preparation was the same as in Comparative Sample 1, except that no mother powder was added. Table 1 shows selected preparation conditions and performance attributes for Samples 1-4 and Comparative Samples 1 and 2. Common phases of LTO include Li2TiO3, Li4Ti5O12, Li2Ti3O7, Li4TiO4, etc., each of which can provide a sintering atmosphere. LTO with high lithium content is relatively easy to decompose to produce Li2O. The sintering atmosphere is mainly provided by Li2TiO3and Li4TiO4. Li2Ti3O7and Li4Ti5O12as a second phase may gather at the LLZO grain boundary. Li2TiO3exemplified as the choice for LTO to illustrate the role of LTO. TABLE 1RelativeIonicLLZO:LTODensityConductivityCCDSampleMass Ratio(%)(mS · cm−1)(mA · cm−2)Comparative 1093.60.6870.4Comparative 2076.990.0123—1100:294.720.4940.92100:495.620.4291.53100:694.100.3651.14100:893.780.3611.0 FIG.1illustrates an x-ray diffraction (XRD) pattern of Li-garnet composite ceramic electrolytes of Samples 1, 2, and 4, according to some embodiments. The XRD peaks of each of Samples 1 (LLZO:LTO=100:2), 2 (LLZO:LTO=100:4), and 4 (LLZO:LTO=100:8) indicate a close match with the XRD fingerprints of the control cubic Li-garnet electrolyte PDF #45-0109 sample, confirming that addition of LTO does not affect the phase composition of LLZO. In some embodiments, a mass ratio of lithium-garnet major phase to lithium-rich minor phase is in a range of 100:2 to 100:8. Because Li2O affects grain growth and densification processes of LLZO, too low of a LLZO:LTO ratio may have insufficient lithium atmosphere, resulting in low densification. Too high of a LLZO:LTO ratio (e.g., LLZO:LTO mass ratio of 1:1) results in unwanted amounts of heterophases (e.g., LaTiO3, LaTaO4, ZrTiO4, etc.) being formed. Moreover, at too high LLZO:LTO ratios, the major phase of the composite may also be adversely affected. Here, c-LLZO can be determined as the absolute major phase of LLZO-LZO in a range of 100:2 to 100:8. Pristine LLZO (e.g. Li7La3Zr2O12) has cubic (c-LLZO) and tetragonal (t-LLZO) phases at different temperature. The c-LLZO has a higher ionic conductivity than t-LLZO (c-LLZO at 10−3˜10−4S·cm−1versus t-LLZO at 10−5˜10−6S·cm−1). The tetragonal phase is a room-temperature stable phase, and it is often necessary to introduce doped ions (e.g., at least one of In, Si, Ge, Sn, V, W, Te, Nb, Ta, Al, Ga, Fe, Bi, Y, etc.) to stabilize cubic phase at room temperature. According to the XRD results ofFIG.1, no t-LLZO phase was detected. Thus, the LLZO used here (e.g., Li6.5La3Zr1.5Ta0.5O12) can be regarded as a single-phase material. For at least this reason, it is important LTO does not affect the phase composition of LLZO. Table 1 above presents selected preparation conditions and performance attributes for Samples 1-4 and Comparative Samples 1 and 2. Comparative Sample 2, in which no mother powder was used and no LTO was added into Li-garnet powder, was not well-sintered, as indicated by the low relative density (as compared to a theoretical maximum density of the ceramic) (76.99%) in comparison with other samples which exceed 90%. Comparative Sample 1, in which mother powder was used but no LTO was added into Li-garnet powder, is able to achieve relative density values comparable to the average of Samples 1-4 (Comparative 1: 93.6% vs Average for Samples 1-4: 94.56%) but not able to achieve CCD values comparable to the average of Samples 1-4 (Comparative 1: 0.4 mA·cm−2vs Average for Samples 1-4: 1.125 mA·cm−2) or even come close to CCD value for Sample 2 (1.5 mA·cm−2). The sintering mechanism of LLZO is a gas-liquid-solid process. Li2O gas condenses into a liquid phase on the surface of the LLZO particles. Dissolution-precipitation promotes material transport, resulting in grain growth and enhanced densification. Both the mother powder and LTO can provide a Li2O atmosphere for LLZO sintering whereby LLZO obtains a Li2O atmosphere from the outside and the inside, respectively. Relative density of Samples 1-4, which comprise LTO increases when firing at 1190° C., suggesting that LTO may help to densify garnet and lower the sintering temperature. As stated above, release of Li2O by LTO promotes LLZO densification. As stated in Example 2 describing the preparation of Li-garnet composite ceramic electrolytes of Samples 1-4, mother powder was not used in the sintering process for Samples 1-4. The relative densities of the LLZO-LTO composites of Samples 1-4 also indicate that inclusion of mother powder is not a critical component of the sintering process since decomposition of LTO can also provide a Li2O sintering atmosphere. Thus, because of this Li2O sintering atmosphere and lowered sintering temperature, the sintering process is simplified and cheaper. Ion conductivity of LLZO is acceptable above from 10−3to 10−4S·cm−1. Indeed, all of Samples 1-4 satisfy this criteria (exceeding 0.35 mS·cm−1), due to the presence of LTO and its decomposition or reaction products at the grain boundary. However, more important is whether the solid-state battery using LLZO can withstand large current charge and discharge and long-term cycling. CCD is an important evaluation metric and so is considered acceptable at some level to sacrifice ionic conductivity in order to improve CCD. LLZO-LTO sintering without use of mother powder is one advantage of LTO as an additive. Comparative Sample 2 has very low conductivity (0.0123 mS·cm−1) since it was not well sintered. Addition of LTO also leads to an increase in CCD of the Li-garnet. CCD reaches 1.5 mA·cm−2when mass ratio of LLZO to LTO is 100:4 and the composite is fired in an Pt crucible. As mentioned above, sintering of LLZO depends on the Li2O atmosphere. While MgO and Pt crucibles are relatively stable with Li2O, Al2O3and ZrO2crucibles easily react with Li2O to form LixAlOyand LixZrOy, respectively, at high temperatures, which makes LLZO difficult to sinter and densify. Thus, Al2O3and ZrO2crucibles often require repeated sintering and may be used for LLZO sintering only after forming a passivation layer. FIG.2illustrates a cross-sectional SEM image of Comparative Sample 1 whileFIGS.3A-3Dillustrate cross-sectional SEM images of Samples 1-4, respectively, according to some embodiments. As observed inFIG.2, no obvious impurities are seen in the grain boundary of Comparative Sample 1. When LTO is added, as in Samples 1-4 (FIGS.3A-3D), it can be seen that LLZO is mainly structured as a transgranular fracture, indicating that the grains are tightly bonded due to the extremely strong fluxing properties of LTO that can bond grain boundaries. In other words, when transgranular fracture occurs, cracks propagate through an inside portion of the grain, which is evidence of strong grain boundary bonding (seeFIGS.3A-3Dcross sections). Contrastingly, Comparative Sample 1 shows an intergranular fracture, which is a type of fracture that occurs when cracks propagate along a grain boundary. Fluxing property of a material refers to that material's ability to lower the softening, melting, or liquefaction temperature of a target substance. At the grain boundary, LTO and LLZO react or eutectic during sintering, and the LLZO grain boundary is bonded. The grain boundary is a main path for growth of lithium dendrites. Thus, bonded grain boundaries having strong binding abilities effectively inhibit growth of lithium dendrites. FIGS.4A-4Dillustrate critical current density (CCD) data for solid-state lithium symmetrical batteries comprising Samples 1-4, respectively, according to some embodiments. With the addition of LTO, the CCD of Li-garnet increases, with the highest value achieved for Sample 2 (mass ratio of LLZO to LTO of 100:4) at 1.5 mA·cm−2. In other words,FIGS.4A-4Dillustrate CCD data for a Li/LLZO-LTO/Li symmetrical battery subjected to rate cycling tests at an initial current density of 0.1 mA·cm−2, followed by increments of 0.1 mA·cm−2. Charge and discharge durations were set to 30 minutes. After current is applied, due to the impedance of the battery, a response voltage appears (in accordance with Ohm's Law). The maximum current density before short circuiting is the CCD, after which point, lithium dendrite growth is observed in the electrolyte, causing the voltage to suddenly drop. Thus, the CCD is used to evaluate the ability of electrolytes to resist lithium dendrite growth. FIGS.5A-5Dillustrate cross-sectional analysis of Sample 2, comprising: a secondary electron (SE) SEM image (FIG.5A), a corresponding back-scattered electron (BSE) SEM image ofFIG.5A(FIG.5B), and energy dispersive spectrometer (EDS) point analysis (FIGS.5C,5D), according to some embodiments. The contrast of the BSE imaging is caused by a difference in atomic number: elements with larger atomic numbers will have brighter contrasts than elements with smaller atomic numbers. BSE imaging may help to distinguish different phases more clearly. At higher magnifications (FIGS.5A and5Bis a magnification view ofFIG.3B), regions with different contrast are observed, with LLZO grain boundaries being bonded by LTO and making LLZO grain boundaries undistinguishable (FIG.5A). Combining the BSE imaging ofFIG.5B, it is determined that phases of the elements in darker contrasting areas have lower atomic numbers (e.g., titanium), with the darkest contrasting areas being the pores. Examination by EDS (FIGS.5C and5D) reveals that different areas of Sample 2 may comprise varying elemental compositions, depending on whether sampling was on the major phase (LLZO) or the minor phase (LTO). For example, Area 1 ofFIG.5Clacks lanthanum (La), indicating LTO and its decomposition or reaction products (i.e., at least one of Li4Ti5O12, LaTiO3, LaTaO4, and ZrTiO4), while Area 2 ofFIG.5Dcomprises mainly lanthanum (La), zirconium (Zr), tantalum (Ta), and oxygen (O), indicating LLZO. The dark-colored regions correspond to elements with a low atomic number (Ti), and the Ti-containing compounds (e.g., LTO) fill LLZO grain boundaries as a minor phase, blocking the dendrite growth route. In other words, for each of Samples 1-4, LTO exists as the minor or second phase in the grain boundary of the composite garnet and helps to bond the grain boundary to block the Li dendrite growth route, leading to an increase of CCD. Current research shows that lithium dendrites preferentially grow through the LLZO grain boundaries and induce short circuits in batteries during cycling. Both LZO and LTO can produce Li2O during the decomposition process, providing a lithium atmosphere for LLZO sintering and promoting densification of the ceramic electrolyte. Differences between LZO and LTO are as follows. The LLZO grain boundary is clear, the substance at the LLZO-LZO grain boundary is mainly Li2ZrO3, with a small amount of LZO, a crystalline phase and an amorphous phase coexist. LTO will partially react or eutectic with LLZO to bond LLZO grain boundaries, LTO and its decomposition or reaction products being at the grain boundary. LZO and LTO also have different relative stabilities to LLZO: while LZO mainly fills the grain boundary, LTO is bonded at the grain boundary. Thus, as presented herein, this disclosure relates to improved lithium-garnet composite ceramic electrolytes for enhanced grain boundary bonding of Li-garnet electrolytes in solid-state lithium metal battery applications. Advantages of the formed Li-garnet composite ceramic electrolytes include: (1) a higher critical current density (CCD), since LTO (LixTiO(x+4)/2(0.66≤x≤4)) has excellent fluxing properties and are distributed at the LLZO grain boundary, which enhances bonding at the LLZO grain boundary and blocks lithium dendrite growth; and (2) a simplified and cheaper sintering process, because (a) Li-garnet is densified at a lower sintering temperature with the addition of LTO powder; and (b) no mother powder is added during ceramic sintering since LTO is able to provide a Li2O sintering atmosphere. It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit or scope of the claimed subject matter. Accordingly, the claimed subject matter is not to be restricted except in light of the attached claims and their equivalents. | 32,143 |
11858855 | DETAILED DESCRIPTION OF EMBODIMENTS Implementations of the disclosure are described in detail with reference to embodiments of the disclosure. The following embodiments are used to illustrate the disclosure, but cannot be used to limit the scope of the disclosure. The disclosure provides a low-temperature sintered microwave dielectric ceramic material. The microwave dielectric ceramic material includes a base material and a low-melting-point glass material; a general chemical formula of the base material is (Zn0.9Cu0.1)0.15Nb0.3(Ti0.9Zr0.1)0.55O2; a percent by weight of the low-melting-point glass material is in a range of 1 wt. % to 2 wt. %, namely that a content of the low-melting-point glass material in the ceramic material is 1% to 2%; chemical compositions of the low-melting-point glass material include A2CO3-M2O3—SiO2, A of which represents a lithium ion (also referred to a Li+), a sodium ion (also referred to a Na+), and a potassium ion (also referred to a K+), and M of which represents a boron ion (also referred to B3+) and a bismuth ion (also referred to Bi3+). A sintering temperature of the ceramic material is in a range of 850 degree Celsius (° C.) to 900° C. A crystal structure of the ceramic material is in coexistence of a tetragonal phase and an orthogonal phase; and under the sintering temperature of 850° C., a dielectric constant of the ceramic material is 52.6, a dielectric loss is as low as 5.34×10−4, a Q×f value is as high as 8,411 gigahertz (GHz), and a τfvalue is as low as 101.2 parts per million per ° C. (ppm/° C.). A mass ratio A2CO3:M2O3:SiO2in the chemical compositions of the low-melting-point glass material is 38:40:22. The A2CO3can be Li2CO3, and/or Na2CO3, and/or K2CO3, which is determined according to actual needs. The M2O3can be B2O3, and/or Bi2O3. In an illustrated embodiment of the disclosure, the A2CO3includes the following components in parts by weight: 15 parts of Li2CO3, and 16 parts of Na2CO3, and 7 parts of K2CO3; and the M2O3includes the following components in parts by weight: 34 parts of B2O3, and 6 parts of Bi2O3. The disclosure further provides a preparation method for preparing the above mentioned low-temperature sintered microwave dielectric ceramic material, including following steps. Proportioning the base material: raw powders of ZnO, CuO, TiO2, ZrO2, Nb2O5are proportioned according to the general chemical formula (Zn0.9Cu0.1)0.15Nb0.3(Ti0.9Zr0.1)0.55O2to obtain a pre-prepared powder. Grinding: the pre-prepared powder is put into a ball milling tank, zirconium balls and deionized water are selected as grinding media, and then ball milling is performed on the pre-prepared powder in a planetary ball mill for 4 hours to 6 hours to obtain a mixed slurry, the mixed slurry is dried in an oven to obtain a first dried powder after the ball milling is completed, and then the first dried powder is sieved by a 100-mesh screen to obtain a ground powder, and the ground powder is pre-sintered in an atmospheric atmosphere at 900° C. to 1000° C. for 4 hours to 6 hours to obtain a pre-sintered material. In the grinding process, a mass ratio of the pre-prepared powder:the zirconium balls:the deionized water is 1:5-7:2-4; Proportioning the chemical compositions of the low-melting-point glass material: raw powders of the chemical compositions of the low-melting-point glass material are weighed and mixed according to a preset ratio to obtain a glass powder, zirconium balls and alcohol are selected as grinding media, and then ball milling is performed on the glass powder in a planetary ball mill for 6 hours to 8 hours to obtain a ball-milled powder, the ball-milled powder is dried to obtain a second dried power, and then the second dried power is pre-sintered for 3 hours to 6 hours at 600° C. to 650° C., followed by heating to 1450° C. to 1550° C. for melting for 4 hours to 6 hours to obtain glass melt, the glass melt is poured into ionized water for cooling to obtain a glass, and the glass is ground into uniform fine powders, thereby obtaining the low-melting-point glass material. The preset ratio is determined according to a percent by weight of the chemical compositions of the low-melting-point glass material, namely that a mass ratio of A2CO3:M2O3:SiO2in the chemical compositions of the low-melting-point glass material is 38:40:22. The raw powders of the low-melting-point glass material include A2CO3powders, M2O3powders, and SiO2powders. Specially, the A2CO3powders include Li2CO3powders, and/or Na2CO3powders, and/or K2CO3powders. In an illustrated embodiment, the A2CO3powders include at least two of a group consisting of Li2CO3powders, Na2CO3powders, and K2CO3powders. The M2O3powders include B2O3powders, and/or Bi2O3powders. In an illustrated embodiment of the disclosure, the raw powders of the chemical compositions of the low-melting-point glass material include the Li2CO3powders, the Na2CO3powders, the K2CO3powders, the B2O3powders, the Bi2O3powders, and the SiO2powders. In the proportioning the chemical compositions of the low-melting-point glass material, a mass ratio of the Li2CO3powders:the Na2CO3powders:the K2CO3powders:the B2O3powders:the Bi2O3powders:the SiO2powders is 15:16:7:34:6:22; and a mass ratio of the glass powder:the zirconium balls:the alcohol is 1:5-7:4-6. Mixing: the obtained low-melting-point glass material is added into the pre-sintered material according to the percent by weight of 1 wt. % to 2 wt. % to obtain a mixed powder, zirconium balls and deionized water are selected as grinding media again, and then ball milling is performed on the mixed powder in a planetary ball mill for 3 hours to 5 hours to obtain a ball-milled mixed powder, the ball-milled mixed powder is dried to obtain a third dried powder, followed by adding a binder into the third dried powder to granulate, thereafter obtaining a ceramic raw material. In the mixing process, a mass ratio of the mixed powder the zirconium balls:the deionized water is 1:4-5:3-5. The binder is an acrylic acid solution. Sintering to prepare the microwave dielectric ceramic material: the ceramic raw material is pressed and molded, and then the ceramic raw material is discharged for 2 hours to 4 hours at a temperature of 400° C. to 450° C. with a heating rate of 2° C. per minute (° C./min) to 4° C./min to obtain a discharged ceramic raw material, and then the discharged ceramic raw material is heated to 850° C. to 900° C. with the same heating rate of 2° C./min to 4° C./min, followed by heat preserving for 4 hours to 6 hours, thereby obtaining the low-temperature sintered microwave dielectric ceramic material. In order to better explain the technical effects of the disclosure, 3 samples for embodiments 1-3 are prepared by the preparation method provided by the disclosure. The chemical compositions of the low-melting-point glass material added in each of the embodiments 1-3 are determined as the illustrated technical solution in the above described preparation method. The mass of each chemical composition in each embodiment and the corresponding sintering temperature of each embodiment are shown in Table 1, and dielectric properties of each embodiment are shown in Table 2. The mass of each chemical composition and the corresponding sintering temperature in the embodiments 1-3 are shown in the following Table 1. Sample number for embodiment123Mass of eachZnO11.17011.17011.170chemicalCuO1.2131.2131.213composition/gramNb2O540.53540.53540.535abbreviated as gTiO240.19140.19140.191ZrO26.8906.8906.890Li2CO30.3000.3000.300Na2CO30.3200.3200.320K2CO30.1400.1400.140B2O30.6800.6800.680Bi2O30.1200.1200.120SiO20.4400.4400.440Sintering temperature (° C.)850875900 Sample numberDielectrictanδQ × fτffor embodimentconstant εr(10−4)(GHz)(ppm/° C.)152.65.348,411101.2252.85.557,978101.8352.65.128,574100.9 It can be seen from the data shown in Table 1 and Table 2 above that in the embodiments, the dielectric constants of the samples are very stable and are close to 52.7, which indicates that when the sintering temperature is at 850° C., the corresponding sample has been sintered compact, and there is no variation for densification when the sintering temperature continues to rise, thereby stabilizing the dielectric constant. Compared with a ceramic material without adding the glass material, the sintering temperature of the sample is greatly reduced (from 1150° C. to 850° C.), and the τfvalue is also greatly reduced from 206.8 ppm/° C. to 101.2 ppm/° C. However, the Q×f value has a small amplitude reduction trend, in view of the comprehensive sintering temperature and the temperature coefficient of resonant frequency, the glass material is excellently matched with the ceramic base material. Therefore, the low-temperature sintered microwave dielectric ceramic material can be applied to the technical field of LTCC. FIGURE illustrates an X-ray diffraction (XRD) diagram of the embodiment 1. After test, the phase composition of the ceramic material is two-phase coexistence, a major crystal phase of which is a tetragonal phase matched with a standard card 79-1186 of the joint committee on powder diffraction standards abbreviated as JCPDS (referred to International Centre for Diffraction data), and a subordination crystal phase of which is an orthogonal phase matched with a standard card 35-0584. In addition, other excess diffraction peaks are not found, indicating that the introduction of the glass material does not change the phase composition. The illustrated embodiments of the disclosure are described above with reference to the embodiments and the attached drawings. Those skilled in the related art can make a variety of variants to implement the disclosure without departing from the scope and substance of the disclosure. For example, some technical features illustrated or described in an embodiment may be used in another embodiment to obtain a still another embodiment. The above description is merely the illustrated embodiments of the disclosure, and are not therefore intended to limit the scope of the disclosure, and the equivalent changes made by the description and the attached drawings of the disclosure are all covered in the scope of the disclosure. | 10,234 |
11858856 | DETAILED DESCRIPTION Problem to be Solved by the Present Disclosure High-hardness conductive diamond polycrystalline body disclosed in Japanese Patent Laying-Open No. 2012-106925 (PTL1) contains boron as a boron compound in a diamond crystal, and thus, boron oxide is formed on a surface of diamond, so that oxidation resistance is improved. Such a boron compound, however, does not have a diamond structure, without high hardness like diamond, and has a thermal expansion coefficient different from that of diamond. Therefore, a problem may occur such as deterioration of wear resistance or occurrence of a crack at a high temperature. Polycrystalline diamond disclosed in Japanese Patent Laying-Open No. 2013-28500 (PTL2) does not contain a boron compound because boron has been dispersed at the atomic level, so that occurrence of a crack or the like is suppressed. However, carbon exposed on the surface is subjected to oxidation, thereby being tuned into COXgas to be consumed. Therefore, a problem may occur such as deterioration of wear resistance. Then, in the polycrystalline diamond, boron is included in the diamond crystal at the atomic level and in an isolated substitutional type, and the surface of the diamond is also covered with a protective film which is an oxide film so as to solve the above-described problems. Thus, an object of the present invention is to provide polycrystalline diamond having high wear resistance and a method for manufacturing the same; a scribe tool, a scribe wheel, a dresser, a rotating tool, a wire drawing die, a cutting tool, and an electrode that are formed using the polycrystalline diamond; and a processing method using the polycrystalline diamond. Advantageous Effect of the Present Disclosure According to the above, in the polycrystalline diamond, boron is included in the diamond crystal at the atomic level and in an isolated substitutional type, and the surface of the diamond is covered with a protective film which is an oxide film so as to solve the above-described problems. Thus, polycrystalline diamond having high wear resistance and a method for manufacturing the same; a scribe tool, a scribe wheel a dresser, a rotating tool, a wire drawing die, a cutting tool, and an electrode that are formed using the polycrystalline diamond; and a processing method using the polycrystalline diamond can be provided. Description of Embodiments First, embodiments of the present invention will be listed and described. [1] The polycrystalline diamond according to an embodiment of the present invention is polycrystalline diamond having a diamond single phase as basic composition, wherein the polycrystalline diamond includes a plurality of crystal grains; the polycrystalline diamond contains boron, hydrogen, oxygen, and a remainder including carbon and trace impurities; the boron is dispersed in the crystal grains at an atomic level, and greater than or equal to 90 atomic % of the boron is present in an isolated substitutional type, the hydrogen and the oxygen are present in an isolated substitutional type or an interstitial type in the crystal grains; each of the crystal grains has a grain size of less than or equal to 500 nm; and the polycrystalline diamond has a surface covered with a protective film. The boron is dispersed in the crystal grains of the polycrystalline diamond at an atomic level, greater than or equal to 90 atomic % of the boron is present in an isolated substitutional type, and the hydrogen and the oxygen are also present in an isolated substitutional type or an interstitial type in the crystal grains, so that the polycrystalline diamond according to the present embodiment maintains a high-hardness diamond structure in the inner portion thereof, and the carbon, the boron, the hydrogen, and the oxygen exposed on the surface of the polycrystalline diamond form an oxide film, and the oxide film covers the surface of the polycrystalline diamond as a protective film. Therefore, the oxidation resistance of the polycrystalline diamond increases and the coefficient of friction is reduced, which in turn improves sliding properties and wear resistance. [2] In the polycrystalline diamond according to the present embodiment, greater than or equal to 99 atomic % of the boron can be present in an isolated substitutional type in the crystal grains. The polycrystalline diamond more easily maintains the high-hardness diamond structure in the inner portion thereof. [3] In the polycrystalline diamond according to the present embodiment, the boron can have an atomic concentration of greater than or equal to 1×1014cm−3and less than or equal to 1×1022cm−3. Since the polycrystalline diamond has a boron concentration of greater than or equal to 1×1014cm−3and less than or equal to 1×1022cm−3, a suitable protective film is formed on its surface. [4] In the polycrystalline diamond according to the present embodiment, the hydrogen can have an atomic concentration of greater than or equal to 1×1017cm−3and less than or equal to 1×1020cm−3. The polycrystalline diamond has a hydrogen concentration of greater than or equal to 1×1017cm−3and less than or equal to 1×1020cm−3, oxygen can be stably contained in the crystal and deterioration of hardness can be suppressed. [5] In the polycrystalline diamond according to the present embodiment, the oxygen can have an atomic concentration of greater than or equal to 1×1017cm−3and less than or equal to 1×1020cm−3. Since the polycrystalline diamond has an oxygen concentration of greater than or equal to 1×1017cm−3and less than or equal to 1×1020cm−3, the formation of the protective film, which is an oxide film, on the surface thereof is accelerated, so that oxidation resistance is improved, the coefficient of friction is reduced, and deterioration of hardness can also be suppressed. [6] In a Raman spectroscopic measurement of the polycrystalline diamond according to the present embodiment, a peak area around 1575 cm−1±30 cm−1with a half width of greater than 10 cm−1and less than or equal to 20 cm−1can be less than 1% of a peak area around 1300 cm−1±30 cm−1with a half width of less than or equal to 60 cm−1. Since a peak area derived from amorphous carbon or graphite carbon (SP2 carbon) around 1575 cm−1±30 cm−1with a half width of less than or equal to 20 cm−1is less than 1% of a peak area derived from diamond carbon (SP3 carbon) around 1300 cm−1±30 cm−1with a half width of less than or equal to 60 cm−1, the graphite carbon is substantially completely (specifically, greater than or equal to 99 atomic %) converted to diamond carbon, so that the polycrystalline diamond has high hardness. [7] The surface (the surface covered with the protective film) of the polycrystalline diamond according to the present embodiment can have a dynamic friction coefficient of less than or equal to 0.06. Since the surface thereof has a low dynamic friction coefficient of less than or equal to 0.06, the polycrystalline diamond has high sliding properties and high wear resistance. [8] The surface (the surface covered with the protective film) of the polycrystalline diamond according to the present embodiment can have a dynamic friction coefficient of less than or equal to 0.05. Since the surface thereof has a low dynamic friction coefficient of less than or equal to 0.05, the polycrystalline diamond has high sliding properties and high wear resistance. [9] In the polycrystalline diamond according to the present embodiment, the protective film can contain a BOXcluster, and at least one of O and OH that are an oxygen end of the carbon. It is considered that the BOXcluster is formed by allowing B (boron) exposed on the surface to react with oxygen in the air and oxygen in the crystal grains (oxygen in the crystal grains in vacuo or in an inert gas) and that O and OH that are an oxygen end of the carbon are formed by allowing the carbon exposed on the surface to react with oxygen in the air and oxygen in the crystal grains (oxygen in the crystal grains in vacuo or in an inert gas). These elements have high slidability and a low coefficient of friction, so that wear resistance is improved. [10] In the polycrystalline diamond according to the present embodiment, the protective film can contain a precipitate precipitated out of the crystal grains. In addition to the BOXcluster and at least one of O and OH that are an oxygen end of the carbon, the protective film further contains the precipitate having high slidability and a low coefficient of friction, so that the wear resistance of the polycrystalline diamond is improved. [11] In the polycrystalline diamond according to the present embodiment, the protective film has an average film thickness of greater than or equal to 1 nm and less than or equal to 1000 nm. Because of the protective film having an average film thickness of greater than or equal to 1 nm and less than or equal to 1000 nm, even though the surface of the polycrystalline diamond is chipped due to mechanical damage to the polycrystalline diamond, the chipped portion is filled with the protective film in a portion other than the chipped portion, so that the polycrystalline diamond maintains a smooth surface. [12] The polycrystalline diamond can contain a graphene nanoribbon. Accordingly, a graphene nanoribbon-derived protective film can be formed on the surface thereof. [13] The polycrystalline diamond can have a peak at a Raman shift of 1554 cm−1±20 cm−1with a half width of less than or equal to 10 cm−1in the Raman spectroscopic measurement. Accordingly, a graphene nanoribbon-derived protective film can be formed on the surface thereof. [14] The polycrystalline diamond can have a peak at a Raman shift of 2330 cm−1±20 cm−1with a half width of less than or equal to 6 cm−1in the Raman spectroscopic measurement. Accordingly, a graphene nanoribbon-derived protective film can be formed on the surface thereof. [15] Specifically, the polycrystalline diamond according to the present embodiment is polycrystalline diamond having a diamond single phase as basic composition, wherein the polycrystalline diamond includes a plurality of crystal grains; the polycrystalline diamond contains boron, hydrogen, oxygen, and a remainder including carbon and trace impurities; the boron is dispersed in the crystal grains at an atomic level, and greater than or equal to 90 atomic % of the boron is present in an isolated substitutional type; the hydrogen and the oxygen are present in an isolated substitutional type or an interstitial type in the crystal grains; each of the crystal grains has a grain size of less than or equal to 500 nm; the polycrystalline diamond has a surface covered with a protective film; the boron has an atomic concentration of greater than or equal to 1×1014cm−3and less than or equal to 1×1022cm−3; the hydrogen has an atomic concentration of greater than or equal to 1×1017cm−3and less than or equal to 1×1020cm−3; the oxygen has an atomic concentration of greater than or equal to 1×1017cm−3and less than or equal to 1×1020cm−3; in a Raman spectroscopic measurement of the polycrystalline diamond, a peak area around 1575 cm−1±30 cm−1with a half width of greater than 10 cm−1and less than or equal to 20 cm−1is less than 1% of a peak area around 1300 cm−1±30 cm−1with a half width of less than or equal to 60 cm−1; the surface (the surface covered with the protective film) of the polycrystalline diamond has a dynamic friction coefficient of less than or equal to 0.05; the protective film contains a BOXcluster, at least one of O and OH that are an oxygen end of the carbon, and a precipitate precipitated out of the crystal grains; the protective film has an average film thickness of greater than or equal to 1 nm and less than or equal to 1000 nm; the polycrystalline diamond contains a graphene nanoribbon; the polycrystalline diamond has a peak at a Raman shift of 1554 cm−1±20 cm−1with a half width of less than or equal to 10 cm−1in the Raman spectroscopic measurement; and the polycrystalline diamond has a peak at a Raman shift of 2330 cm−1±20 cm−1with a half width of less than or equal to 6 cm−1in the Raman spectroscopic measurement. Since the polycrystalline diamond has the above-described characteristics, the oxidation resistance thereof increases and the dynamic friction coefficient is reduced, which in turn improves sliding properties and wear resistance. [16] A method for manufacturing polycrystalline diamond according to another embodiment of the present invention includes a first step of preparing graphite containing carbon, boron, hydrogen, and oxygen; a second step of placing the graphite in a vessel under an inert gas atmosphere; and a third step of converting the graphite to diamond by pressure heat treatment in the vessel, wherein the boron is dispersed in a crystal grain of the graphite at an atomic level, and greater than or equal to 90 atomic % of the boron is present in an isolated substitutional type. In the method for manufacturing polycrystalline diamond according to another embodiment of the present invention, since the graphite is directly converted to diamond, polycrystalline diamond of the above embodiment having high oxidation resistance, a low dynamic friction coefficient, high sliding properties, and high wear resistance (i.e., polycrystalline diamond containing boron, hydrogen, and oxygen, in which the boron is dispersed in the crystal grains at the atomic level, and greater than or equal to 90 atomic % of the boron is present in an isolated substitutional type; and the hydrogen and the oxygen are present in an isolated substitutional type or an interstitial type in the crystal grains) can be manufactured. [17] In the method for manufacturing polycrystalline diamond according to the present embodiment, the first step includes a sub-step of forming a graphite base material containing carbon and boron on a base material by a vapor phase method, and the boron is dispersed in a crystal grain of the graphite base material at an atomic level, and greater than or equal to 90 atomic % of the boron is present in an isolated substitutional type. According to the method for manufacturing polycrystalline diamond, the graphite base material can be suitably produced by the vapor phase method. [18] In the method for manufacturing polycrystalline diamond according to the present embodiment, the first step can further include a sub-step of including the hydrogen and the oxygen in the graphite base material by a vapor phase method. According to the method for manufacturing polycrystalline diamond, the graphite can be suitably produced by including the hydrogen and the oxygen in the graphite base material by the vapor phase method. [1] In the method for manufacturing polycrystalline diamond according to the present embodiment, the first step can further include a sub-step of including the hydrogen and the oxygen in the graphite base material under vacuum condition. According to the method for manufacturing polycrystalline diamond, the graphite can be suitably produced by including the hydrogen and the oxygen in the graphite base material under vacuum condition. [20] In the method for manufacturing polycrystalline diamond according to the present embodiment, the first step can include a step of forming the graphite on a base material by simultaneously mixing the carbon, the boron, the hydrogen, and the oxygen with one another in vapor phase by a vapor phase method. According to the method for manufacturing polycrystalline diamond, the graphite can be suitably produced by simultaneously mixing the carbon, the boron, the hydrogen, and the oxygen with one another in vapor phase by the vapor phase method, and then allowing these elements to react with one another. [21] In the method for manufacturing polycrystalline diamond according to the present embodiment, the first step can include a sub-step of forming a gas mixture containing the carbon, the boron, the hydrogen, and the oxygen; and a sub-step of forming the graphite on the base material by thermally decomposing the gas mixture at a temperature of greater than or equal to 1500° C. and feeding the gas mixture toward the base material, and the gas mixture can include a gas containing the boron, the hydrogen, and the oxygen, and a hydrocarbon gas. According to the method for manufacturing polycrystalline diamond, the graphite can be suitably produced in good yield by feeding the gas mixture including the hydrocarbon gas containing the carbon, and the gas containing the boron, the hydrogen, and the oxygen toward the base material. [22] In the method for manufacturing polycrystalline diamond according to the present embodiment, the hydrocarbon gas can be a methane gas. According to the method for manufacturing polycrystalline diamond, the graphite of the above embodiments can be suitably produced by using a methane gas as the hydrocarbon gas. [23] In the method for manufacturing polycrystalline diamond according to the present embodiment, in the third step, the graphite can be directly subjected to pressure heat treatment in a pressure heat treatment apparatus. According to the method for manufacturing polycrystalline diamond, the polycrystalline diamond of the above embodiment can be suitably manufactured by directly subjecting the graphite to pressure heat treatment in the pressure heat treatment apparatus. [24] In the method for manufacturing polycrystalline diamond according to the present embodiment, the pressure heat treatment can be performed under conditions of greater than or equal to 6 GPa and greater than or equal to 1200° C. According to the method for manufacturing polycrystalline diamond, the polycrystalline diamond of the above embodiment can be suitably manufactured by performing pressure heat treatment under conditions of greater than or equal to 6 GPa and greater than or equal to 1200° C. [25] In the method for manufacturing polycrystalline diamond according to the present embodiment, the pressure heat treatment can be performed under conditions of greater than or equal to 8 GPa and less than or equal to 30 GPa, and greater than or equal to 1200° C. and less than or equal to 2300° C. According to the method for manufacturing polycrystalline diamond, the polycrystalline diamond of the above embodiment can be suitably manufactured by performing pressure heat treatment under conditions of greater than or equal to 8 GPa and less than or equal to 30 GPa, and greater than or equal to 1200° C. and less than or equal to 2300° C. [26] The scribe tool according to still another embodiment of the present invention can be formed using the polycrystalline diamond of the above embodiment. The scribe tool according to the present embodiment has high wear resistance because it is formed using the polycrystalline diamond of the above embodiment. [27] The scribe wheel according to still another embodiment of the present invention can be formed using the polycrystalline diamond of the above embodiment. The scribe wheel according to the present embodiment has high wear resistance because it is formed using the polycrystalline diamond of the above embodiment. [28] The dresser according to still another embodiment of the present invention can be formed using the polycrystalline diamond of the above embodiment. The dresser according to the present embodiment has high wear resistance because it is formed using the polycrystalline diamond of the above embodiment. [29] The rotating tool according to still another embodiment of the present invention can be formed using the polycrystalline diamond of the above embodiment. The rotating tool according to the present embodiment has high wear resistance because it is formed using the polycrystalline diamond of the above embodiment. [30] The wire drawing die according to still another embodiment of the present invention can be formed using the polycrystalline diamond of the above embodiment. The wire drawing die according to the present embodiment has high wear resistance because it is formed using the polycrystalline diamond of the above embodiment. [31] The cutting tool according to still another embodiment of the present invention can be formed using the polycrystalline diamond of the above embodiment. The cutting tool according to the present embodiment has high wear resistance because it is formed using the polycrystalline diamond of the above embodiment. [32] The electrode according to still another embodiment of the present invention can be formed using the polycrystalline diamond of the above embodiment. The electrode according to the present embodiment has high wear resistance because it is formed using the polycrystalline diamond of the above embodiment. [33] In the processing method according to still another embodiment of the present invention, an object can be processed using the polycrystalline diamond of the above embodiment. In the processing method according to the present embodiment, the object can be efficiently processed at low cost because it is processed using the polycrystalline diamond of the above embodiment. [34] In the processing method according to still another embodiment of the present invention, the object can be an insulator. In the processing method according to the present embodiment, the object is processed using the polycrystalline diamond of the above embodiment having conductivity. Therefore, even though the object is an insulator, it can be efficiently processed at low cost without generating abnormal wear and tear caused by triboplasma or the like. [35] In the processing method according to still another embodiment of the present invention, the insulator as the object can have a resistivity of greater than or equal to 100 kΩ·cm. In the processing method according to the present embodiment, the object is processed using the polycrystalline diamond of the above embodiment having conductivity. Therefore, even though the object is an insulator having a resistivity of greater than or equal to 100 kΩ·cm, the object can be efficiently processed at low cost without etching caused by triboplasma. DETAILS OF EMBODIMENTS OF INVENTION Embodiments according to the present invention will be described in further detail below. Here, the notation “A to B” in this specification means upper and lower limits of the range (i.e., greater than or equal to A and less than or equal to B), and in the case where not A but only B is expressed in units, the unit of A is the same as that of B. Unless an atom ratio is not particularly limited when a compound or the like is represented by a chemical formula in this specification, the compound has any previously known atom ratio, and the atom ratio should not be limited only to one in a stoichiometric range. Embodiment 1: Polycrystalline Diamond The polycrystalline diamond according to the present embodiment is polycrystalline diamond having a diamond single phase as basic composition, in which the polycrystalline diamond includes a plurality of crystal grains; the polycrystalline diamond contains boron, hydrogen, oxygen, and the remainder including carbon and trace impurities; the boron is dispersed in the crystal grains at an atomic level, and greater than or equal to 90 atomic % of the boron is present in an isolated substitutional type; the hydrogen and the oxygen are present in an isolated substitutional type or an interstitial type in the crystal grains; each of the crystal grains has a grain size of less than or equal to 500 nm; and the polycrystalline diamond has a surface covered with a protective film. Since the polycrystalline diamond according to present embodiment has a diamond single phase as basic composition, it does not contain a binding phase (binder) composed of both or one of a sintering aid and a catalyst, and grain dropping does not occur due to the difference in thermal expansion coefficient even under a high temperature condition. Further, since the polycrystalline diamond is a polycrystal formed of a plurality of crystal grains having a grain size of less than or equal to 500 nm, it does not have orientation and cleavage properties like a single crystal and has hardness and wear resistance that are isotropic in all directions. Since the polycrystalline diamond contains boron, hydrogen, and oxygen in the crystal grains, the surface thereof is covered with a protective film which is an oxide film. Accordingly, the oxidation resistance increases, and the dynamic friction coefficient is reduced, which in turn improves sliding properties and wear resistance. In the polycrystalline diamond according to the present embodiment, from the viewpoint of having hardness and wear resistance that are isotropic in all directions, the maximum grain size of the crystal grains of the polycrystalline diamond is less than or equal to 500 nm, preferably less than or equal to 200 nm, and more preferably less than or equal to 100 nm. From the viewpoint of high hardness, the minimum grain size of the crystal grains of the polycrystalline diamond may be greater than or equal to 1 nm, and preferably greater than or equal to 20 nm. The polycrystalline diamond having a grain size of less than or equal to 500 nm can obtain an effect of having isotropic hardness. Further, the polycrystalline diamond having a grain size of greater than or equal to 1 nm can obtain an effect of having mechanical strength specific to diamond. The polycrystalline diamond has more preferably a grain size of greater than or equal to 20 nm and less than or equal to 200 nm. In addition, it is more preferable that an aspect ratio of a major axis a to a minor axis b of each grain satisfies the relationship of a/b<4. The grain size of the polycrystalline diamond can be measured by electron microscopy such as SEM or TEM. Any surface of the polycrystalline diamond is polished to prepare a polished surface for observation for the measurement of the grain size. Then, any one location (one visual field) on the polished surface for observation is observed, for example, using SEM at a magnification of 20000. Since approximately 120 to 200000 crystal grains of the polycrystalline diamond appear in one visual field, 10 of those crystal grains are measured to determine their grain sizes, and it is confirmed that all of them have a grain size of less than or equal to 500 nm. Such measurement is performed on all of the visual fields in all sample sizes, and therefore, it can be confirmed that the polycrystalline diamond has a grain size of less than or equal to 500 nm. The grain size of the polycrystalline diamond can also be measured by an X-ray diffraction method (XRD method) based on the following conditions. Measuring apparatus: Trade name (product number) “X'pert”, manufactured by PANalytical B.V.X-ray light source: Cu-Kα ray (wave length: 1.54185 Å)Scan axis: 2θScan range: 20θ to 120°Voltage: 40 kVCurrent: 30 mAScan speed: 1°/min The half width was determined by the Scherrer's equation (D=Kλ/B cos θ) through peak fitting. Here, D is a crystal grain size of the diamond; B is a diffraction line width; λ is an X-ray wavelength; θ is a Bragg angle; K is a correction factor (0.9) determined by correlation with an SEM image. <Elements in the Crystal Grains> In the polycrystalline diamond according to the present embodiment, the boron is dispersed in the crystal grains at the atomic level, and greater than or equal to 90 atomic % of the boron is present in an isolated substitutional type; and the hydrogen and the oxygen are also present in an isolated substitutional type or an interstitial type in the crystal grains, so that the boron, the hydrogen, and the oxygen exposed on the surface of the polycrystalline diamond form an oxide film, and the oxide film covers the surface of the polycrystalline diamond as a protective film. Therefore, the oxidation resistance of the polycrystalline diamond increases and the coefficient of friction is reduced, which in turn improves sliding properties and wear resistance. In the polycrystalline diamond according to the present embodiment, since the boron is dispersed at the atomic level and greater than or equal to 90 atomic % of the boron is present in an isolated substitutional type, a protective film which is an oxide film is formed only on the surface thereof when the surface thereof is damaged due to wear and/or breakage, and the diamond structure is maintained inside the polycrystalline diamond, so that the hardness is maintained. In addition, the boron is dispersed at the atomic level, and greater than or equal to 90 atomic % of the boron is present in an isolated substitutional type, the boron does not aggregate as clusters inside, and the boron also does not aggregate at a crystal grain boundary of diamond. Therefore, there is no segregation of impurities that could be a starting point of a crack due to temperature change and/or impact. In addition, since the boron is dispersed at the atomic level and greater than or equal to 90 atomic % of the boron is present in an isolated substitutional type, a protective film which is an oxide film localized on a desired exposed surface is formed over the entire polycrystalline diamond, and positive holes are excessively present as electric charge. Therefore, further oxygen is likely to be attracted to its surface only. In the polycrystalline diamond according to the present embodiment, the “boron is dispersed at the atomic level” refers to a dispersed state at such a level that, when carbon and boron are mixed in a vapor phase state to thereby produce polycrystalline diamond, different elements such as boron are dispersed in the carbon that forms a crystal of the polycrystalline diamond, each element having a finite activation energy without changing the diamond crystal structure. That is, such a dispersed state refers to a state where a different element to be isolated and precipitated and a different compound other than diamond are not formed. In addition, the “isolated substitutional type” refers to an existence form in which different elements such as boron, hydrogen, and oxygen are isolated and substituted for carbon located at a lattice point of the polycrystalline diamond or graphite crystal lattice. The “interstitial type” refers to an existence form in which different elements such as hydrogen and oxygen are entered into spaces between carbons located at lattice points of the polycrystalline diamond crystal lattice. The dispersed state and existence form of boron, hydrogen, and oxygen in the polycrystalline diamond according to the present embodiment can be observed with a transmission electron microscope (TEM). It can be confirmed by temperature dependence of electrical resistance, detection of activation energy, or a time-of-flight secondary ion mass spectrometry (TOF-SIMS) that the boron is “dispersed at the atomic level” and an “isolated substitutional type”. The existence of the hydrogen and the oxygen in an “isolated substitutional type” or an “interstitial type” can be confirmed by TOF-SIMS. With the TEM used for confirmation of the dispersed state and existence form as described above, the polished surface for observation for measuring the grain size of the polycrystalline diamond can be confirmed by observing any ten locations (ten visual fields) on the polished surface for observation at a magnification of 20000 to 100000. Using TOF-SIMS, for example, analysis can be performed under the following conditions, so that it can be confirmed that each of the elements is “dispersed at the atomic level” and that each of the elements is an “isolated substitutional type” or an “interstitial type”.Measuring apparatus: Time-of-flight secondary ion mass spectrometer (TOF-SIMS)Primary ion source: Bismuth (Bi)Primary acceleration voltage: 25 kV The secondary ion mass spectrometry (SIMS) is used to measure concentrations of the boron, the hydrogen, and the oxygen inside the polycrystalline diamond, and the TOF-SIMS is used to measure those concentrations on the surface of the polycrystalline diamond and in the vicinity thereof (e.g., the oxide film as the protective film, and the polycrystalline diamond in the vicinity thereof, from the surface to a depth of 100 nm). Further, the dispersed state and the existence form as described above can be evaluated by X-ray diffraction (XRD), Raman spectroscopy, or the like. In addition, the concentration of the trace impurities formed of elements other than the carbon, the boron, the hydrogen, and the oxygen in the polycrystalline diamond according to the present embodiment is measured by SIMS or inductively coupled plasma-mass spectrometry (ICP-MS). Using SIMS, for example, analysis can be performed under the following conditions, so that the atomic concentrations of the boron, the hydrogen, and the oxygen and the atomic concentration of the trace impurities inside the polycrystalline diamond can be measured.Measuring apparatus: Trade name (product number): “IMS-7f”, manufactured by AMETEK Inc.Primary ion species: Cesium (Cs+)Primary acceleration voltage: 15 kVDetection area: 30 (μm φ)Measurement accuracy: ±40% (2σ) In the polycrystalline diamond according to the present embodiment, from the viewpoint of easily maintaining the high-hardness diamond structure inside the polycrystalline diamond, greater than or equal to 90 atomic/o of the boron is in an isolated substitutional type, preferably greater than or equal to 95 atomic % thereof is in an isolated substitutional type, and more preferably greater than or equal to 99 atomic % is in an isolated substitutional type. The ratio of the isolated substitutional boron to the total boron is determined by measuring the ratio of the number of boron atoms responsible for the Hall effect to the total number of boron atoms using SIMS in known hall measurement, measurement of temperature dependence of electrical resistance, and C-V measurement. (Boron Atom Concentration) In the polycrystalline diamond according to the present embodiment, from the viewpoint of suppressing increase of the crystal grain size to form a protective film which is a suitable oxide film on the surface thereof, the boron preferably has an atom concentration of greater than or equal to 1×1014cm−3and less than or equal to 1×1022cm−3, and more preferably greater than or equal to 1×1014cm−3and less than or equal to 1×1021cm−3. As compared with the preferable range, the more preferable range further suppresses the formation of a crystal grain having a grain size exceeding 500 nm, so that the yield is improved from greater than or equal to 30% to greater than or equal to 90%. Within the boron concentration range described above, the polycrystalline diamond exhibits electrical properties as a p-type semiconductor in the range of less than 1×1019cm−3and exhibits electrical properties as a metallic conductor in the range of greater than or equal to 1×1019cm−3. (Hydrogen Atom Concentration) In the polycrystalline diamond according to the present embodiment, from the viewpoint such that the oxygen can be stably contained in the crystal, and deterioration of hardness and increase of the crystal grain size can be suppressed, the hydrogen preferably has an atomic concentration of greater than or equal to 1×1017cm−3and less than or equal to 1×102cm−3, and more preferably greater than or equal to 1×1017cm−3and less than or equal to 1×1019cm−3. However, even though the hardness is deteriorated, the polycrystalline diamond has higher hardness than a cubic boron nitride having a Knoop hardness of approximately 50 GPa and an industrial Ib-type diamond single crystal having a Knoop hardness of approximately 90 GPa. Therefore, the polycrystalline diamond is sufficiently useful for applications taking advantage of wear resistance properties (e.g., for wire drawing dies, for sliding parts, etc.). In the case where there is no hydrogen in the crystal, the oxygen reacts with the carbon in the polycrystalline diamond to produce a carbon oxide (COX) gas, and such a gas has a high temperature and is readily released, which makes it difficult to add oxygen into the crystal of the polycrystalline diamond. (Oxygen Atom Concentration) In the polycrystalline diamond according to the present embodiment, from the viewpoint such that the formation of the protective film, which is an oxide film, on the surface thereof is accelerated, so that oxidation resistance is improved, the coefficient of friction is reduced, and deterioration of hardness and increase of the crystal grain size can also be suppressed, the oxygen preferably has an atomic concentration of greater than or equal to 1×1017cm−3and less than or equal to 1×1020cm−3, and more preferably greater than or equal to 1×1018cm−3and less than or equal to 1×1019cm−3. (Concentration of Trace Impurities) The trace impurities contained in the polycrystalline diamond collectively refers to compounds which may be contained in trace amounts during manufacturing of the polycrystalline diamond. The content of each of the impurities contained as the trace impurities (each atomic concentration) is greater than or equal to 0 cm−3and less than or equal to 1016cm−3, and the total content of all the impurities contained as the trace impurities (total atomic concentration) is greater than or equal to 0 cm−3and less than or equal to 1017cm−3. Therefore, the trace impurities may or may not be contained in the polycrystalline diamond. The trace impurities include B4C, B2O3, B3O6, and the like. The trace impurities other than these may include a compound containing a metal element categorized as a transition metal element, and the like. (SIMS Measurement) FIG.1is a graph showing an example of SIMS results of the polycrystalline diamond according to the present embodiment. The polycrystalline diamond shown inFIG.1is obtained by directly converting graphite to diamond under conditions of 16 GPa and 2100° C., the graphite being obtained by adding hydrogen and oxygen under a vacuum atmosphere of 1×10−2Pa to a graphite base material containing boron that has been formed by a chemical vapor deposition (CVD) method. The measurement conditions of SIMS are as follows.Measuring apparatus: Trade name (product number): “IMS-7f”, manufactured by AMETEK Inc.Primary ion species: Cesium (Cs+)Primary acceleration voltage: 15 kVDetection area: 30 (μm φ)Measurement accuracy: ±40% (2σ) With reference toFIG.1, the polycrystalline diamond according to the present embodiment contains the boron, the hydrogen, and the oxygen in uniform concentrations from the surface to the inside thereof. (TOF-SIMS Measurement) FIG.2is a graph showing an example of TOF-SIMS results of a surface of the polycrystalline diamond according to the present embodiment. The polycrystalline diamond shown inFIG.2is polycrystalline diamond used in SIMS shown inFIG.1. The measurement conditions of TOF-SIMS are as follows.Measuring apparatus: Time-of-flight secondary ion mass spectrometer (TOF-SIMS)Primary ion source: Bismuth (Bi)Primary acceleration voltage: 25 kV With reference toFIG.2, three chemical species of BO2, O, and O2are detected as oxygen-containing species included in the oxide film as the protective film covering the surface of the polycrystalline diamond. Here, boron is detected as BO2in the oxide film. Therefore, it is considered that in the crystal inside the polycrystalline diamond, the boron is dispersed at the atomic level and most of the boron is present in the isolated substitutional type. (Raman Spectroscopic Measurement) In the Raman spectroscopic measurement of the polycrystalline diamond according to the present embodiment, the peak area around 1575 cm−1±30 cm−1with a half width of greater than 10 cm−1and less than or equal to 20 cm−1is preferably less than 1%, and more preferably less than 0.2%, of the peak area around 1300 cm−1±30 cm−1with a half width of less than or equal to 60 cm−1. Since the peak area derived from amorphous carbon or graphite carbon (SP2 carbon) around 1575 cm−1±30 cm−1with a half width of greater than 10 cm−1and less than or equal to 20 cm−1is less than 1% of the peak area derived from diamond carbon (SP3 carbon) around 1300 cm−1±30 cm−1with a half width of less than or equal to 60 cm−1, the graphite carbon is substantially completely (specifically, greater than or equal to 99 atomic %) converted to diamond carbon, so that the polycrystalline diamond has high hardness. (Dynamic Friction Coefficient) The surface (the surface covered with the protective film) of the polycrystalline diamond according to the present embodiment preferably has a dynamic friction coefficient of less than or equal to 0.06, more preferably less than or equal to 0.05, further preferably less than or equal to 0.04, particularly preferably less than or equal to 0.03, and most preferably less than or equal to 0.02. The polycrystalline diamond has high sliding properties and high wear resistance because the surface thereof has a low dynamic friction coefficient of less than or equal to 0.06. (Protective Film) In the polycrystalline diamond according to the present embodiment, the oxide film formed as the protective film that covers the surface thereof preferably contains a BOXcluster, and at least one of O and OH that are an oxygen end of the carbon. It is considered that the BOXcluster is obtained by allowing B (boron) exposed on the surface to react with oxygen in the air and oxygen in the crystal (oxygen in the crystal in vacuo or in an inert gas) and that O and OH that are an oxygen end of the carbon are obtained by allowing the carbon exposed on the surface to react with oxygen in the air and oxygen in the crystal grains (oxygen in the crystal grains in vacuo or in an inert gas). These elements have high slidability and a low coefficient of friction, so that wear resistance is improved. With reference toFIG.2, an example of TOF-SIMS results of the surface of the polycrystalline diamond according to the present embodiment shows that three chemical species of BO2, O, and O2are present as oxygen-containing species included in the oxide film of the protective film. BO2is derived from the BOXcluster, and it is considered that the BOXcluster is present in the form of BO2, B2O4, B3O6, and the like. It is considered that O and O2are derived from at least one of O and OH that are an oxygen end of the carbon. In the polycrystalline diamond according to the present embodiment, the protective film preferably further contains a precipitate precipitated out of the crystal grains. In addition to the BOXcluster and at least one of O and OH that are an oxygen end of the carbon, the protective film further contains the precipitate having high slidability and a low coefficient of friction, so that the wear resistance of the polycrystalline diamond is improved. The precipitate is not particularly limited, and predominantly contains a boron oxide such as B2O3. It is considered that the B2O3is formed by allowing B (boron) and BO2that are separated from the surface of the polycrystalline diamond to react with oxygen in the air and oxygen in the crystal (oxygen in the crystal in vacuo or in an inert gas). The precipitate also contributes to reduction in the coefficient of friction because it remains and is accumulated as debris (specifically, deposits formed of polishing chips) and has a lubricating action. From the viewpoint such that even though the surface of the polycrystalline diamond according to the present embodiment is chipped due to mechanical damage to the polycrystalline diamond, the chipped portion is filled with the protective film in a portion other than the chipped portion, so that the polycrystalline diamond maintains a smooth surface, the protective film preferably has an average film thickness of greater than or equal to 1 nm and less than or equal to 1000 nm, and more preferably greater than or equal to 10 nm and less than or equal to 500 nm. Here, the average film thickness of the protective film can be measured by a stylus type surface shape measuring apparatus (e.g., Dektak (registered trademark) Stylus Profilometer, manufactured by the Bruker Corporation) and TEM. Specifically, it is preferable that the polycrystalline diamond according to the present embodiment is polycrystalline diamond having a diamond single phase as basic composition, in which the polycrystalline diamond includes a plurality of crystal grains, the polycrystalline diamond contains boron, hydrogen, oxygen, and the remainder including carbon and trace impurities; the boron is dispersed in the crystal grains at the atomic level, and greater than or equal to 99 atomic % of the boron is present in an isolated substitutional type; the hydrogen and the oxygen are present in an isolated substitutional type or an interstitial type in the crystal grains; each of the crystal grains has a grain size of less than or equal to 500 nm; the polycrystalline diamond has a surface covered with a protective film; the boron has an atomic concentration of greater than or equal to 1×1014cm−3and less than or equal to 1×1022cm−3; the hydrogen has an atomic concentration of greater than or equal to 1×1017cm−3and less than or equal to 1×1020cm−3; the oxygen has an atomic concentration of greater than or equal to 1×1017cm−3and less than or equal to 1×1020cm−3; in a Raman spectroscopic measurement of the polycrystalline diamond, a peak area around 1575 cm−1±30 cm−1with a half width of less than or equal to 20 cm−1is less than 1% of a peak area around 1300 cm−1±30 cm−1with a half width of less than or equal to 60 cm−1; the surface (the surface covered with the protective film) of the polycrystalline diamond has a dynamic friction coefficient of less than or equal to 0.05; the protective film contains a BOXcluster, at least one of O and OH that are an oxygen end of the carbon, and a precipitate precipitated out of the crystal grains; and the protective film has an average film thickness of greater than or equal to 1 nm and less than or equal to 1000 nm. Since the polycrystalline diamond has the above-described characteristics, the oxidation resistance of the polycrystalline diamond increases and the coefficient of friction is reduced, which in turn improves sliding properties and wear resistance. (Graphene Nanoribbon) The polycrystalline diamond according to the present embodiment preferably contains a graphene nanoribbon. Accordingly, a graphene nanoribbon-derived protective film can be formed on the surface of the polycrystalline diamond. In this case, the polycrystalline diamond preferably has a peak at a Raman shift of 1554 cm−1±20 cm−1with a half width of less than or equal to 10 cm−1in the Raman spectroscopic measurement. Further, the polycrystalline diamond more preferably has a peak at a Raman shift of 2330 cm−1±20 cm−1with a half width of less than or equal to 6 cm−1in the Raman spectroscopic measurement Specifically, according to the present embodiment, polycrystalline diamond containing a graphene nanoribbon may be obtained depending on the conditions for the manufacturing method to be described later. In this case, the graphene nanoribbon is preferably present in close vicinity to the surface of the polycrystalline diamond. Accordingly, when the graphene nanoribbon appears on the surface of the polycrystalline diamond, it reacts with oxygen in the air and oxygen in the crystal grains (oxygen in the crystal grains in vacuo or in an inert gas) to become an oxide, so that the graphene nanoribbon-derived protective film can be formed on the surface of the polycrystalline diamond. Since the graphene nanoribbon-derived protective film improves the sliding properties and reduces the dynamic friction coefficient, wear resistance can be improved. In particular, it can contribute to set the dynamic friction coefficient to less than or equal to 0.02. Further, even though the graphene nanoribbon-derived protective film is simultaneously present with the above-described BOXcluster that forms the other protective film on the surface of the polycrystalline diamond and any one of O and OH that are an oxygen end of the carbon, they are not interfered with one another, which may not affect their sliding properties. Hereinafter, the confirmation and evaluation of the properties of the polycrystalline diamond according to the present embodiment will be described in detail by way of specific examples. (Confirmation of Formation of Protective Film) The surface of the polycrystalline diamond (boron concentration of 6.8×1020cm−3, hydrogen concentration of 6.0×1018cm−3, oxygen concentration of 3.0×1018cm−3) according to the present embodiment is chemically analyzed by auger electron spectroscopy (AES), and oxygen is thereby detected in a surface layer from the surface to a depth of approximately 0.5 nm. This shows that an oxide film is formed as the protective film on the surface thereof even at room temperature (e.g., 25° C.) FIG.3is a graph showing an example of mass change of the polycrystalline diamond according to the present embodiment during heating in the air. With reference toFIG.3, the polycrystalline diamond containing boron, hydrogen, and oxygen and the polycrystalline diamond containing boron alone slightly increases their masses until the temperature reaches approximately 800° C. This suggests that the formation of the protective film, which is an oxide film, on the surface thereof under high temperature is accelerated. Further, the mass of the polycrystalline diamond not containing boron is rapidly reduced at a temperature from approximately 800° C., and the mass of the polycrystalline diamond containing boron alone is gradually reduced at a temperature from approximately 800° C. In contrast to these, the reduction of the mass of the polycrystalline diamond containing boron, hydrogen, and oxygen is not observed until the temperature reaches approximately 1000° C. That is, in the polycrystalline diamond containing boron, hydrogen, and oxygen, it is considered that a stable oxide film is formed, and such a film is served as a protective film to improve the oxidation resistance of the polycrystalline diamond. (Evaluation of Dynamic Friction Coefficient) FIG.4is a graph showing an example of dynamic friction coefficient measurement results in a pin-on-disk sliding test of the polycrystalline diamond according to the present embodiment. The pin-on-disk sliding test is performed under the following conditions.Material of ball: SUSLoad: 10 NNumber of revolutions: 400 rpmSliding radius: 1.25 mmTest time: 100 minutesTemperature: Room temperatureAtmosphere: Air (at 25° C. and 30% relative humidity) With reference toFIG.4, the dynamic friction coefficient of the polycrystalline diamond containing boron is reduced to less than or equal to 0.25 times, and the dynamic friction coefficient of the polycrystalline diamond containing boron, hydrogen, and oxygen is reduced to 0.20 times, as that of the polycrystalline diamond with no element added, under dry atmosphere (e.g., at 25° C., a relative humidity of less than or equal to 30%). Since the oxide film as the protective film formed on the surface of the polycrystalline diamond according to the present embodiment is water-soluble, it is preferably used in a dry-atmosphere environment. If used in the air, the oxide film preferably has less than or equal to the moisture content equivalent to a relative humidity of 30% at 25° C., and more preferably less than or equal to the moisture content equivalent to a relative humidity of 20% at 25° C. If used in atmosphere other than the air (e.g., argon (Ar) atmosphere or mineral oil atmosphere), the oxide film preferably has a water content of less than or equal to 25%, and more preferably a water content of less than or equal to 20%. (Evaluation of Hardness) FIG.5is a graph showing an example of Knoop hardness measurement results of the polycrystalline diamond according to the present embodiment. The Knoop hardness is measured with a measurement load of 4.9 N in conformity with JIS Z2251:2009. With reference toFIG.5, the Knoop hardness of the polycrystalline diamond containing boron somewhat decreases with an increase in the concentration of the boron, and the Knoop hardness of the polycrystalline diamond containing boron, hydrogen, and oxygen further somewhat decreases with an increase in the concentrations of the boron, hydrogen, and oxygen, as compared with the Knoop hardness of the polycrystalline diamond with no element added. It is considered that the boron, the hydrogen, and the oxygen contained in the polycrystalline diamond become starting points of plastic deformation and somewhat lower the hardness. However, the Knoop hardness of the polycrystalline diamond having a boron atom concentration of 4.0×1020cm−3, a hydrogen atom concentration of 1.0×1019cm−3, and an oxygen atom concentration of 1.0×1019cm−3is equivalent to or greater than the Knoop hardness of a normal synthetic single-crystal diamond (Ib-type single-crystal diamond, an isolated substitutional nitrogen concentration of 1.7×1019cm−3). (Evaluation of Wear Resistance) According to the wear test (a load of 2.5 kgf/mm2, a sliding rate of 200 mm/min) in which polycrystalline diamond is processed into a cylindrical shape having a diameter of φ 1 mm and a height of 2 mm, and a metal-bond diamond wheel #800 (manufactured by A.L.M.T. Corp.) is used, the wear rate of the polycrystalline diamond containing boron (atom concentration of 2.5×1019cm−3to 4.0×1020cm−3), hydrogen (atom concentration of 2.2×1018cm−3to 3.5×1019cm−3), and oxygen (atom concentration of 2.2×1018cm−3to 2.2×1019cm−3) is from 2.5 to 3 mm3/h, so that the wear resistance thereof is increased to 3 to 4 times as high as that of the polycrystalline diamond with no element added having a wear rate of 10 mm3/h. In the wear test using the metal bond diamond wheel, mechanical wear and thermochemical wear synergistically proceed. Then, mechanical wear properties and thermochemical wear properties are evaluated as shown below. In order to evaluate the mechanical wear properties of polycrystalline diamond, a low-speed and long-time sliding test is performed with aluminum oxide (Al2O3) in which mechanical wear primarily proceeds. A frustoconical test piece having a φ 0.3-mm diameter test face at its tip end produced using polycrystalline diamond containing boron (atom concentration of 0 cm−3to 4.0×1020cm−3), hydrogen (atom concentration of 0 cm−3to 4.0×1019cm−3), and oxygen (atom concentration of 0 cm−3to 4.0×1020cm−3) is used in a machining center, pressed against a sintered Al2O3body (a purity of 99.9% by mass) under a constant load of 0.3 MPa, and slid at a low speed of 5 m/min for a distance of 10 km, and an amount of wear is calculated from the extent of the tip end diameter. The amount of wear of the polycrystalline diamond containing the boron, the hydrogen, and the oxygen is approximately 0.05 times as large as the polycrystalline diamond with no element added, so that the wear resistance is significantly improved. It is considered that the lubricating effect of a protective film, which is an oxide film, formed on the surface to be renewed by the wear of the polycrystalline diamond containing the boron, the hydrogen, and the oxygen contributes to significant improvement of the sliding properties, and mechanical wear is remarkably suppressed. In order to evaluate the thermochemical wear properties of the polycrystalline diamond, a sliding test is performed against silicon dioxide (SiO2) in which thermochemical wear primarily proceeds. A frustoconical test piece having a φ 0.3-mm diameter test face at its tip end produced using polycrystalline diamond containing boron (atom concentration of 0 cm−3to 4.0×1020cm−3), hydrogen (atom concentration of 0 cm−3to 4.0×1019cm−3), and oxygen (atom concentration of 0 cm−3to 4.0×1020cm−3) is secured, and while a φ 20-mm diameter synthetic quartz (SiO2) is rotated at 6000 rpm (sliding speed of 260 to 340 m/min) as a grinder, it is pressed against the test face of the secured test piece with 0.1 MPa and then slid.FIG.6is a graph showing an example of wear rate measurement results of the polycrystalline diamond according to the present embodiment against silicon dioxide. As shown inFIG.6, the wear rate of the polycrystalline diamond containing boron, hydrogen, and oxygen decreases as compared with that of the polycrystalline diamond with no element added, so that the wear resistance is improved. In particular, the wear rate of the polycrystalline diamond having a boron atom concentration of 2.0×1019cm−3to 2.0×1020cm−3greatly decreases, so that the wear resistance is significantly improved. Damage of the polycrystalline diamond by the silicon dioxide occurs due to wear caused by chemical reaction. It is, however, considered that the lubricating effect of a protective film, which is an oxide film, formed on the surface to be renewed by the wear of the polycrystalline diamond containing the boron, the hydrogen, and the oxygen contributes to significant improvement of the sliding properties, and thermochemical wear is remarkably suppressed. The suppression of mechanical wear and the suppression of thermochemical wear due to suppression of heat generated by wearing in the polycrystalline diamond containing the boron, the hydrogen, and the oxygen are suitable for processing of a hard-to-cut material such as cemented carbide or aluminum alloy. As described above, in the polycrystalline diamond according to the present embodiment, an oxide is formed on a surface thereof with the boron that is dispersed in the crystal grains at the atomic level and greater than or equal to 90 atomic % of which being present in an isolated substitutional type and the hydrogen and the oxygen that are present in an isolated substitutional type or an interstitial type in the crystal grains. The oxidation resistance, wear resistance, and sliding properties are improved by the oxidation resistance and lubricity of the protective film which is an oxide film. Further, since the polycrystalline diamond according to the present embodiment has conductivity because of the contained boron, abnormal wear and tear caused by triboplasma, as seen in polycrystalline diamond with no element added, normal single-crystal diamond, and the like, is also suppressed. Therefore, it is expected that the polycrystalline diamond according to the present embodiment exhibits high performance for processing of an insulating object such as ceramics, plastics, glass, or quartz. Embodiment 2: Method for Manufacturing Polycrystalline Diamond As shown inFIG.7, the method for manufacturing polycrystalline diamond according to the present embodiment includes first step S10of preparing graphite containing carbon, boron, hydrogen, and oxygen; second step S20of placing the graphite in a vessel under an inert gas atmosphere; and third step S30of converting the graphite to diamond by pressure heat treatment in the vessel, in which the boron is dispersed in a crystal grain of the graphite at an atomic level, and greater than or equal to 90 atomic % of the boron is present in an isolated substitutional type. In the method for manufacturing polycrystalline diamond according to the present embodiment, since the graphite is directly converted to diamond, the polycrystalline diamond according to Embodiment 1 having high oxidation resistance, a low coefficient of friction, high sliding properties, and high wear resistance (i.e., polycrystalline diamond containing boron, hydrogen, and oxygen, in which the boron is dispersed in the crystal grains at the atomic level, and greater than or equal to 90 atomic % of the boron is present in an isolated substitutional type, and the hydrogen and the oxygen are present in an isolated substitutional type or an interstitial type in the crystal grains) can be manufactured. In the method for manufacturing polycrystalline diamond according to the present embodiment, the “boron is dispersed at the atomic level” refers to a dispersed state at such a level that, when carbon and boron are mixed in a vapor phase state to thereby produce a graphite base material or the graphite, different elements such as boron are dispersed in the carbon that forms a crystal of the graphite base material or the graphite, each element having a finite activation energy without changing the crystal structure of the graphite base material or the graphite. That is, such dispersed state refers to a state where a different element to be isolated and precipitated and a different compound other than graphite base material or the graphite are not formed. In addition, the “isolated substitutional type” refers to an existence form in which different elements such as boron, hydrogen, and oxygen are isolated and substituted for carbon located at a lattice point of the graphite base material or graphite crystal lattice. The dispersed state and existence form of boron in the graphite base material or boron, hydrogen, and oxygen in the graphite in the method for manufacturing polycrystalline diamond according to the present embodiment can be confirmed by the same method as that for confirming the dispersed state and existence form of these elements in the polycrystalline diamond. The “boron is dispersed at the atomic level”, “isolated substitutional type” or “interstitial type”, the concentrations of boron, nitrogen, and silicon, and the concentration of trace impurities can also be confirmed by the same method as that for confirming them in the polycrystalline diamond. (First Step) First step S10in the method for manufacturing polycrystalline diamond according to the present embodiment is a step of preparing graphite containing carbon, boron, hydrogen, and oxygen, in which the boron is dispersed in the crystal grains at the atomic level, and greater than or equal to 90 atomic % of the boron is present in an isolated substitutional type. Such graphite is converted to diamond by pressure heat treatment, so that the polycrystalline diamond according to Embodiment 1 is obtained. First step S10is not particularly limited, and preferably includes a sub-step of forming a graphite base material containing carbon and boron on a base material by a vapor phase method, in which the boron is dispersed in a crystal grain of the graphite base material at the atomic level, and greater than or equal to 90 atomic % of the boron is present in an isolated substitutional type, from the viewpoint of efficiently producing the graphite with high quality. In the method for manufacturing polycrystalline diamond according to the present embodiment, the vapor phase method refers to a method for growing a crystal in vapor phase state, and though not particularly limited, a chemical vapor deposition (CVD) method is preferable from the viewpoint of efficiently producing the graphite with high quality. In CVD, a carbon-containing gas and a boron-containing gas are preferably allowed to react on the base material at a temperature of greater than or equal to 1500° C. and less than or equal to 2500° C. When a method for forming a solid solution of boron in graphite with no element added is used in the sub-step of forming the graphite base material, it is necessary to use a non-graphite and non-diamond compound such as B4C to form a solid solution of boron in the graphite with no element added. Therefore, higher concentration of the carbon to be added requires higher concentration of the non-graphite and non-diamond compound such as B4C, which decreases the bond strength of the polycrystalline diamond. In the method for manufacturing polycrystalline diamond according to the present embodiment, since the vapor phase method is used, the rate of B4C incorporated is less than 1% by mass, which is extremely low, so that high-quality polycrystalline diamond is obtained. First step S10is not particularly limited, and preferably includes a sub-step of including the hydrogen and the oxygen in the graphite base material by a vapor phase method, from the viewpoint of efficiently producing the graphite with high quality. The vapor phase method is not particularly limited, and a chemical vapor deposition (CVD) method is preferable from the viewpoint of efficiently producing the graphite with high quality. In CVD, a hydrogen-containing gas and an oxygen-containing gas are preferably allowed to react with the graphite base material at a temperature of greater than or equal to 1500° C. and less than or equal to 2500° C. First step S10is not particularly limited, and preferably further includes a sub-step of including the hydrogen and the oxygen in the graphite base material under vacuum condition, from the viewpoint of efficiently producing the graphite with high quality. Though not particularly limited, the vacuum condition is preferably less than or equal to 10 Pa, more preferably less than or equal to 1 Pa, and further preferably less than or equal to 10−2Pa, from the viewpoint of reducing incorporation of trace impurities. In addition, the ambient temperature is preferably less than or equal to 600° C., and more preferably 300° C., from the viewpoint of suppressing oxidation of carbon. The method for including the hydrogen and the oxygen in the base material under vacuum condition is not particularly limited, and a hydrogen-containing gas and an oxygen-containing gas can be included in the graphite base material under vacuum condition. Further, first step S10is not particularly limited, and preferably includes a step of forming the graphite (specifically, graphite containing carbon, boron, hydrogen, and oxygen, in which the boron is dispersed in the crystal grain at the atomic level, and greater than or equal to 90 atomic % of the boron is present in an isolated substitutional type) on a base material by simultaneously mixing carbon, boron, hydrogen, and oxygen with one another in vapor phase by a vapor phase method, from the viewpoint of particularly efficiently producing the graphite with high quality. The vapor phase method is not particularly limited, and a chemical vapor deposition (CVD) method is preferable from the viewpoint of particularly efficiently producing the graphite with high quality. In CVD, a carbon-containing gas, a boron-containing gas, a hydrogen-containing gas, and an oxygen-containing gas are preferably allowed to react at a temperature of greater than or equal to 1500° C. and less than or equal to 2500° C. When first step S10includes the step of forming the graphite on a base material by simultaneously mixing the carbon, the boron, the hydrogen, and the oxygen with one another in vapor phase by a vapor phase method, it preferably includes a sub-step of forming a gas mixture containing the carbon, the boron, the hydrogen, and the oxygen; and a sub-step of forming the graphite on a base material by thermally decomposing the gas mixture at a temperature of greater than or equal to 1500° C. and feeding the gas mixture toward the base material, in which the gas mixture includes a gas containing the boron, the hydrogen, and the oxygen, and a hydrocarbon gas, from the viewpoint of particularly efficiently producing the graphite with high quality. After the gas mixture containing the carbon, the boron, the hydrogen, and the oxygen is formed, the graphite is formed from the gas mixture, so that the graphite with the boron, the hydrogen, and the oxygen more uniformly dispersed is obtained. In first step S10described above, first, a base material is heated to a temperature of greater than or equal to 1500° C. and less than or equal to 2500° C. in a vacuum chamber. Though not particularly limited, any metal, inorganic ceramic material, or carbon material can be used as the base material, so long as it is a material capable of withstanding a temperature approximately from 1500° C. to 2500° C. Then, a gas containing boron, hydrogen, and oxygen, and a hydrocarbon gas are simultaneously introduced in the vacuum chamber under an atmosphere at a temperature of greater than or equal to 1500° C. and less than or equal to 2500° C. High temperature exceeding 2500° C. is not preferable because the hydrogen is released from the graphite to be formed, and because the oxygen and the carbon significantly react with each other to be volatilized as a carbon oxide gas. Here, when the gas containing boron, hydrogen, and oxygen, and the hydrocarbon gas are simultaneously introduced, from the viewpoint of more uniformly desperseing the boron, the hydrogen, and the oxygen in the graphite to be formed, to increase yield of polycrystalline diamond, it is preferable that the gas containing boron, hydrogen, and oxygen, and the hydrocarbon gas are previously mixed to produce a gas mixture, and the gas mixture is then introduced. For example, when the gas containing boron, hydrogen, and oxygen, and the hydrocarbon gas are injected from separate nozzles, the yield of the polycrystalline diamond is less than 20%. However, when the gas containing boron, hydrogen, and oxygen, and the hydrocarbon gas are mixed in a gas mixing chamber and the resulting gas mixture is injected from the same nozzle, the yield of the polycrystalline diamond is increased to greater than or equal to 80%. The gas containing boron, hydrogen, and oxygen is not limited to one gas containing all these elements, and may be a gas mixture containing at least one of boron, hydrogen, and oxygen. As the one gas containing all these elements, trimethyl borate gas, triethyl borate gas, or the like is preferable. The hydrocarbon gas is not particularly limited, and from the viewpoint of more uniform distribution of the boron, the hydrogen, the oxygen in the crystal of carbon, a hydrocarbon gas having a small number of carbon atoms is preferable; methane gas, ethane gas, ethylene gas, acetylene gas, and the like are preferable; and methane gas is particularly preferable. The gas mixture is thermally decomposed at a temperature of greater than or equal to 1500° C. and less than or equal to 2500° C. and is fed toward the base material, so that the carbon, the boron, the hydrogen, and the oxygen formed in atomic form by the thermal decomposition are allowed to react with one another on the base material to thereby form the graphite on the base material. The graphite is not particularly limited, and is a polycrystalline containing a crystallized portion in at least a portion thereof from the preferred viewpoint of formation of the polycrystalline diamond. The concentration of the trace impurities in the graphite is preferably less than or equal to the detection limit of SIMS and/or ICP-MS, from the viewpoint of forming high-quality polycrystalline diamond with few trace impurities. From such a viewpoint also, the formation of the graphite by a vapor phase method, particularly, CVD is effective. The grain size of the graphite is preferably less than or equal to 10 μm, and more preferably less than or equal to 1 μm, from the viewpoint of forming polycrystalline diamond having a small grain size of less than or equal to 500 nm and having uniform distribution of the boron, the hydrogen, and the oxygen. From such a viewpoint also, the formation of the graphite by a vapor phase method, particularly, CVD is effective. The graphite has a density of preferably greater than or equal to 0.8 g/cm3, and more preferably greater than or equal to 1.4 g/cm3and less than or equal to 2.0 g/cm3, from the viewpoint of improving yield by making volume change smaller during the conversion from the graphite to the polycrystalline diamond in the third step. (Second Step) Second step S20in the method for manufacturing polycrystalline diamond according to the present embodiment is a step of placing the graphite in a vessel under an inert gas atmosphere. Since the graphite is placed in a predetermined vessel under an inert gas atmosphere, it is possible to suppress incorporation of trace impurities into the graphite and the polycrystalline diamond to be formed. Here, the inert gas is not particularly limited as long as it can suppress incorporation of trace impurities into the graphite and the polycrystalline diamond to be formed, and examples thereof include argon (Ar) gas, krypton (Kr) gas, helium (He) gas, and the like. (Third Step) Third step S30in the method for manufacturing polycrystalline diamond according to the present embodiment is a step of converting the graphite to diamond by pressure heat treatment in the vessel. In third step S30, when the graphite is converted to the polycrystalline diamond, it is preferable that the graphite is directly converted (specifically, converted without adding a sintering aid and/or a catalyst) by directly subjecting the graphite to heat treatment, from the viewpoint of suppressing incorporation of trace impurities into the polycrystalline diamond to be formed. The pressure heat treatment refers to heat treatment under pressure. The pressure heat treatment in third step S30is performed preferably under conditions of greater than or equal to 6 GPa and greater than or equal to 1200° C., and more preferably under conditions of greater than or equal to 8 GPa and less than or equal to 30 GPa, and greater than or equal to 1200° C. and less than or equal to 2300° C., from the viewpoint of suitably manufacturing polycrystalline diamond in which the boron is dispersed in the crystal grains of the polycrystalline diamond at the atomic level, greater than or equal to 90 atomic % of the boron is present in an isolated substitutional type, and the hydrogen and the oxygen are also present in an isolated substitutional type or an interstitial type in the crystal grains. Here, in the case of performing the pressure heat treatment in third step S30under conditions of about 7 to 15 GPa, the polycrystalline diamond tends to be manufactured containing a graphene nanoribbon. In this case, it can be confirmed that the polycrystalline diamond contains a graphene nanoribbon, by confirming at least one of the polycrystalline diamond having a peak at a Raman shift of 1554 cm−1±20 cm−1with a half width of less than or equal to 10 cm−1and the polycrystalline diamond having a peak at a Raman shift of 2330 cm−1±20 cm−1with a half width of less than or equal to 6 cm−1, in the Raman spectroscopic measurement. Specifically, according to the present embodiment, polycrystalline diamond containing a graphene nanoribbon may be obtained depending on the conditions for the manufacturing method as described above. In this case, a graphene nanoribbon-derived protective film is formed on the surface of the polycrystalline diamond, thereby improving the sliding properties and reducing the dynamic friction coefficient, so that wear resistance can be improved. In view of the above, by the method for manufacturing polycrystalline diamond according to the present embodiment, polycrystalline diamond having high oxidation resistance, high sliding properties, high wear resistance, and a low dynamic friction coefficient can be manufactured. The polycrystalline diamond is manufactured in any shape and any thickness with a diameter of approximately 15×15 t (t: thickness). For example, in the case where the graphite has a volume density of approximately 1.8 g/cm3, the volume of the polycrystalline diamond is shrunk to 70 to 80% of that of the graphite by pressure heat treatment, but the polycrystalline diamond has the same shape or substantially the same shape as the graphite. Embodiment 3: Scribe Tool The scribe tool according to the present embodiment can be formed using the polycrystalline diamond according to Embodiment 1. The scribe tool according to the present embodiment has high wear resistance because it is formed using the polycrystalline diamond according to Embodiment 1. Embodiment 4: Scribe Wheel The scribe wheel according to the present embodiment can be formed using the polycrystalline diamond according to Embodiment 1. The scribe wheel according to the present embodiment has high wear resistance because it is formed using the polycrystalline diamond according to Embodiment 1. Embodiment 5: Dresser The dresser according to the present embodiment can be formed using the polycrystalline diamond according to Embodiment 1. The dresser according to the present embodiment has high wear resistance because it is formed using the polycrystalline diamond according to Embodiment 1. Embodiment 6: Rotating Tool The rotating tool according to the present embodiment can be formed using the polycrystalline diamond according to Embodiment 1. The rotating tool according to the present embodiment has high wear resistance because it is formed using the polycrystalline diamond according to Embodiment 1. Embodiment 7: Wire Drawing Die The wire drawing die according to the present embodiment can be formed using the polycrystalline diamond according to Embodiment 1. The wire drawing die according to the present embodiment has high wear resistance because it is formed using the polycrystalline diamond according to Embodiment 1. Embodiment 8: Cutting Tool The cutting tool according to the present embodiment can be formed using the polycrystalline diamond according to Embodiment 1. The cutting tool according to the present embodiment has high wear resistance because it is formed using the polycrystalline diamond according to Embodiment 1. Embodiment 9: Electrode The electrode according to the present embodiment can be formed using the polycrystalline diamond according to Embodiment 1. The electrode according to the present embodiment has high wear resistance because it is formed using the polycrystalline diamond according to Embodiment 1. Embodiment 10: Processing Method In the processing method according to the present embodiment, an object can be processed using the polycrystalline diamond according to Embodiment 1. In the processing method according to the present embodiment, the object can be efficiently processed at low cost because it is processed using the polycrystalline diamond according to Embodiment 1. In the processing method according to the present embodiment, the object is preferably an insulator. In the processing method according to the present embodiment, the object is processed using the polycrystalline diamond having conductivity according to the Embodiment 1. Therefore, even though the object is an insulator, it can be efficiently processed at low cost without generating abnormal wear and tear caused by triboplasma or the like. In the processing method according to the present embodiment, the insulator as the object preferably has a resistivity of greater than or equal to 100 kΩ·cm. In the processing method according to the present embodiment, the object is processed using the polycrystalline diamond having conductivity according to Embodiment 1. Therefore, even though the object is an insulator having a resistivity of greater than or equal to 100 kΩ·cm, the object can be efficiently processed at low cost without etching caused by triboplasma. EXAMPLES Example 1: Manufacturing of Polycrystalline Diamond 1. Preparation of Graphite Containing Boron, Hydrogen, and Oxygen A degree of vacuum within a reaction vessel was reduced to less than or equal to 10−2Pa, and the reaction vessel was thereafter filled with an inert gas (Ar gas) to create an atmosphere of 20 kPa. In the case of Examples 1 to 5, a gas mixture containing methane, trimethyl borate, oxygen, and hydrogen at a predetermined ratio was fed, and in the case of Comparative Examples 1 to 3, a gas mixture containing methane and trimethyl borate at a predetermined ratio was fed. Here, an inert gas was used to feed trimethyl borate. The gas mixture was allowed to react at an ambient temperature of 1500° C., so that graphite with 20 mm-thick containing boron, hydrogen, and oxygen was grown. 2. Housing of Graphite in Vessel The graphite thus obtained was processed into a tablet form, and thereafter encapsulated with Ar gas in the vessel (cell for high-pressure press: cylindrical shape having a diameter of φ 10 mm and a height of 10 mm). 3. Conversion from Graphite to Polycrystalline Diamond The vessel in which the graphite was encapsulated was placed in a pressure heat treatment apparatus, and then subjected to pressure heat treatment under conditions of 16 GPa and 2100° C., so that the graphite was directly converted to polycrystalline diamond. It was confirmed by X-ray diffraction (XRD) and electron diffraction (EBD) that each of the polycrystalline diamonds thus obtained in Comparative Examples 1 to 3 and Examples 1 to 5 had a diamond single phase as basic composition, did not contain a binding phase, and did not have a different phase made of B4C or the like. Further, for each of the polycrystalline diamonds of Comparative Examples 1 to 3 and Examples 1 to 5, it was confirmed by TEM, measurement of temperature dependence of electrical resistance, and TOF-SIMS that the boron was dispersed at the atomic level, and greater than or equal to 90 atomic % of the boron was present in an isolated substitutional type. Further, for each of the polycrystalline diamonds of Examples 1 to 5, it was confirmed by TEM, near edge X-ray absorption fine structure (NEXAFS), TOF-SIMS, measurement of temperature dependence of electrical resistance, and X-ray photoelectron spectroscopy (XPS) that the hydrogen and the oxygen were present in an isolated substitutional or interstitial type. Further, atomic concentrations of the boron, the hydrogen, the oxygen, and the trace impurities in each of the polycrystalline diamonds of Comparative Examples 1 to 3 and Examples 1 to 5 were measured by SIMS. In the polycrystalline diamonds of Comparative Examples 1 to 3 and Examples 1 to 5, the trace impurities were not detected. The above results are summarized in Table 1. Here, in Table 1, the oxygen atom concentration was a detection limit of 1×1016cm−3, and the hydrogen atom concentration was a detection limit of 1×1017cm−3. Further, it was confirmed from the half width for the (111) peak with an X-ray diffractometer (XRD) that each of the polycrystalline diamonds of Comparative Examples 1 to 3 and Examples 1 to 5 had a crystal grain size of 30 to 60 nm. TABLE 1Boron(cm−3)Oxygen (cm−3)Hydrogen (cm−3)Comparative1 × 1014Detection limit or lessDetection limit or lessExample 1Comparative1 × 1018Detection limit or lessDetection limit or lessExample 2Comparative1 × 1019Detection limit or lessDetection limit or lessExample 3Example 11 × 10171 × 10172 × 1017Example 21 × 10183 × 10172 × 1017Example 31 × 10191 × 10175 × 1017Example 41 × 10203 × 10181 × 1018Example 51 × 10211 × 10185 × 1019 (Raman Spectroscopic Measurement) The Raman spectroscopic measurement was performed for the polycrystalline diamonds of Comparative Example 1, Example 1, and Example 2 as described above, using a Raman spectrophotometer (trade name: Raman microscope “RAMANtouch”, manufactured by Nanophoton). The conditions for the measurement are as follows. Wavenumber measurement range: From 1200 to 1700 cm−1(532 nm excitation) Resolution: Spectral resolution 0.36 cm−1 Further, the dynamic friction coefficients of these polycrystalline diamonds were determined by the above-described measurement method (pin-on-disk sliding test). These measurement results (shift (peak) position and line width (half width), presence or absence of graphene nanoribbon, dynamic friction coefficient) are shown in Table 2. Further, the Raman spectrum obtained for the polycrystalline diamond of Example 1 is shown inFIG.8. According toFIG.8, it is understood that the polycrystalline diamond of Example 1 contains a graphene nanoribbon because peaks of the graphene nanoribbon appear at a Raman shift of 1554±20 cm−1with a half width less than or equal to 10 cm−1and at a Raman shift of 2330±20 cm−1with a half width less than or equal to 6 cm−1. Further, Table 2 showed that each of the polycrystalline diamonds of Examples 1 and 2 contained a graphene nanoribbon, so that their dynamic friction coefficients were an order of magnitude lower than that of the polycrystalline diamond of Comparative Example 1. TABLE 21554 ± 20 (cm−1)2330 ± 20 (cm−1)Presence/absence ofShirtLine widthShirtLine widthCoefficient ofnanoribbon(peak)(half width)(peak)(half width)frictionComparativeAbsence0.2Example 1Example 1Presence1554.16.132328.13.640.02Example 2Presence1553.27.02327.23.70.02 Example II: Production and Evaluation of Scribe Tool The polycrystalline diamond of Comparative Example 2 according to Example I was used to produce a scribe tool having four points at a tip end (having a quadrangular two-dimensional shape). The produced scribe tool was used to form 200 scribe grooves each having a length of 50 nm in a sapphire substrate at a load of 20 gf. Thereafter, an amount of wear of the polycrystalline diamond at the tip end portion of the scribe tool was observed with an electron microscope. Then, the amount of wear of the scribe tool was 0.2 times that were small, as compared with that of the scribe tool made of Ib-type single-crystal diamond. Further, when the polycrystalline diamond of Example 2 according to Example I was used to produce a scribe tool in the same manner as above and the same experiment was conducted, the amount of wear of the scribe tool was 0.02 times that were extremely small, as compared with that of the scribe tool made of Ib-type single-crystal diamond, and was 0.1 times that were extremely small, as compared with that of the scribe tool made of the polycrystalline diamond of Comparative Example 2. The same effect was observed in the scribe wheel produced by using each of the polycrystalline diamonds of Comparative Example 2 and Example 2 according to Example I. Example III: Production and Evaluation of Dresser The polycrystalline diamond of Comparative Example 2 according to Example I was used to produce a dresser having a single point at a tip end (having a conical shape). The produced dresser was worn with a wet method by using a white alumina (WA) grindstone under such conditions as a peripheral speed of the grindstone of 30 m/sec. and a depth of cut of 0.05 mm. Thereafter, an amount of wear of the dresser was measured with a height gauge, and the amount of wear of the polycrystalline diamond was 0.3 times that were small, as compared with that of the dresser made of Ib-type single-crystal diamond. Further, when the polycrystalline diamond of Comparative Example 2 according to Example I was used to produce a dresser in the same manner as above and the same experiment was conducted, the amount of wear of the dresser was 0.03 times that were extremely small, as compared with that of the dresser made of Ib-type single-crystal diamond, and was 0.1 times that were extremely small, as compared with that of the dresser made of the polycrystalline diamond of Comparative Example 2. Example IV: Production and Evaluation of Rotating Tool The polycrystalline diamond in Comparative Example 2 according to Example I was used to produce a drill having a diameter of φ1 mm and a blade length of 3 mm. The produced drill was used to drill a hole through a 1.0 mm-thick plate made of cemented carbide (WC—Co plate) (composition: 12% by mass of Co, the remainder was WC) under such conditions as a number of revolutions of 4000 rpm and a feed rate of 2 μm/rev. The number of holes that could be drilled until the drill was worn or broken was 5 times that were large, as compared with that of a drill made of Ib-type single-crystal diamond. Further, when the polycrystalline diamond of Example 2 according to Example I was used to produce a drill in the same manner as above and a similar experiment was conducted, the number of holes that could be drilled until the drill was worn or broken was 50 times that were extremely large, as compared with that of the drill made of Ib-type single-crystal diamond, and was 10 times that were extremely large, as compared with the dresser made of the polycrystalline diamond of Comparative Example 2. Example V: Production and Evaluation of Cutting Tool I The same method as in Examples 1 to 5 according to Example I was used to prepare graphite having a bulk density of 2.0 g/cm−3, a boron atom concentration of 1×1021cm−3measured by ICP-MS, and an oxygen atom concentration of 1×1018s cm−3and a hydrogen atom concentration of 2.5×1018cm−3measured by SIMS. Such graphite was directly converted to polycrystalline diamond by pressure heat treatment under conditions of 15 GPa and 2200° C. using an isotropic high pressure generator. The resulting polycrystalline diamond had a grain size of 10 nm to 100 nm. No precipitation of B4C was observed in X-ray patterns. The polycrystalline diamond thus obtained was used to fabricate a main body of a cutting tool by a conventional known method. The polycrystalline diamond was joined to the main body of the cutting tool with the use of an active brazing material in an inert atmosphere. After a surface of the polycrystalline diamond was polished, a flank face was cut with electric discharge machining, to thereby produce an R cutting tool (testing tool 1) having a corner R of 0.4 mm, a relief angle of 11°, and a rake angle of 0°. For comparison, a tool (comparative tool A) made of sintered diamond containing a conventional cobalt (Co) binder was similarly produced through electric discharge machining. Accuracy of a ridge line of a cutting edge made through electric discharge machining in comparative tool A made of sintered diamond was approximately from 2 μm to 5 μm depending on the grain size of contained diamond abrasive grains. Accuracy of a ridge line of a cutting edge made through electric discharge machining in the tool (testing tool 1) made of the polycrystalline diamond was less than or equal to 0.5 μm, which was good. In addition, the processing time was also the same as comparative tool A. Further, an R cutting tool (testing tool 2) having a corner R of 0.4 mm, a relief angle of 11°, and a rake angle of 0°, which was processed by polishing its flank face; a cutting tool (comparative tool B) made of polycrystalline diamond with no element added; and a cutting tool (comparative tool C) made of Ib-type single-crystal diamond were produced, and cutting was evaluated with the test contents as shown in the following paragraph. In both testing tool 2 and comparative tool B, accuracy of a ridge line of a cutting edge was less than or equal to 0.1 μm and minute accuracy of a cutting edge was obtained. Next, with testing tools 1 and 2, and comparative tools A to C, an intermittent cutting evaluation test was performed by turning under the following conditions.Shape of tool: Corner R of 0.4 mm, a relief angle of 11°, and a rake angle of 0°Work material: Material—aluminum alloy A390Cutting fluid: Water-soluble emulsionCutting condition: Cutting speed Vc=800 m/min, depth of cut ap=0.2 mm, feed rate f=0.1 mm/rev.Cutting distance: 10 km After the cutting evaluation test as described above was performed, the cutting edge of the tool was observed, and a state of wear and tear was checked. Then, in comparative tool A, an amount of wear of a flank face was as great as 45 μm, and a shape of the cutting edge was lost, whereas in testing tool 1, an amount of wear of a flank face was 2 μm, which was satisfactory. On the other hand, testing tool 2 in which finishing with polishing was performed had an amount of wear of 0.5 μm, and it was much better than comparative tool B having an amount of wear of 3.5 m and comparative tool C having an amount of wear of 3.5 μm. It was found that testing tool 2 exhibited wear resistance properties equal to or higher than conventional polycrystalline diamond with no element added, and it was excellent in tool life. Example VI: Production and Evaluation of Cutting Tool II The same method as in Examples 1 to 5 according to Example I was used, except that a gas mixture containing trimethylboron, methane, hydrogen, and oxygen was introduced, so that graphite having a bulk density of 2.0 g/cm−3, a boron atom concentration of 1×1018cm−3, an oxygen atom concentration of 1×1018cm−3, and a hydrogen atom concentration of 2.5×1018cm−3measured by SIMS was prepared. Such graphite was directly converted to polycrystalline diamond by pressure heat treatment under conditions of 15 GPa and 2200° C. using an isotropic high pressure generator. The polycrystalline diamond had a grain size of 10 nm to 100 nm. No precipitation of B4C was observed in X-ray patterns. The polycrystalline diamond was joined to a main body of a cutting tool with the use of an active brazing material in an inert atmosphere, and the surface of the polycrystalline diamond was polished. Further, a tool (testing tool 3) made of the polycrystalline diamond of which a flank face was processed by polishing, a tool (comparative tool B) made of polycrystalline diamond with no element added, and a tool (comparative tool C) made of Ib-type single-crystal diamond were produced, and cutting was evaluated with the same contents as in Example V. After the cutting evaluation test as described above was performed, the cutting edge of the tool was observed, and a state of wear and tear was checked. Then, testing tool 3 having an amount of wear of 0.1 μm was much smaller and better than comparative tool B having an amount of wear of 3.5 μm and comparative tool C having an amount of wear of 3.5 μm. It was found that testing tool 3 exhibited wear resistance properties equal to or higher than conventional polycrystalline diamond with no element added, and it was excellent in tool life. Example VII: Production and Evaluation of Cutting Tool III A gas mixture containing diborane, methane, hydrogen, and oxygen was introduced in a reaction vessel, and graphite was fabricated while the degree of vacuum in the chamber was kept constant at 26.7 kPa. Thereafter, the degree of vacuum was reduced to less than or equal to 10−2Pa, the ambient temperature was cooled to 300° C., and a gas mixture containing hydrogen and oxygen was further introduced to the graphite at 1 standard cubic centimeter per minute (sccm). Thus, graphite having a bulk density of 1.9 g/cm−3, a boron atom concentration of 1×102: cm−3, an oxygen atom concentration of 1×1018cm−1, and a hydrogen atom concentration of 2.5×1019cm−3measured under the same conditions as in Example I by SIMS was prepared. Such graphite was directly converted to polycrystalline diamond by pressure heat treatment under conditions of 15 GPa and 2200° C. using a high pressure generator. The resulting polycrystalline diamond had a grain size of 10 nm to 100 nm. This polycrystalline diamond had a Knoop hardness of 120 GPa. A test piece having a size of 3 mm×1 mm square was cut from the polycrystalline diamond and electrical resistance of the test piece was measured, and it was 10Ω. The polycrystalline diamond having conductivity was joined to a main body of a cutting tool with the use of an active brazing material in an inert atmosphere, and the surface of the polycrystalline diamond was polished. A flank face was cut with electric discharge machining, to thereby produce a ball end mill (testing tool 4) having a diameter of φ 0.5 mm with two twisted cutting blades. For comparison, a tool (comparative tool A-2) made of sintered diamond containing a conventional cobalt (Co) binder was similarly produced through electric discharge machining. Accuracy of a ridge line of a cutting edge made through electric discharge machining was approximately from 2 μm to 5 μm, depending on the grain size of contained diamond abrasive grains in comparative tool A-2 made of sintered diamond, and was less than or equal to 0.03 μm in the tool (testing tool 4) made of the polycrystalline diamond, which was good. In addition, polycrystalline diamond with no element added was used to produce an end mill shape having the same shape with laser machining, and then a tool (comparative tool B-2) of which a flank face was locally polished to finish a cutting edge grade was produced. Next, with testing tool 4, and comparative tools A-2 and B-2, an intermittent cutting evaluation test was performed by turning under the following conditions.Shape of tool: φ 0.5 mm double-bladed ball end millWork material: Material—STAVAX cemented carbide (composition: 12% by mass of Co, the remainder was WC)Cutting fluid: KeroseneCutting condition: Tool revolution speed of 420000 rpm, depth of cut ap=0.003 mm, feed rate f=120 mm/rev When the cutting evaluation test was performed, the tool life of testing tool 4 was 5 times as long as that of comparative tool A-2 and 1.5 times as long as that of comparative tool B-2, which was very good. The embodiment and examples disclosed herein are merely an exemplification in every respect and should not be considered as limitative. The scope of the present invention is given by claims rather than the above-described embodiments and examples, and intended to include meanings equivalent to claims, and all changes within the scope of claims. REFERENCE SIGNS LIST S10: First step, S20: Second step, S30: Third step | 97,434 |
11858857 | DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be explained below referring to the attached drawings. It should be noted that the present invention is not restricted to the embodiments below, and that modifications and improvements may be made within the scope of the present invention. [1] Ceramic Honeycomb Structure The silicon carbide ceramic honeycomb structure of the present invention comprises large numbers of axially penetrating flow paths partitioned by porous silicon carbide cell walls, the cell walls comprising silicon carbide particles as aggregate and binder layers binding the silicon carbide particles, the binder layers comprising at least a cordierite phase and a spinel phase, and the cordierite phase having a molar ratio M1 [=cordierite phase/(cordierite phase+spinel phase)] of 0.4-0.9. Because the binder layers comprise at least a cordierite phase and a spinel phase, and because the cordierite phase has a molar ratio M1 [=cordierite phase/(cordierite phase+spinel phase)] of 0.4-0.9, the binder layers can have sufficient strength and heat shock resistance. The molar ratio M1 of the cordierite phase is a ratio determined from the molar number of the cordierite phase and the molar number of the spinel phase, by the formula of [cordierite phase (mol)/(cordierite phase (mol)+spinel phase (mol))]. When the molar ratio M1 of the cordierite phase is less than 0.4, the strength is low, and the coefficient of thermal expansion is large, resulting in poor heat shock resistance. On the other hand, when the molar ratio M1 of the cordierite phase exceeds 0.9, the heat resistance becomes low, with cell walls having low porosity. The molar ratio M1 of the cordierite phase is preferably 0.45-0.70. The binder layer may contain, in addition to the cordierite phase and the spinel phase, cristobalite, mullite, forsterite and other crystal phases, and amorphous phases. The molar ratio M1 of the cordierite phase [=cordierite phase/(cordierite phase+spinel phase)] can be determined as follows. First, part of a sintered ceramic honeycomb structure is pulverized to powder, and subjected to X-ray diffraction measurement to obtain a powder diffraction chart, on which the peak intensity of a (110) plane of cordierite and the peak intensity of a (311) plane of spinel are determined. With these peak intensities, the mass ratio of cordierite to spinel in the overall ceramic honeycomb structure is calculated. With 1 mol of cordierite having a mass of 585.0 and 1 mol of spinel having a mass of 142.3, the above mass ratio is converted to the molar ratio of cordierite to spinel, determining the molar ratio M1 of the cordierite phase per a sum of the cordierite phase and the spinel phase. Because the cell walls have porosity of 35-50%, the silicon carbide ceramic honeycomb structure of the present invention can keep low pressure loss, while maintaining high strength. When the porosity is less than 35%, the ceramic honeycomb structure suffers large pressure loss. On the other hand, when it exceeds 50%, it is difficult to provide the ceramic honeycomb structure with sufficient strength. The lower limit of the porosity is preferably 38%, and more preferably 40%. On the other hand, the upper limit of the porosity is preferably 49%, and more preferably 48%. Because the cell walls have a median pore diameter of 5-20 μm, the silicon carbide ceramic honeycomb structure of the present invention can keep high strength. When the median pore diameter is less than 5 μm, the ceramic honeycomb structure suffers large pressure loss. On the other hand, when it exceeds 20 μm, it is difficult to provide the ceramic honeycomb structure with sufficient strength. The lower limit of the median pore diameter is preferably 8 μm, and more preferably 9 μm. On the other hand, the upper limit of the median pore diameter is preferably 18 μm, and more preferably 16 μm. The silicon carbide ceramic honeycomb structure of the present invention can be used as a honeycomb segment211as shown inFIG.2, so that large numbers of honeycomb segments211are integrally bonded by binder layers29to provide a composite silicon carbide ceramic honeycomb structure210as shown inFIG.3. After integrally bonding large numbers of honeycomb segments211by binder layers29, the resultant composite honeycomb structure is machined to have an outer periphery having a circular, oval, triangular, rectangular or any other desired shape in a cross section perpendicular to its flow paths, and the machined outer periphery is covered with a coating material to form an outer peripheral wall21. Flow paths on the exhaust-gas-introducing side25aor exhaust-gas-discharging side25bin the silicon carbide ceramic honeycomb structure210formed by integral bonding can be plugged alternately in a checkerboard pattern by a known method to provide a ceramic honeycomb filter200. Plugs26a,26bof the flow paths may be formed in green bodies before sintering or sintered honeycomb segments, or after they are integrally bonded by binder layers29. These plugs may be formed on end surfaces of the flow paths on the exhaust-gas-introducing or exhaust-gas-discharging side, or in inner portions of the flow paths inside the inlet-side end surface25aor the outlet-side end surface26b. [2] Production Method of Silicon Carbide Ceramic Honeycomb Structure An example of the production methods of the silicon carbide ceramic honeycomb structure of the present invention will be explained. First, silicon carbide particles as aggregate, a binder comprising at least alumina source particles and magnesia source particles, and an organic binder are formulated and blended. The alumina source particles and the magnesia source particles are respectively particles of compounds including alumina and particles of compounds including magnesia, and they may include particles of compounds including alumina and magnesia. The silicon carbide particles contained as aggregate are bound by binder layers in such a manner as to form pores. The silicon carbide particles preferably have an average particle diameter of 30-50 μm. The alumina source particles and the magnesia source particles as binders are added preferably at a molar ratio M2 [=(Al2O3)/(Al2O3+MgO)] of 0.32-0.50. With such ratio, the binder layers can contain at least a cordierite phase and a spinel phase. The molar ratio M2 is calculated from the masses of the alumina source particles and magnesia source particles added as follows. The molar number of an alumina component (Al2O3) in the alumina source particles and the molar number of a magnesia component (MgO) in the magnesia source particles are calculated, and the molar number of the alumina component (Al2O3) per the total molar number of the alumina component (Al2O3) and the magnesia component (MgO) is expressed by the molar ratio M2 [=(Al2O3)/(Al2O3+MgO)]. In the case of using aluminum hydroxide [Al(OH)3] as the alumina source and magnesium hydroxide [Mg(OH)2] as the magnesia source, for example, the alumina content in aluminum hydroxide and the magnesia content in magnesium hydroxide are respectively expressed by Al(OH)3=(1/2)Al2O3+(3/2)H2O, and Mg(OH)2=MgO+H2O. Accordingly, the alumina content per 1 mol of aluminum hydroxide is calculated as 0.5 mol, and the magnesia content per 1 mol of magnesium hydroxide is calculated as 1 mol. Using these relations, the molar numbers of the alumina component and magnesia component are determined as described above, to determine the molar ratio M2. Similarly, when particles of a compound (for example, spinel) containing both alumina and magnesia are used, the alumina content (Al2O3) and the magnesia content (MgO) in this compound are calculated to determine the molar ratio M2. When the molar ratio M2 is less than 0.32 or more than 0.50, the heat shock resistance is low. The lower limit of the molar ratio M2 is preferably 0.35, and further preferably 0.40. The upper limit is preferably 0.48. The total amount of the alumina source particles and the magnesia source particles is preferably 6-15% by mass per 100% by mass of silicon carbide particles. When it is less than 6% by mass, the binder layers binding silicon carbide particles have low binding strength, resulting in a ceramic honeycomb structure having low strength. On the other hand, when it is more than 15% by mass, the heat shock resistance is low. The lower limit of the total amount of the alumina source particles and the magnesia source particles is preferably 7% by mass, and more preferably 8% by mass, per 100% by mass of silicon carbide particles. On the other hand, and the upper limit is preferably 14% by mass, and more preferably 13% by mass. The average particle diameter of the alumina source particles is preferably 1-15 μm. The average particle diameter of the magnesia source particles is preferably 1-15 μm. The alumina source particles are preferably alumina or aluminum hydroxide particles, and the magnesia source particles are preferably magnesium oxide or hydroxide particles. Using alumina or aluminum hydroxide particles as the alumina source particles, and magnesium oxide or hydroxide particles as the magnesia source particles, sintering can preferably be conducted at a lower sintering temperature than ever without needing a non-oxidizing atmosphere, as described later. It is particularly preferable to use alumina particles as the alumina source particles, and magnesium hydroxide particles as the magnesia source particles. The binder may further contain particles of spinel, mullite, forsterite, etc., which are compounds of alumina and/or magnesia, in addition to the alumina source particles and the magnesia source particles. The organic binder may be methylcellulose, ethylcellulose, ethyl methylcellulose, carboxymethyl cellulose, hydroxypropyl methylcellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxyethyl ethylcellulose, etc. Among them, hydroxypropyl methylcellulose and/or methylcellulose are preferable. The organic binder is preferably 5-15% by mass per 100% by mass of the moldable material (silicon carbide particles plus binder). The mixed starting material is then blended with water to form a plasticized moldable material. The amount of water added, which is adjusted to provide the moldable material with moldable hardness, is preferably 20-50% by mass based on the starting material. The formed moldable material is extrusion-molded through a known honeycomb-structure-molding die by a known method, to form a honeycomb-structured green body. This green body is dried, machined in its end surfaces, outer peripheral surface, etc., if necessary, and then sintered in a temperature range of 1200-1350° C. in an oxidizing atmosphere to produce a silicon carbide ceramic honeycomb structure. Though not particularly restrictive, the drying method may be, for example, hot-air drying, microwave-heating drying, high-frequency-heating drying, etc. In a temperature range of 1200-1350° C., the alumina source particles and the magnesia source particles are sintered to form binder layers binding silicon carbide particles. Because sintering can be conducted at such a relatively low sintering temperature, sintering cost for forming the binder layers can be made lower than ever. When the sintering temperature is lower than 1200° C., the binder phase insufficiently binds silicon carbide particles, failing to obtain sufficient strength. On the other hand, when it is higher than 1350° C., the heat shock resistance is low. Because of the lower sintering temperature, a non-oxidizing atmosphere for suppressing oxidation is not needed unlike in the conventional technology, and sintering can be conducted in an oxidizing atmosphere, thereby avoiding cost increase in the sintering process. The present invention will be explained below in further detail referring to Examples, without intention of restricting the present invention to thereto. Examples 1-10, and Comparative Examples 2 and 3 Silicon carbide particles and binder particles (alumina source particles and magnesia source particles) having the particle diameters shown in Table 1 were formulated and blended in the amounts shown in Table 1, together with hydroxypropyl methylcellulose as an organic binder. The mixed starting materials were blended with water to form plasticized moldable materials, each of which was extruded through a honeycomb-structure-molding die in a screw-molding machine, forming a honeycomb-structured green body in the quadrangular prism shape of 34 mm in each side and 304 mm in length. This green body was dried at 120° C. for 2 hours in a hot-air drying machine, and sintered at the highest temperature of 1300° C. in an oxidizing atmosphere to obtain each silicon carbide ceramic honeycomb structure of Examples 1-10 and Comparative Examples 2 and 3 having a cell wall thickness of 8 mil (0.20 mm) and a cell density of 300 cpsi (46.5 cells/cm2). Comparative Example 1 The silicon carbide ceramic honeycomb structure of Comparative Example 1 was obtained in the same manner as in Example 1, except that the types and amounts of the silicon carbide particles and the binder particles were changed as shown in Table 1, that a degreasing step at 550° C. for 3 hours was added after the hot-air drying of the green body, and that sintering was conducted at the highest temperature of 1450° C. for 2 hours in an argon atmosphere. With respect to one of the silicon carbide ceramic honeycomb structures obtained in each of Examples 1-10 and Comparative Examples 1-3, the measurements of porosity, median pore diameter, coefficient of thermal expansion, and A-axis compression strength were conducted as described below. The results are shown in Table 2. (a) Measurement of Porosity and Median Pore Diameter The measurement of porosity and median pore diameter was conducted by mercury porosimetry. A test piece (10 mm×10 mm×10 mm) cut out of the ceramic honeycomb structure was set in a measurement cell in Autopore III available from Micromeritics, and the cell was evacuated. Thereafter, mercury was introduced into the cell under pressure to determine the relation between pressure and the volume of mercury pressed into pores in the test piece. The pressure was converted to pore diameter, and a cumulative pore volume (corresponding to the volume of mercury) determined by cumulating the pore diameter from the larger side to the smaller side was plotted against the pore diameter, to obtain a graph showing the relation between the pore diameter and the cumulative pore volume. The mercury-introducing pressure was 0.5 psi (0.35×10−3kg/mm2), and constants used to calculate the pore diameter from the pressure were a contact angle of 130° and a surface tension of 484 dyne/cm. The cumulative pore volume at a mercury pressure of 1800 psi (1.26 kg/mm2corresponding to a pore diameter of about 0.1 μm) was regarded as the total pore volume. The total pore volume, and a median pore diameter at which the cumulative pore volume was 50% of the total pore volume were determined from the mercury porosimetry measurement results. (b) Measurement of Coefficient of Thermal Expansion A test piece having a cross section shape of 4.5 mm×4.5 mm and a length of 50 mm was cut out of the ceramic honeycomb structure with its longitudinal direction substantially in alignment with the flow path direction, and heated from room temperature to 800° C. at a temperature-elevating speed of 10° C./minute, to measure longitudinal length increase under a constant load of 20 g by ThermoPlus available from Rigaku Corp., which was a compression-load-type and differential-expansion-type thermomechanical analyzer (TMA), to determine an average coefficient of thermal expansion between 40° C. and 800° C. (c) A-Axis Compression Fracture Strength A test piece of 24.5 mm in diameter and 24.5 mm in length cut out of each ceramic honeycomb structure was measured with respect to A-axis compression fracture strength, according to M505-87, “Test Method of Monolithic Ceramic Carrier for Automobile Exhaust Gas Cleaning Catalyst” of the Society of Automotive Engineers of Japan. TABLE 1Binder (Alumina Source ParticlesSilicon CarbideAnd Magnesia Source Particles)ParticlesTotalSintering ConditionsAmountAluminaMagnesiaAmountHighest(% byD50(1)SourceD50(1)SourceD50(1)(% byTemperatureTimeNo.mass)(μm)Particles(2)(μm)Particles(3)(μm)massM2(4)(° C.)(hr)AtmosphereExample 19040Alumina10Magnesium11100.4513004AirHydroxideExample 29040Alumina10Magnesium11100.4013002AirHydroxideExample 39040Alumina10Magnesium11100.3513002AirHydroxideExample 49040Alumina10Magnesium11100.5013002AirHydroxideExample 59040Alumina10Magnesium11100.8013002AirHydroxideExample 69040Alumina10Magnesium11100.3013502AirHydroxideExample 79040Alumina10Magnesium11100.4513502AirHydroxideExample 89040Alumina10Magnesium11100.5013502AirHydroxideExample 99040Alumina10Magnesium11100.3014002AirHydroxideExample 109040Alumina10Magnesium11100.4014002AirHydroxideCom. Ex. 18033Si4——20—14502ArCom. Ex. 29040Alumina10Magnesium11100.3012502AirHydroxideCom. Ex. 39040Alumina10Magnesium11100.5012502AirHydroxideNote:(1)D50 means “median particle diameter.”(2)A compound forming the alumina source particles.(3)A compound forming the magnesia source particles.(4)Molar ratio M2 [=(Al2O3)/(Al2O3+ MgO)]. TABLE 2Crystal Phases inHoneycomb StructureBinder LayersMedianEvaluation ResultsCordieriteSpinelPoreA-Axis(Molar(MolarPorosityDiameterCTE(3)StrengthNo.Ratio M1)(1)Ratio)(2)(%)(μm)(×10−7/° C.)(MPa)Example 10.700.3044.310.547.713.3Example 20.630.3741.018.046.910.0Example 30.890.1142.011.944.611.3Example 40.610.3944.89.948.010.2Example 50.790.2146.08.550.810.2Example 60.830.1735.313.252.614.1Example 70.880.1241.210.947.613.3Example 80.820.1843.110.146.911.9Example 90.840.1634.014.152.617.2Example 100.860.1436.114.350.118.7Com. Ex. 1——49.09.046.18.7Com. Ex. 20.240.7646.68.447.78.1Com. Ex. 30.300.7046.28.349.47.3Note:(1)Cordierite (molar ratio M1) = cordierite (mol)/[cordierite (mol) + spinel (mol)].(2)Spinel (molar ratio) = spinel (mol)/[cordierite (mol) + spinel (mol)].(3)CTE means “coefficient of thermal expansion.” It is clear from Tables 1 and 2 that the ceramic honeycomb filters of Examples 1-10 in the present invention, which had heat resistance equal to or higher than that of the ceramic honeycomb filters of Comparative Examples 1-3, were produced more inexpensively than in Comparative Examples 1-3, because they were able to be sintered at lower highest temperatures without needing a non-oxidizing atmosphere. | 18,620 |
11858858 | DETAILED DESCRIPTION The following description is made for the purpose of illustrating the general principles of the present invention and is not meant to limit the inventive concepts claimed herein. Further, particular features described herein can be used in combination with other described features in each of the various possible combinations and permutations. Unless otherwise specifically defined herein, all terms are to be given their broadest possible interpretation including meanings implied from the specification as well as meanings understood by those skilled in the art and/or as defined in dictionaries, treatises, etc. It must also be noted that, as used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless otherwise specified. The term “about” as used herein indicates the value preceded by the term “about,” along with any values reasonably close to the value preceded by the term “about,” as would be understood by one of skill in the art. When not indicated otherwise, the term “about” denotes the value preceded by the term “about” ±10% of the value. For example, “about 10” indicates all values from and including 9.0 to 11.0. The present disclosure includes several descriptions of exemplary “inks” used in an additive manufacturing process to form the 3D bodies described herein. It should be understood that “inks” (and singular forms thereof) may be used interchangeably and refer to a composition of matter comprising a plurality of particles coated with/dispersed throughout a liquid phase such that the composition of matter may be “written,” extruded, printed, or otherwise deposited to form a layer or filament that substantially retains its as-deposited geometry and shape without excessive sagging, slumping, or other deformation, even when deposited onto other layers or filaments of ink, and/or when other layers or filaments of ink are deposited onto the respective layer or filament. As such, skilled artisans will understand the presently described inks to exhibit appropriate rheological properties to allow the formation of monolithic structures via deposition of multiple layers or filaments of the ink (or in some cases multiple inks with different compositions and/or an ink with varying composition) in sequence. The following description discloses several preferred structures that can be used to construct 3D printed products formed via additive manufacturing processes, such as direct ink writing (DIW), extrusion freeform fabrication, or other equivalent techniques. The 3D printed products exhibit unique structural and compositional characteristics conveyed via the precise control allowed by such printing techniques. In accordance with the invention, the 3D printed products can be infiltrated with one or more infiltration materials to form an infiltrated component. The following description discloses several preferred embodiments of ceramic-based ink formulations and/or related systems and methods. In some examples, the ceramic-based ink formulations, and products formed therefrom, are constructed using ultra-high temperature ceramic materials. Examples of ultra-high temperature ceramic materials include boron carbide (B4C), zirconium diboride (ZrB2), hafnium carbide (HfC), hafnium diboride (HfB2), zirconium carbide (ZrC) and silicon carbide (SiC). In some examples the ceramic-based ink formulations are configured so that they can be used to generate parts using direct ink writing in an environment that is maintained at room temperature. Three-dimensional printed bodies can be printed using a direct ink writing technique. Referring toFIGS.1and2, an apparatus100for direct ink writing a 3D printed body102is illustrated. Apparatus100is configured to extrude ink, in the form of a filament104, onto a work surface that is supported by a print platform106. In general, the apparatus100includes a print head108, the print platform106, and a controller110. The print head108is configured to dispense ink based on signals sent from the controller110. The print head108generally includes a frame112, a material reservoir114, a material dispenser116, and a nozzle118. Frame112is a structure that is configured to support the material reservoir114and the nozzle118. The material reservoir114and the nozzle118are in fluid communication so that ink can be fed from the material reservoir114to the nozzle118. The material dispenser116is coupled to the material reservoir114and provides the driving force that forces material held in the material reservoir114to travel into, and through, the nozzle118. In an example, the material reservoir114is a syringe barrel that is loaded with an ink formulation and coupled to the nozzle118by a Luer lock. The material dispenser116can be an air-driven dispenser that includes an air output fluidly coupled to the material reservoir114and configured to drive a piston in the material reservoir114. The print head108can also include one or more mechanisms configured to move the nozzle118relative to the print platform106. For example, the frame112can include a fixed portion and a movable portion. An actuator can be incorporated into the frame112and interposed between the fixed portion and the movable portion and configured to translate and/or rotate the movable portion relative to the fixed portion. The actuator can be driven electromechanically, pneumatically, manually, or using combinations thereof. The nozzle118is configured to discharge the ink from the material reservoir114in the form of filament104. Filament104has a predetermined configuration that can be selected based on the desired configuration of the printed body102and the type of ink that is used. For example, the nozzle118can be configured to discharge the ink so that the filament104has a selected cross-sectional shape, such as a circular or polygonal cross-sectional shape. Additionally, the size of the nozzle118can be selected to provide a filament104having a desired size and to provide consistent flow of a selected ink. Various nozzles118can be selected and configured to deposit a filament having any size. In some embodiments, the size of the nozzle118can be selected relative to the size of the ceramic particles so that the ink is able to flow through the nozzle without clogging. In some embodiments, the nozzle118is configured to deposit a filament104having a diameter of at least 200 μm based on the ceramic particles of the ink. There is no upper limit on the filament size beyond the desired geometry of the printed product. In some embodiments, the nozzle118is configured to deposit a filament104having a diameter in a range between about 200 μm and about 800 μm. In at least one embodiment, the opening of the nozzle has a diameter of about 400 μm to form a filament having a diameter of about 400 μm. The extruded ink is selectively deposited under control of the controller110to progressively build the structure of the three-dimensional printed body102. The print platform106supports the work surface, and the work surface supports the ink that is deposited by the nozzle118during the construction of the printed body102. In some embodiments, the work surface can be a part of the print platform106. In other embodiments, the work surface can be a portion of a substrate that is mounted on the print platform106. In at least some examples, the substrate can be a graphite substrate, glass, or any other hard surface. It should be appreciated that the substrate can be coated with a release agent such as petroleum jelly, or PTFE. The print platform106can be configured to move the work surface so that relative motion between the nozzle118and the work surface can be provided. In an example, the print platform106can be a movable bed that is configured to translate the work surface in the direction of any, or all, of the X, Y, and Z axes. Additionally, the print platform106can be configured to rotate the work surface about any, or al, of the X, Y, and Z axes. A movable print platform106can be used in combination with, or as an alternative to, a print head108that includes a movable portion. The relative motion between the nozzle118and the work surface can be computer-controlled or manually operated, and the movement can be driven using electro-mechanical and/or pneumatic actuators. The controller110is configured to communicate with the print head108and the print platform106and to provide instructions so that ink is deposited in a predetermined configuration on the work surface. For example, controller110is configured to provide instructions to print head108and print platform106that control relative motion between the nozzle118and the work surface. Controller110is also configured to provide instructions to the material dispenser116to control the delivery of the ink from the material reservoir114to the nozzle118. Controller110can include one or more processors configured to send signals120,122that include instructions to the print head108and the print platform106, respectively, to control the ink delivery and relative movement. Using those signals, the controller110can be configured to control the print speed and print geometry while constructing the printed body102. The ink that is used to form the printed bodies described herein is generally an aqueous thixotropic ink that exhibits shear-thinning behavior. The ink can be tuned so that the flowability allows for the material to be effectively extruded from the nozzle while preventing excessive slumping of the extruded structure after the ink is deposited. Inks with a specific rheology used in 3D printing allow the resulting 3D printed structures to retain their shape for an extended period of time as a green body, i.e., before final curing. According to various embodiments, an ink is formulated to produce ceramic printed bodies that incorporates a high concentration of ceramic particles. The ink can be configured so that the printed structure does not exhibit warpage or distortion prior to a final cure, even after being subjected to drying. In various examples, an ink was formulated with a suspension of a ceramic particles having a high solid loading of ceramic particles. The ink formulations were also created to have simple compositions that provide a long storage life. For example, the ink formulations were designed to have a storage life was at least one week when stored in a refrigerator at a temperature in a range between 32° F. and 42° F. FIG.3depicts a flowchart300of an example method of preparing an ink in accordance with at least one embodiment. The method of flowchart300can be used to generate an ink for use in a direct ink writing apparatus, such as the direct ink writing apparatus100shown inFIGS.1and2, to produce 3D printed bodies. Further compositional, structural, and operational embodiments will be apparent to persons skilled in the relevant art(s) based on the discussion regarding flowchart300. As shown inFIG.3, the method of flowchart300begins at step302. In step302, ceramic particles are added to deionized water as a first step in creating an aqueous suspension. The ceramic particles have a selected size, or selected combination of sizes, and are formed from a selected ceramic material that is the desired ceramic material for the 3D printed body. Particles formed from a variety of ceramic materials, and having a variety of sizes, can be selected to form the aqueous suspension. The type and size of ceramic particles utilized to formulate the ink can be selected to provide the desired attributes of the final product, such as strength, coefficient of thermal expansion, mass, etc. In some embodiments, the selected ceramic material can be selected to construct a printed body formed from an ultra-high temperature ceramic material so that the printed body can be subjected to subsequent high temperature processes and/or high temperature environments. In various examples, an ultra-high temperature ceramic is selected so that the printed body offers geometric and physical stability at temperatures exceeding 2000° C. Examples of ceramic materials that can be used to form the ink include, but are not limited to, various borides, carbides, nitrides, and oxides. In some embodiments, the ceramic material is selected from B4C, ZrB2, ZrC, HfC, and HfB2. The size of the ceramic particles can be selected based on the type of ceramic and a predetermined solid loading of the ceramic particles in the ink. In various embodiments, the ceramic particles include B4C particles that have sizes of 0.8-5 μm (e.g., 3000 F and 1500 F boron carbide particles produced by 3M Advanced Materials Division, of St. Paul, MN), and ZrB2, ZrC, HfC, HfB2particles that have an average particle size in a range of 3-5 μm. In some embodiments, particles having different sizes can be combined. The combination of particle size can be selected based on weight. In at least one example, a combination of equal amounts of 1500 F. (˜5 μm) and 3000 F. (˜0.8 μm) B4C particles by weight (i.e., 50:50 by weight) was used to form an aqueous suspension having a particle concentration greater than 50 vol. %. At step304, the combination of the ceramic particles and the deionized water is mixed to disperse the particles throughout the water to form the aqueous suspension. The mixing can be accomplished using a mixing device, such as a planetary centrifugal mixer. In an example, the combination was mixed using a planetary centrifugal mixer (e.g., an AR-250 mixer produced by Thinky U.S.A. of Laguna Hills, CA) at 2000 rpm for 2 minutes. A combination306of step302and step304can be repeated such as by incrementally adding ceramic particles to deionized water and mixing the combination until an aqueous suspension having a desired dispersion (e.g., uniform or near-uniform dispersion), and a desired particle load, is formed. In some embodiments, the ceramic particles are mixed with deionized water so that the resulting suspension has a ceramic particle solid loading that is greater than 40 vol. %. In some embodiments, the aqueous suspension has a ceramic particle solid loading that is in a range between 50 vol. % and 59.3 vol. %. A dispersing agent can be added during the formation of the aqueous suspension to improve the dispersion of the ceramic particles in the aqueous suspension. In some examples, ceramic particles were suspended in deionized water containing polyethyleneimine (PEI). In addition to acting as an effective dispersing agent, the PEI molecules act as a green body binder due to its polycationic characteristics. As a result, the PEI can also improve the dimensional stability of the deposited ink before the printed body is subjected to a final curing step. In at least some examples, PEI having an average molecular weight of 25000 g/mol was included in the aqueous suspension. At step308, at least one viscosifier is added to the aqueous suspension to tune the viscosity and to formulate a printable ink. The viscosifier is added to the suspension to create an ink that has a desired balance between flowability through a nozzle and dimensional stability after deposition. In some examples the viscosifer is configured to increase the viscosity of the suspension and the amount of viscosifier added to the suspension is generally inversely proportional to the solid loading of the ceramic particles in the suspension. In examples of inks having relatively high volume percentage solid loading of ceramic particles in the suspension, i.e., having a ceramic particle solid loading greater than 40 vol. %, the amount of viscosifier required to formulate a printable ink is generally lower than known inks. In particular, the required amount of viscosifier is lower because of the increased viscosity of the suspension resulting from the higher particle loading prior to adding the viscosifier. In an example, Pluronic F-127 was used as a viscosifier and added to the suspension. Pluronic F-127 can be used to form a stiff hydrogel during mixing due to its amphiphilic characteristic and the viscosifier acts as a surfactant to form a thixotropic paste that can be printed using a direct ink writing apparatus, such as apparatus100ofFIG.1. Additionally, the hydrogel formed using Pluronic F-127 is sensitive to temperature, so a resulting ink can be stored in a refrigerator to provide a longer shelf life. In an example, storing the ink in a refrigerator provides of shelf life of 1-2 weeks when the ink is held in a sealed container. The viscosifier can be chosen based on the cleanliness of its burn off to reduce the presence of materials form contaminants during curing. The amount of viscosifier is selected to complement the viscosity of the aqueous suspension so that the final ink is printable. In various examples, the amount of viscosifier is in a range between about 1 weight % (wt. %) and about 18 wt. %. In other examples, the amount of viscosifier is in a range of between about 1 wt. % and about 8 wt. %. In still further examples, the amount of viscosifier is in a range of between about 4 wt. % and about 8 wt. %. In still further examples the amount of viscosifier is in a range of between about 1 wt. % and about 5 wt. %. The amount of viscosifier can vary dependent on the type of ceramic particles used. In an exemplary ink formed with B4C particles, Pluronic F-127 was included in a range between 4 wt. % and 8 wt. %. In some examples, ink formed with B4C particles can include a viscosifier in a range between 6% and 8%. In exemplary Zr-based inks formed with ZrB2or ZrC particles, Pluronic was included in a range of between about 1 wt. % and about 5 wt. %. In exemplary Hf-based inks formed with HfC or HfB2particles, Pluronic was included in a range of between about 1 wt. % and about 5 wt. %. In some examples, ink formed with denser particles, such as ZrB2or HfB2, can include a viscosifier in a range between 3% and 5%. At step310, additional modifiers can be added to alter other attributes of the ink such as chemical, rheologic, or other physical attributes. For example, a pH modifier can be added to alter the pH of the ink to change the working, or open, time of the ink. In some embodiments, the ink is formulated to have a target working time greater than 10 minutes, in some examples the target working time is about 20 minutes. Suitable pH modifiers include, but are not limited to, glacial acetic acid, hydrochloric acid, and nitric acid. In accordance with some embodiments, glacial acetic acid in a range of about 0.06 wt. % and about 2 wt. % can be added to reduce the overall pH of the suspension thereby increasing the working time so that drying of the suspension was avoided to allow a longer time to prepare the thixotropic ink. In some embodiments, about 1 wt. % of glacial acetic acid can be added. A pH modifier may not be desired depending on the type of ceramic particles used to formulate the ink because inks formulated with some ceramic particles have less of a tendency to dry out which would otherwise reduce the working time to print. For example, a pH modifier can be advantageous for inks based on boron carbide, while a pH modifier may not be advantageous for inks based on Zr or Hf. In an example, ink was formulated with boron carbide using about 1 wt. % glacial acetic acid to modify the pH of the ink. Furthermore, the additional modifiers can include additives that form a hydrogel. The hydrogel-forming additives can be water soluble. The hydrogel-forming additives can include cellulose and polyethylene glycol. Rheological characteristics can be used to describe the behavior of inks. Referring toFIG.4, a curve400illustrating the viscosity of an exemplary B4C ink is illustrated relative to shear rate. As shown inFIG.4, the ink can be formulated to have a generally shear-thinning behavior which is characterized as having viscosity that decreases with an increase in shear rate. As a result, the ink is configured to flow through a conical nozzle and retains its shape immediately after deposition. In particular, as shown inFIG.4, the viscosity of the ink dropped as a function of shear rate, until about 100 (1/s) and then drastically decreases at higher shear rates. It is desirable that inks used for DIW are formulated to provide sufficient stiffness to withstand the built-up structure of DIW, in addition to exhibiting shear thinning and high viscosity. Referring now toFIG.5, a comparison of storage modulus relative to oscillation stress is shown for an aqueous suspension created with B4C particles and for an ink formulated with the suspension created with B4C particles. The curve500is shown for the exemplary B4C-based suspension in comparison to a curve502for the exemplary B4C-based ink. The storage modulus is a measure of elastic response of the ink and measures the stored energy in the ink and can be used to predict slumping behavior of the ink. As is apparent from the graph ofFIG.5, the addition of at least one viscosifier to the suspension to form an ink results in an increase in the storage modulus over a large range of oscillation stress. As illustrated inFIG.5, the exemplary ink demonstrates a larger storage modulus over a wide range of oscillation stress compared to the exemplary suspension. The ink exhibits a longer elastic plateau with a constant storage modulus of about 100 kPa until a shear stress of about 1000 Pa, i.e., the storage modulus of the exemplary ink remains over about 100 kPa over a range of oscillation stress up to about 1000 Pa. The storage modulus of the exemplary ink also remains above the maximum storage stress of the exemplary suspension (˜20 kPa) for all oscillation stress values below a value of about 1800 Pa. The storage modulus of the exemplary suspension drops drastically from greater than about 10 kPa to below 20 Pa over a range of oscillation stress between about 3 Pa and about 10 Pa and remains below 20 Pa at oscillation stresses greater than about 10 Pa. The inks described above can be used in DIW processes to construct three-dimensional printed bodies. In preparation for direct ink writing, the formulated ink is loaded into a material reservoir of a DIW apparatus, such as material reservoir114of DIW apparatus100. As an example, the material reservoir can be a syringe barrel. The loading of the ink into the material reservoir can include steps to prevent print defects, such as performing additional mixing processes to remove air bubbles in the ink. In an example, the ink is loaded into a 10 ml syringe barrel and centrifuged at a rate of 4500 rpm for one minute to remove air bubbles. After loading the ink, the material reservoir is loaded into a print head of a direct ink writing apparatus, such as print head108of apparatus100described above. The material reservoir is coupled to a material dispenser, such as material dispenser116of apparatus100as shown inFIG.1. The material dispenser is configured to force the ink from the material reservoir, through a nozzle, and onto a work surface of the direct ink writing apparatus. The material dispenser can be configured to drive a piston in a syringe barrel using pressurized air to force the ink from the material reservoir. In an example embodiment, the fluid dispenser applies pressurized air in a range of 30-45 psi. The material dispenser forces the ink to be extruded through a nozzle that is fluidly coupled to the material reservoir. For example, the ink can be extruded through nozzle118of apparatus100, shown inFIG.1. The nozzle is selected to extrude the ink in the form of a filament having desired dimensions. In an example, the nozzle is a smooth-flow tapered micro nozzle having an inner diameter that tapers from about 600 μm to about 400 μm, and an outlet having a diameter of about 400 μm. In example embodiments, the nozzle can be coupled to the material reservoir by a removable coupling, such as a Luer lock. The ink is deposited onto a work surface that can be provided on a print platform, such as print platform106of DIW apparatus100, or can be provided by a substrate coupled to the print platform. The work surface can be treated, such as with a lubricant or other release material, to limit the adhesion between the extruded ink and the work surface. In an example, the work surface was provided by a graphite substrate and petroleum jelly was spread on the surface to reduce the adhesion between the printed ink and the substrate after the ink was dried. The speed that the ink is deposited on the work surface, i.e., the writing speed, can be controlled by a controller, such as controller110of DIW apparatus100. The writing speed can be varied throughout the process of constructing a printed body. In various embodiments, the writing speed can be maintained in a range of 1-10 mm/s. In some examples, the writing speed was maintained at about 5 mm/s. After the ink is deposited on the work surface and formed into a 3D printed body, the printed body can be air dried. In an example, the 3D printed body was dried in ambient air overnight and later in an oven at a temperature of 80° C. for 24 hours to remove water from the deposited ink. An additional step of curing the 3D body can be performed to remove binders, additional water, and any other volatile compounds that are present in the deposited ink. The additional step of curing can include heat treating the 3D printed body in an inert gas environment. In an example, the additional step of curing can include heat treating the 3D printed body at 1050° C. for 1 hour in flowing 4% Hz/Argon gas. The 3D printed bodies constructed using ink formulation described above can have many different configurations. Referring first toFIG.6, an example of a 3D printed body630is constructed from a plurality of layers having alternating configuration. The 3D printed body630is configured as a simple cubic lattice with multiple orthogonal layers of parallel cylindrical filaments, or rods, that were printed alternately. As shown, 3D printed body630is constructed from a of plurality of first layers632alternately stacked with a plurality of second layers634. Each of the first layers632has a first configuration formed by a plurality of parallel filaments636having a first orientation. Each of the second layers634has a second configuration that is different than the first configuration. The second configuration is formed by a plurality of parallel filaments636having a second orientation that is different than the first orientation. In the illustrated example, the first orientation is orthogonal to the second orientation, and the center-to-center spacing (L) of the filaments is constant for all of the first layers632and the second layers634. It should be appreciated that the center-to-center spacing of the filaments can be varied throughout the 3D printed body to vary the density of the printed material throughout the structure, thereby creating a graded density. In the illustrated example, adjacent parallel filaments are constructed as a continuous bead of material in which the adjacent filaments636are coupled by a return638that is formed when the direction of travel of the nozzle of a DIW apparatus is reversed while depositing ink. It should be appreciated that incorporating an intermittent flow of ink and altering the pattern of printing of the 3D printed body can be used so that the returns638are omitted from the structure. In some examples, the diameter (d) of each filament636equals a diameter of the opening in the nozzle used to deposit the ink. The inter-layer z-spacing (z), i.e., the center-to-center distance between adjacent layers resulting from the distance the nozzle is moved in the z-direction between layers, is less than the diameter of the filaments636so that each subsequently deposited layer is effectively pressed into the prior layer during printing to ensure good connectivity and adhesion between successive layers. In some examples the z-spacing is selected to be less than the diameter of the filaments636, such as in a range of 50%-70% of the diameter of the filaments636. In at least one example, the z-spacing is selected to be about 60% of the diameter of the filaments636. For example, for a 400 μm diameter nozzle the z-spacing can be 240 μm, and for a 800 μm diameter nozzle the z-spacing can be 480 μm. The z-spacing can also be controlled in combination with the nozzle size and number of layers to vary the overall height of the 3D printed body. Referring toFIG.7, another example of a 3D printed body constructed from an ink formulation described herein using a DIW apparatus will be described. In particular, a 3D printed body740is generally constructed as a helical spline. The printed body740includes a plurality of repeated layers742having different orientations. Each layer742is constructed as a single filament of ink extruded into the shape of a gear, or star, having a plurality of teeth744, or cogs. In the illustrated embodiment, each layer742is shaped as a gear having ten (10) teeth744. The layers740are oriented so that each layer742is rotated relative to the adjacent layer742about a longitudinal axis A to form the helical spline structure. It should be appreciated that the 3D printed body can be constructed as distinct sequentially printed layers. Referring toFIG.8, another example of a 3D printed body constructed from an ink formulation described herein using a DIW apparatus will be described. In particular, a 3D printed body850is generally constructed as a fluted cone. The printed body850includes a plurality of layers852having different sizes and configurations. The shapes of layers852transition from a first shape at a first end854to a second shape at a second end856. The layers852also have a maximum outer dimension that varies from the first end854to the second end856. The shape of the layers generally transitions from the shape of a gear closest to the first end854to the shape of a circular ring closest to the second end856. As shown, the gear shape includes a plurality of teeth858(e.g., 10 teeth as shown). The transitioning shape and outer dimension results in the flutes and taper that form the fluted conical shape of the 3D printed body850. Referring toFIG.9, a still further example of a 3D printed body constructed from an ink formulation described herein using a DIW apparatus will be described. In particular, a 3D printed body960is constructed as a ring structure including a plurality of concentric rings962that are coupled by a radial rib964. The concentric rings962are spaced by an inter-ring spacing that can be constant, or variable, through the construction. It should be appreciated that although only a single radial rib is illustrated, a plurality of radial ribs can be included. The 3D printed bodies produced using the inks, methods, and structures described herein can be combined with other materials to form components for larger systems. For example, the printed bodies can be used to provide a scaffolding for an infiltration material to construct an infiltrated component. As an example, a 3D printed body constructed using a ceramic-based ink can be infiltrated with a metallic material to form an armor plate component used in a lightweight armor system. FIG.10depicts a flowchart1000of an example method of forming an infiltrated component in accordance with at least one embodiment. The method of flowchart1000can be used to infiltrate a 3D printed body, such as the printed bodies described herein, using an infiltration material. Steps included in the method of forming an infiltrated component are also shown schematically inFIG.11. Further compositional, structural, and operational embodiments will be apparent to persons skilled in the relevant art(s) based on the discussion regarding flowchart1000. As shown inFIG.10, the method of flowchart1000begins at step1002. In step1002, a 3D printed body that is configured for infiltration of a molten material is formed. The 3D body can have many different configurations, such as for example any of the configurations described herein, including the configurations shown inFIGS.6-9, the configurations shown inFIG.11, or the configurations shown inFIGS.12and13. In at least some examples, the 3D printed body can have a lattice structure that is configured to interact with the molten material so that the infiltration of the molten material through the 3D printed body can be driven, at least in part, by capillary action. Gravity or pressure are other means for infiltrating 3D printed bodies. A 3D printed body constructed for infiltration of the molten material can also include a graded density, such as the graded density shown in 3D printed body1280aofFIG.12and 3D printed body1280bofFIG.13. The graded density is produced by varying the density of the ceramic material throughout the 3D printed body structure. As shown inFIGS.12and13, the 3D printed bodies1280a,bhave constructions similar to the 3D printed body630ofFIG.6. In particular, the 3D printed bodies1280a,bare configured as cubic lattices with multiple orthogonal layers of parallel cylindrical filaments that were printed using an ink comprising B4C. However, the filaments used to construct the 3D printed body1280a, shown inFIG.12, vary in center-to-center spacing between layers throughout the 3D body1280aso that the 3D printed body1280ahas a graded density that changes from higher density in the lower layers to lower density in the upper layers in the Z-axis direction. The filaments used to construct the 3D printed body1280b, shown inFIG.13, vary in center-to center spacing between layers and within each layer throughout the 3D body1280bso that the 3D printed body1280bhas a graded density that changes from higher density in the lower left corner ofFIG.13to lower density in each of the positive X and Y directions from that corner. Each of the 3D printed bodies1280a,bis constructed from a of plurality of stacked first layers1282and second layers1284. Each of the first layers1282and the second layers1284is constructed from filaments1286that are spaced by a center-to-center distance (L). The center-to-center distance between adjacent filaments that can vary within a layer and/or between different layers. Accordingly, the center-to-center spacing of the filaments throughout the 3D printed body can vary in directions parallel to the X-axis and/or the Y-axis. In a first layer1282, such as the top layer shown inFIG.13, the center-to-center spacing varies in a direction parallel to the Y-axis from a first spacing L1to a second spacing L2that is greater than the first spacing L1. Similarly, the center-to-center spacing between filaments1286in a second layer1284, e.g., the layer immediately adjacent and below the top layer shown inFIG.13, varies in a direction parallel to the X-axis from a third spacing L3to a fourth spacing L4that is greater than the third spacing L3. The center-to-center spacing between filaments in 3D bodies intended for infiltration was selected to be less than 1 mm to provide complete infiltration. In some embodiments, the center-to-center spacing was selected to be less than 800 μm, in some embodiments less than 600 μm, and in some embodiments less than 400 μm. Additionally, the range of center-to-center spacing within the layers can vary throughout a thickness of the 3D printed body. For example, the range of center-to-center spacing can change dependent on the Z-axis position of the layers within the structure so that the average center-to-center spacing for each layer is different throughout the 3D printed body. As shown inFIG.12, the lowest layer of the 3D printed body1280ain the Z direction has an average center-to-center spacing that is smaller than an average center-to-center spacing of the layers positioned further in the +Z direction from the lowest layer, i.e., above the lowest layer. As a result, a density of the ceramic material decreases from a first end1288(i.e., the bottom layer) to a second end1289(i.e., the top layer) of the 3D printed body1280a. In at least one embodiment, a gradient through the thickness of the 3D body was approximately 30% to 60% B4C. In an example embodiment, the 3D body is constructed from layers each having a thickness equal to the thickness of the filament and an overall square plan shape having 0.75 inch (19.1 mm) sides that are stacked so that the 3D printed body1280has height of 0.3 inch (7.6 mm). Referring again toFIG.10, in step1004the 3D printed body is infiltrated with an infiltration material. The infiltration of the 3D printed body can be used to increase the overall density of portions of the 3D printed body. In an example embodiment, the 3D printed body1280was infiltrated with 6061-T6 aluminum to form a graded B4C—Al cermet. The step of infiltrating the 3D body can be accomplished by subjecting the body to a vacuum environment in a furnace at, or above, a melting temperature of the desired infiltration material and placing the 3D body in contact with the infiltration material. It should be appreciated that the 3D printed body1280can be in a green state (i.e., a green 3D printed body) when infiltrated with the infiltration material. As shown inFIG.11, the 3D body1170can be positioned in direct contact with a source of infiltration material1172, such as 6061-T6 aluminum. In an example, the 3D printed body1170and the infiltration material1172were loaded into a furnace1174. The furnace1174defined an environment that was controlled so that the infiltration material melted and flowed into the 3D printed body1170at a temperature of 1050° C. for 1 hour in vacuum of less than 90 mTorr. In an alternative embodiment, the 3D body1170and the infiltration material1172were placed in a furnace1174at a temperature of 1100° C. for 2 hours in vacuum of less than 50 mTorr, with a temperature ramp rate of 5° C./min. Alumina bubbles1176were also positioned in the furnace so that they were adjacent to and circumscribed at least a portion of the infiltration material to control movement of the molten infiltration material away from the 3D printed body1170. The infiltration material1172was constructed to include a volume of infiltration material that was in a range between 110% and 125% of the porosity of the 3D body1170(i.e., void space volume) so that the amount of infiltration material provided would be sufficient to occupy the entire porosity, or void space, of the 3D body1170. In an example embodiment, the infiltration material1172is provided in the form of a plate. The 3D printed body can be oriented and positioned relative to the infiltration material source to alter the interaction between the printed body and the infiltration material. In at least one example embodiment, 3D body1170was oriented so that the layers of the 3D body1170having higher density (e.g., layers with center-to-center spacing of 100 μm) were positioned at the top and the lower density layers (e.g., layers with center-to-center spacing of 800 μm) were positioned at the bottom. The infiltration material1172can be placed against the top and bottom of the 3D printed body1170so that the molten infiltration material can fill the void space from both directions. Alternatively, the infiltration material can be placed against the top or the bottom of the 3D printed body. In step1006, excess infiltration material is removed. As shown inFIG.11, after infiltrating the 3D printed body excess infiltration material1178can remain outside of the confines of the 3D printed body1170. The excess infiltration material1178can be removed by material removal techniques such as machining, grinding, polishing, etc. In an example, a 120 μm grit grinding wheel was used to remove excess infiltration material1178and to flatten the infiltrated 3D printed body1170. Referring toFIG.14, an example of an infiltrated component1490will be described. The infiltrated component1490is constructed with a 3D printed body having the structure generally corresponding to that of 3D printed body1280shown inFIGS.12and13that has been infiltrated with an aluminum alloy. As shown by the image ofFIG.14, the gradation of the densities of the ceramic material1492and the infiltration material1494are visible. The center-to-center spacing between filaments1496of the ceramic material1492varies in a direction parallel to the Y-axis from a first spacing L1of 0.1 mm to a second spacing L2of 1.25 mm. Similarly, the center-to-center spacing between filaments in a second layer varies in a direction parallel to the X-axis from a third spacing L3of 0.1 mm to a fourth spacing L4of 1.25 mm. Because of the construction of the graded ceramic printed body, in the infiltrated component1490, the density of the ceramic material1492(i.e., the density of the ceramic particles in the printed body) varies inversely relative to the density of the infiltration material1494. As described above, the combined ceramic material and infiltration material form an infiltrated component, such as infiltrated component1490ofFIG.14. Referring back toFIG.10, in step1008the infiltrated body can be heat treated to alter the physical attributes, such as hardness, of the infiltrated body. In an example, the infiltrated component was heat treated in air at 800° C. for 8 hours. Portions of the infiltrated component1490were hardness tested before and after applying the heat treatment. It was determined that in each of the portions, the hardness measurement increased after heat treatment as shown inFIG.15. In particular, the hardness testing was performed at a front face, at the center, and at a back face of the infiltrated component. The front face corresponds to an end face of a portion of the infiltrated component1490having a higher ceramic density, such as end1288of 3D printed body1280shown inFIGS.12and13, but a lower aluminum density. The back face corresponds to an end face of a portion of the infiltrated component1490having a lower ceramic density, such as end1289of 3D printed body1280shown inFIGS.12and13, but a higher aluminum density. The center corresponds to an intermediate location within the 3D printed body. As shown byFIG.15, the hardness of the infiltrated component1490measured at a plurality of locations on the infiltrated component generally increased at all locations after the infiltrated component1490was subjected to heat treatment. In an example, the hardness at the back face increased by about 47%, the hardness at the center increased by about 22%, and the hardness on the front side increased about 9%. Overall, the infiltrated component1490generally had hardness in a range between about 20 HRA and about 78 HRA in the Rockwell A scale before heat treatment, and hardness in a range between 40 HRA and 82 HRA in the Rockwell A scale after heat treatment. The formulations and methods described herein can be used to construct components, such as infiltrated component described above, that are embedded with functionally graded materials that utilize lightweight materials. Those components can be constructed for extreme applications, including applications that absorb and disperse energy applied to a body by a projectile such as lightweight body armor. As described above, the components can be constructed, at least in part, utilizing scalable processes such as direct ink writing. The B4C—Al cermet construction of the exemplary infiltrated component can be used to form monolithic armor plates that can be constructed with varying properties through the thickness of the armor plate. The hardness and fracture strength throughout the component can be controlled by controlling the densities of the B4C material and the aluminum material using the geometry of a 3D printed body and applying heat treatment to provide desired hardness in selected portions of the component. In an example of a B4C—Al body armor component, the front face has high hardness to blunt the nose of an incoming projectile, an intermediate portion has improved fracture toughness to continue eroding the main body of the projectile, and a back side of the component requires tensile and fracture strength to support the impact and erosion sequence during the penetration of the projectile. The infiltrated component having graded density that is constructed to achieve the desired properties and to be capable of maximizing the effect of the sequence of events applied to the projectile can be provided by constructing the selected graded material using the various techniques described herein. In an example of an infiltrated component used for light weight armor, direct ink writing can be used to deposit layers of B4C ceramic inks having different B4C densities ranging from 65% B4C at the front face to 40% B4C at a back face of the armor component. The density can be controlled either by controlling the quantity of ink that is deposited in each layer, such as by altering the spacing between filaments, or by changing the composition of the ink during printing. After the ink is deposited to form a 3D printed body, an aluminum alloy can be used as an infiltration material to produce fully dense structures. In some examples, the relative densities of the ceramic material and infiltration material are selected to provide a hardness gradient throughout the infiltrated body that varies from 20 HRA to 90 HRA. In other example embodiments the hardness gradient throughout the infiltrated body varies from 40 HRA to 70 HRA. In still further example embodiments, the hardness gradient throughout the infiltrated body varies from 600 to 1000 on a Vickers scale. The chemical composition of the infiltrated component1490was analyzed using scanning electron imaging and energy-dispersive X-ray spectroscopy (EDS) techniques, the results of which are illustrated inFIGS.16A-F. In particular,FIG.16Ais a magnified image of a portion of the infiltrated component1490.FIG.16Bis an EDS layered image that illustrates the concentrations of aluminum, carbon, and oxygen in the portion of the infiltrated component1490ofFIG.16A.FIG.16Cillustrates the concentration of aluminum throughout the portion of the infiltrated component1490shown inFIG.16A. Each ofFIGS.16D and16Eillustrates the concentration of carbon and oxygen, respectively, in the portion of the infiltrated component1490ofFIG.16A. Finally,FIG.16Fis a graph illustrating the EDS spectrum of the infiltrated component1490. The inventive concepts disclosed herein have been presented by way of example to illustrate the myriad features thereof in a plurality of illustrative scenarios, aspects, and/or implementations. It should be appreciated that the concepts generally disclosed are to be considered as modular, and may be implemented in any combination, permutation, or synthesis thereof. In addition, any modification, alteration, or equivalent of the presently disclosed features, functions, and concepts that would be appreciated by a person having ordinary skill in the art upon reading the instant descriptions should also be considered within the scope of this disclosure. While various aspects have been described above, it should be understood that they have been presented by way of example only, and not limitation. Thus, the breadth and scope of an aspect of the present invention should not be limited by any of the above-described exemplary aspects, but should be defined only in accordance with the following claims and their equivalents. | 47,521 |
11858859 | DESCRIPTION OF EMBODIMENTS FIG.1shows a device100for implementing an example of a method according to the invention. In this example, the coating precursor140is present in the liquid state in the reactor120and the diluent gas200a,200bis directly injected into the liquid precursor140. The device100comprises a microwave generator110, a reactor120, and a scrolling device (not shown) which allows to move the yarn150in the reactor120. The treated yarn150is made of carbon or ceramic, for example of silicon carbide. The material of the yarn150is chosen so as to be coupled with the microwave field in the reaction zone115in order to cause its heating. In an exemplary embodiment, the yarn150can be made of silicon carbide having an oxygen content less than or equal to 1% in atomic percentage. It is possible, for example, to use a yarn of the Hi-Nicalon type S type marketed by the Japanese company NGS. It will be noted that the treated yarn150may or may not already be coated with another material. The microwave generator110here comprises a resonator111defining a resonant cavity112, the resonator111is connected to a wave generator (not shown). In operation, the resonant cavity112is traversed by a microwave field. The microwave field can be characterized by its power (or amplitude) and its frequency, which can be easily determined by the person skilled in the art to obtain a surface temperature of the yarn suitable for forming the coating from a given coating precursor. The microwave field may have a main frequency comprised between 2.35 GHz and 2.55 GHz. For example, the use of a microwave generator with a main frequency of 2.45 GHz allows the heating of a yarn made up of around500silicon carbide filaments. The heating is then done in a very localized manner only on the yarn: the heating is then qualified as direct coupling in a cold-wall reactor. The reactor120can be made of a material transparent to microwaves, for example quartz. The reactor120may have the shape of a tube, having for example a U-shape. The reactor120may have a base portion (here a horizontal portion)121, a first branch (here a first vertical portion)122and a second branch (here a second vertical portion)123, each of the vertical portions122and123being connected to the horizontal portion121. The first vertical portion122can be connected to a first end of the horizontal portion121and the second vertical portion123at a second end of the horizontal portion121, opposite the first end. The second vertical portion123of the reactor120is here present at least partly in the resonant cavity112of the resonator111, that is to say that it traverses the resonator111. The portion of the reactor120present in the resonant cavity112forms the reaction zone115. The yarn150can be placed at an antinode of the microwave field in the reaction zone115. Only a branch or a vertical portion123of the reactor120can be present in the microwave field. The shape of the reactor120allows to introduce a liquid precursor140. The level of liquid can be regulated by adding a precursor in one of the two vertical portions122and123, for example in the first vertical portion122using a dropping funnel143connected to the reactor120as in the non-limiting example illustrated. The amount of liquid can be regulated manually or controlled by a sensor at the precursor and an automated precursor supply device. In the latter case, it is possible to use a liquid flowmeter connected upstream to a pressurized canister, the regulation of the level being able to be done by an optical sensor of the level of liquid in the portion122, said sensor controlling the regulation valve of the flowmeter. Furthermore, the reactor120can be provided with a purge valve126in order to evacuate the precursor140at the end of the deposition. The meniscus145of the precursor140is located below the resonant cavity112or below the reaction zone115. In particular, there is no liquid precursor140in the reaction zone115in the example illustrated. A yarn portion156acontiguous to the yarn segment156present in the microwave field is heated by thermal conduction. The portion156acontacted with the liquid precursor140allows its evaporation at the meniscus145. The precursor140thus evaporated spreads towards the reaction zone115to carry out the deposition on the yarn. Pumping can be performed to force this natural propagation of the precursor140towards the reaction zone115. The coating is formed from the gas phase in the reaction zone by chemical vapor infiltration, the coating covering the surface of the filaments forming the yarn150and being deposited in the inter-filament spaces. The distanced from the meniscus145to the reaction zone115can be greater than or equal to 1 cm, for example greater than or equal to 5 cm, for example comprised between 1 cm and 15 cm, for example comprised between 5 cm and 15 cm. This distance may depend on the temperature imposed on the yarn in the reaction zone, as will be detailed below. The reactor120is further provided with two centralizers125present respectively at the two junctions between the horizontal portion121and the two vertical portions122and123of the reactor120. The centralizers125can be in the shape of rollers provided with a groove (not visible in the figures) which have the function of keeping the yarn150centered in the reactor120. The centralizers125are present inside the reactor120. The second vertical portion123and the horizontal portion121each comprise at least one additional centralizer124aand124b. All or part of the additional centralizers124aand124bcan locally narrow the section of the reactor120. It is also possible to add an additional centralizer (not shown) in the first vertical portion122. The device is provided with a scrolling device which may include a first mandrel (not shown) from which the yarn150can be unwound, the first mandrel can be a storage mandrel for the yarn150before it is coated, and a second mandrel (not shown) on which the yarn150can be wound once coated. The yarn may be continuous, extending continuously between the first mandrel and the second mandrel through the reactor120. The yarn150may be moved in the reactor120during the method. A segment to be treated of the yarn150can thus circulate in the reactor120from the first mandrel to the second mandrel. Elements125and124a-bfor centering the yarn150in the reactor120reduce the risk of the yarn150touching the wall of the reactor120. The scrolling device can be controlled by control means not shown, so as to scroll the yarn150in the device100continuously or step by step. The scrolling of the yarn150can be controlled depending on the method parameters, and in particular on the deposition kinetics, in order to finely control the thickness of the coating deposited. In the example ofFIG.1, the yarn150circulates in the reactor120and is partly immersed in the liquid precursor140. The movement of the yarn can be continuous (uninterrupted) or step by step. A segment156of the treated yarn initially circulates in the first vertical portion122without being immersed in the liquid precursor140, the segment is then immersed in the liquid precursor140in the first vertical portion122, then remains immersed in the liquid precursor140in the horizontal portion121and in a portion of the second vertical portion123. The segment of the yarn150then leaves the liquid precursor140to be routed to the reaction zone115where the coating is formed on its surface from the gas phase in a microwave field. The following describes the formation of the gas phase in this example. The liquid precursor140is here evaporated by thermal conduction along the yarn from the segment156heated in the reaction zone115to the meniscus145. The reactor120is provided with at least one channel154a,154bfor introducing a diluent gas200a,200b. The reactor120is here provided with several channels154a,154bfor introducing the diluent gas200a,200b. When several channels154aand154bare present, the diluent gas200aand200bintroduced into each can be identical or different, for example the diluent gas200acan be reactive and the diluent gas200binert. In the example ofFIG.1, the channel(s)154a,154bemerge under the meniscus145of the liquid precursor140. The channel(s)154a,154bcan be carried by the second vertical portion123and emerge therein. The channel(s)154a,154bcan be located below the reaction zone115. When it is introduced into the reactor, the diluent gas200a,200bis directly mixed with the liquid precursor140, as illustrated in the example ofFIG.1. The diluent gas200a,200bis here contacted with the liquid precursor140as it is introduced into the reactor120. The diluent gas200a,200bcan be introduced into the second vertical portion123. The mixture of the diluent gas200a,200band the precursor140can take place in the second vertical portion123. The mixing of the diluent gas200a,200band the precursor140can take place in a zone of movement of the yarn150. The mixing of the diluent gas200a,200band of the precursor140can take place below the reaction zone115. In this example, the diluent gas200a,200bbubbles in the liquid precursor140present in the reactor120. The mixing between the diluent gas200a,200band the precursor140is carried out before the arrival of the gas phase in the reaction zone115. Regardless of the example considered, the distance separating the mixing zone between the precursor and the diluent gas and the reaction zone can be less than or equal to 15 cm, and for example comprised between 1 cm and 15 cm. In this case in the example illustrated, the diluent gas200a,200bis first mixed with the liquid precursor140, which is then evaporated so as to obtain the gas phase comprising a mixture of the diluent gas and the coating precursor at the vapor state, this gas phase then propagates towards the reaction zone115and is introduced into this zone115so as to form the coating on the treated yarn. The diluent gas is separate from the coating precursor in the vapor state. As indicated above, the reaction zone115is in particular devoid of liquid coating precursor, the coating precursor being therein only in vapor form in the example illustrated. It will also be noted that the reactor does not have a heating system at the liquid precursor140. The system can nevertheless include a device for regulating the temperature (not shown) of the liquid precursor140in order to maintain it at a moderate temperature if this is desired depending on the precursor used, for example less than or equal to 20° C. The diluent gas200a,200bcan be reactive or inert with respect to the precursor140. Thus, the diluent gas200a,200bcan react with the carbon of the coating precursor in order to consume the excess carbon compared to the stoichiometry desired for the deposition before introduction of the coating precursor in the vapor state into the reaction zone115. This reaction can take place in the gas phase before its introduction into the reaction zone115, the diluent gas200a,200breacting with the excess carbon of the precursor coating in the vapor state. Alternatively or in combination and as indicated above, the diluent gas200a,200bcan react with the excess carbon of the coating formed in the reaction zone115. The reactive diluent gas200a,200bcan be hydrogen or ammonia. The inert diluent gas200a,200bcan be dinitrogen or argon. By way of example, the liquid coating precursor140can be a silicon carbide precursor. In this case, the precursor140may include one or more silicon atoms, one or more carbon atoms and optionally hydrogen. In particular, the precursor140may include at least one Si—C bond, and optionally at least one Si—H bond and/or at least one Si—Si bond. As examples of usable silicon carbide precursors140, mention may be made of 1,3,5 Trisilacyclohexane (TSCH), hexamethyldisilane (HMDS) or else triethylsilane. In the case of the use of HMDS, it may be advantageous to choose a diluent gas capable of consuming the excess carbon of the precursor in order to obtain pure SiC on the yarn150. By way of example, in the case of a deposition of silicon carbide, the temperature of the yarn150in the reaction zone115can be comprised between 800° C. and 1300° C., for example between 950° C. and 1200° C. Alternatively, the coating precursor140may be a boron nitride precursor. In this case, the precursor140may include one or more boron atoms, one or more nitrogen and hydrogen atoms, and optionally one or more carbon atoms. The precursor140can be an aminoborane. The precursor140may include at least one B—N bond and optionally at least one N—C bond and/or at least one B—C bond. As an example of usable boron nitride precursor140, mention may be made of tris(dimethylamino)borane (TDMAB) or triethylaminoborane (TEAB) optionally mixed with ammonia NH3. The use of TDMAB can advantageously be accompanied by the use of a diluent gas reactive with the carbon in order to consume the excess carbon. By way of example, in the case of a deposition of boron nitride, the temperature of the yarn150in the reaction zone115can be comprised between 900° C. and 1500° C., for example between 1200° C. and 1400° C. Further alternatively it is also possible to form a silicon nitride coating, for example by using hexamethyldisilazane as coating precursor140. The portion of the reactor120between the meniscus145and the reaction zone115can be placed under negative pressure to promote the evaporation of the precursor towards the reaction zone115. The pressure in this portion can nevertheless remain greater than or equal to the vapor pressure of the precursor at the temperature at the meniscus145, in order to avoid too rapid evaporation of the precursor. The pressure in this portion can generally range from 1 mbar to 3 bar. The choice of the pressure to be imposed depending on the precursor used falls within the general knowledge of the person skilled in the art. For example for TDMAB, the pressure in the reactor can be greater than or equal to 3 mbar at 30° C. or greater than or equal to 160 mbar at 100° C. For TEAB, the pressure in the reactor can for example be greater than or equal to 3 mbar at 75° C. or greater than or equal to 16 mbar at 96° C. For triethylsilane, the pressure in the reactor can for example be greater than or equal to 125 mbar at 50° C. The flow rate of diluent gas introduced into the reactor120can be greater than or equal to the flow rate of precursor140evaporated or introduced into the reaction zone115, for example greater than or equal to twice this flow rate. This allows to obtain a gas phase having a volume fraction of diluent gas greater than or equal to the volume fraction of precursor in the vapor state. It will be noted that the reactor120further comprises additional gas inlet157a,157cand outlet159a,159cchannels downstream of the reaction zone115. Thus, the segment156passes successively into the reaction zone115then these channels157a,157cand159a,159c. A buffer gas, for example dinitrogen or argon, can be is introduced through the channels157a,157band157cand159a,159band159cin order to avoid any risk of parasitic deposit at the mandrels of the scrolling device. The gas outlets159a-159callow to evacuate the buffer gas introduced as well as any residual vapor phase precursor. As illustrated, each of the two vertical portions122and123can include at least one inlet channel157a-cand outlet channel159a-cpair. The example of reactor120illustrated comprises a first buffer gas inlet157aand outlet159apair located between the reaction zone115and a centralizer124a, a second buffer gas inlet channel157band outlet channel159bpair located on the vertical portion122upstream of the reaction zone115and a third buffer gas inlet channel157cand outlet channel159cpair located downstream of the centralizer124a. In particular, a reduction in the passage section at the centralizer124a, downstream of the reaction zone115will be noted. This advantageously allows to further reduce the leakage of precursor in the residual vapor state and to improve the centering of the yarn. Of course, the reduction of the passage section is not necessarily ensured by the addition of a specific part124aand can simply be obtained by a local modification of the diameter of the tube forming the reactor. In a variant not shown, the system does not have this passage section reduction. The example of device101inFIG.2which will now be described uses the same structure as device100inFIG.1but supplements it in particular by adding an additional heat treatment zone210. The portions identical to the device100ofFIG.1bear the same reference symbols and are not described again for the sake of brevity. The reactor220ofFIG.2is thus equipped with an additional treatment zone210which is distinct from the reaction zone115and downstream of the latter. Thus, the segment156of treated yarn passes successively through the reaction zone115then through the additional treatment zone210where it undergoes a heat treatment. This zone210can thus be provided with heating means, it is again possible to use microwave heating but the person skilled in the art will recognize that other heating means are possible. The temperature imposed during the heat treatment in the zone210can be greater than or equal to the temperature in the reaction zone115. The temperature in the zone210can be greater than or equal to 1100° C., for example greater than or equal to 1200° C. This temperature can be comprised between 1100° C. and 1700° C., for example between 1200° C. and 1500° C. As indicated above, the heat treatment carried out in the zone210can result in dehydrogenation, crystallization or stabilization of the coating formed in the reaction zone115. It is possible, for example, to carry out, in the zone210, a crystallization or stabilization of a coating of boron nitride by imposing on the yarn a temperature comprised between 1200° C. and 1500° C. Alternatively, it is possible to carry out a heat treatment for the dehydrogenation of a silicon carbide coating by imposing on the yarn150a temperature comprised between 1100° C. and 1500° C. The reactor220is further provided with an inlet157dand an outlet159dfor buffer gas on either side of the zone210in order to inert this zone and avoid parasitic depositions. Alternatively, a reactive gas can be introduced through the inlet157dallowing the dehydrogenation of the coating formed in the reaction zone115.FIG.2illustrates an additional treatment zone210distinct and offset from the reaction zone115along the direction of movement of the yarn150. Nevertheless, the scope of the invention is not departed from when the reaction zone115is heated to a sufficient temperature to both carry out the deposition on the yarn as well as a heat treatment for modifying this deposition, for example dehydrogenation, crystallization or stabilization as carried out in zone210. In the latter case, taking into account the high temperatures imposed in the reaction zone115, it may be advantageous to provide a sufficient distanced between the reaction zone115and the precursor meniscus145, in order to carry out the desired additional treatment without disturbing the evaporation of the precursor by thermal conduction along the yarn. By way of example, this distance may be greater than or equal to 5 cm, for example comprised between 5 cm and 15 cm. The examples of the method which have just been described in connection withFIGS.1and2relate to an introduction of the diluent gas directly into the liquid precursor140.FIG.3, which will now be described, relates to a device102in which the diluent gas is mixed directly with the precursor in the vapor state. The portions identical to those described above are omitted for reasons of brevity. The reactor320illustrated inFIG.3comprises at least one diluent gas introduction channel254a,254bwhich emerges between the meniscus145and the reaction zone115. The diluent gas no longer bubbles in the liquid precursor140but is mixed with the precursor in the vapor state upstream of the reaction zone115after the evaporation of the liquid precursor140in the reactor320. The diluent gas is here introduced above liquid precursor meniscus140. The gas phase obtained after this mixture then propagates to the reaction zone115to form the coating. In a variant not illustrated, it would be possible to combine an introduction of the diluent gas both into the liquid precursor and into the precursor in the vapor state. Also, an additional treatment zone210can be added downstream of the reaction zone115as described inFIG.2. The variant ofFIG.4relates to the case where the precursor is directly introduced in the vapor state into the reactor. In the example of device103ofFIG.4, the diluent gas200a,200bis injected into the reactor420and mixed directly with a flow of precursor in the vapor state240. The pressure in the reactor420can be comprised between 1 mbar and 3 bar. The flow rate of diluent gas200a,200bintroduced into the reactor420may be greater than or equal to the flow rate of precursor240in the vapor state introduced into the reactor420, for example greater than or equal to twice this flow rate of precursor introduced into the reactor420. This allows to obtain a gas phase having a volume fraction of diluent gas greater than or equal to the volume fraction of the precursor in the vapor phase. The figures illustrate devices100-103in which a single yarn150is treated but the invention also applies to simultaneous treatment of a plurality of yarns in the reactor. The treatment of a yarn can, moreover, comprise several passages of the yarn in the reactor so as to deposit each time an additional coating on the coating formed during the preceding passage. The coating thus deposited can be monomaterial or multimaterial. In the examples illustrated, there is no liquid precursor in the reaction zone, however the scope of the invention is not departed from when liquid precursor is present in the reaction zone in addition to the gas phase introduced into this zone. The method can continue by manufacturing a composite material part from several yarns coated in the manner described above. The manufacture of the part may thus include the manufacture of a fibrous preform, intended to form the fiber reinforcement of the part, from a plurality of coated yarns. The fibrous preform can be obtained by weaving, for example by three-dimensional weaving, of the coated yarns. An interlock weave pattern can be used, for example. The porosity of the fibrous preform can then be filled with a die in order to obtain the composite material part. The matrix may be an at least partially ceramic matrix. In a manner known per se, this matrix can be formed by chemical vapor infiltration or by a Melt-Infiltration (“MI”) technique. The matrix may comprise silicon carbide. The part obtained can be a part of a turbomachine, for example of an aeronautical turbomachine or an industrial turbomachine. The part obtained can be a turbine part. The part obtained can be a turbomachine blade, for example a turbine blade. The part obtained can alternatively be a sector of a turbine ring. EXAMPLES Example 1: Deposition of Silicon Carbide A test was carried out using the device100illustrated inFIG.1. The precursor used was HMDS, the temperature of the reaction zone115was maintained at 1070° C. for 3 minutes. Nitrogen was used as the diluent gas200a,200b. The volume fractions of diluent gas and precursor in the gas phase were each 50%. The SiC deposition is effective with reaction zone kinetics of 500 μm/min. In the test carried out, the yarn was static.FIG.5is a cross-sectional view of the resulting coated yarn. Example 2: Deposition of Boron Nitride A test was carried out using the device100illustrated inFIG.1. The precursor used was TDMAB, the temperature of the reaction zone115was maintained at 1270° C. for 12 minutes. Nitrogen was used as the diluent gas200a,200b. The volume fractions of diluent gas and precursor in the gas phase were each 50%. The deposition of BN is effective with a kinetics in the reaction zone of 1.7 μm/min. In the test carried out, the yarn was static. A composite material part was then formed from the coated yarns obtained.FIG.6is a cross-sectional view of the resulting coated yarn. The expression “comprised between . . . and . . . ” must be understood as including the limits. | 24,386 |
11858860 | DETAILED DESCRIPTION Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings. In the drawings, thicknesses of layers or regions are exaggerated for clarity of the specification. The present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. It will be understood that when an element is referred to as being “on” or “above” another element, the element may be in direct contact with the other element or other intervening elements may be present. In the following embodiments, the singular forms include the plural forms unless the context clearly indicates otherwise. It should be understood that, when a part “comprises” or “includes” an element in the specification, unless otherwise defined, it is not excluding other elements but may further include other elements. The use of the term “the” and an instructional term similar to the “the” may be applied to both singular forms and the plural forms. With respect to operations that constitute a method, the operations may be performed in any appropriate sequence unless the sequence of operations is clearly described or unless the context clearly indicates otherwise. The operations may not necessarily be performed in the order of sequence. All examples or example terms (for example, etc.) are simply used to explain in detail the technical scope of the disclosure, and thus, the scope of the disclosure is not limited by the examples or the example terms as long as it is not defined by the claims. It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments. FIG.1is a schematic perspective view of a sintering jig100according to an embodiment. Referring toFIG.1, the sintering jig100may include a first plate110and/or a second plate120. The second plate120may be stacked on the first plate110. The first plate110may be referred to as a lower plate, and the second plate120may be referred to as an upper plate. The first plate110and the second plate120are a jig used for sintering a ceramic pellet formed of ceramic powder and may include a material that does not react with the ceramic at a high temperature. The first plate110and the second plate120may include zirconia. FIG.2is a cross-sectional view taken along line A-A ofFIG.1.FIG.3is a magnified view of a portion ofFIG.2. Referring toFIGS.1through3, the first plate110includes a plurality of protrusions115formed on a first surface110aof the flat plate110. The first plate110according to an embodiment includes six protrusions115, but embodiments are not limited thereto. The first plate110may include more than six or less than six protrusions115. The protrusions115may have cylindrical shape. Upper surfaces115aof the protrusions115may have a low surface roughness so that a reaction of the protrusions115with the sintering ceramic powder is reduced. For example, the surface roughness of the upper surfaces115aof the protrusions115may be 0.2 μm or less. When the upper surfaces115aof the protrusions115are polished to a surface roughness of 0.2 μm or less, a phenomenon of cohesion of the ceramic powder onto the upper surfaces115aof the protrusions115by pressure in a forming process may be solved. The surface roughness is a sum of a height and a depth from a level of a surface thereof, and the degree of the surface roughness may be measured by using an optical microscope. The second plate120may include through holes150that combine with the protrusions115. The through holes150are hollowed empty spaces. The through holes150may include cylindrical portions151through which the protrusions115enter and exit and conical portions152having a taper shape widening towards an upper surface120aof the second plate120from the cylindrical portions151. Bars192(refer toFIG.4) of a manual press190(refer toFIG.4) may enter and exit in the conical portions152. In the case that the second plate120is combined with the first plate110, the upper surfaces115aof the protrusions115may be located in the cylindrical portions151. That is, the protrusions115may occupy a portion of a region of the cylindrical portions151. The protrusions115may have a height h1less than a height h2of the cylindrical portions151. Ceramic powder is supplied onto the protrusions115through the through holes150. FIG.4is a schematic cross-sectional view of a manual press190for making a ceramic pellet by filling ceramic powder in the sintering jig100according to an embodiment. Referring toFIG.4, the manual press190includes a plate191and a plurality of bars192extending from the plate191. The bars192may be formed equal to the number of the protrusions115. As depicted inFIG.4, an edge of each of the bars192may have a shape almost matching to the shape of the conical portion152of the through hole150. However, embodiments are not limited thereto. For example, the shape of the bars192may match to the shape of the cylindrical portions151of the through holes150. The manual press190may include plastic, for example, polyether ether ketone (PEEK). The sintering jig100according to the present embodiment may form ceramic pellets such that, after placing prepared ceramic powder on the first plate110through the through holes150of the second plate120that is stacked on the first plate110, the ceramic powder is pressed by using the manual press190so that the bars192of the plate191enter and exit towards the conical portions152of the through holes150. Thus, the ceramic pellets are formed. Next, the forming of ceramic samples is completed by sintering the ceramic pellets that are filled in the sintering jig100in a state that the manual press190is removed from the second plate120. An optimum ceramic composition having desired physical properties may be found by measuring the characteristics of the sintered ceramic samples. Since ceramic pellets formed on the upper surfaces having a low surface roughness of the protrusions115of the first plate110of the sintering jig100are sintered, a phenomenon of coherence of some of the ceramic pellets onto the first plate110due to reaction of the ceramic pellets with the first plate110of the sintering jig100may be reduced. Also, since a plurality of through holes150are formed in the sintering jig100, the sintering jig100may be used for detecting a useful material by using an HTS method. FIG.5is a schematic cross-sectional view of a sintering jig200according to another embodiment.FIG.6is a magnified view of a portion ofFIG.5. Like reference numerals are used to indicate constituent elements that are substantially identical to the constituent elements of the sintering jig100described with reference toFIG.1, and thus, the detailed description thereof will be omitted. Referring toFIGS.5and6, the sintering jig200may include a first plate210and a second plate220. The second plate220may be stacked on the first plate210. The first plate210may be referred to as a lower plate, and the second plate220may be referred to as an upper plate. The first plate210and the second plate220may be jigs used for sintering ceramic and may include a material that does not react with the ceramic to sinter at a high temperature. The first plate210and the second plate220may include zirconia. The first plate210includes a plurality of protrusions215formed on a first surface210aof the flat plate210. The first plate210according to the present embodiment includes six protrusions215. The protrusions215may be convex units protruding from a first surface210aof the first plate210, and may include convex upper surfaces215a. a central part of each of the protrusions215may convex than peripheral areas thereof. Ceramic pellets formed by the convex protrusions215using ceramic powder may contract during a sintering process, and thus, the sintered ceramic may have reduced contact area with the protrusions215. The upper surfaces215aof the protrusions215should have a surface roughness so that a reaction between the upper surfaces215aof the protrusions215and the sintered ceramic is reduced. For example, the upper surfaces215aof the protrusions215may have a surface roughness of 0.2 μm or less. The second plate220may include through holes250that combine with the protrusions215. The through holes250may include cylindrical portions251through which the protrusions215enter and exit and conical portions252having a taper shape widening upwards from the cylindrical portions251. When the second plate220is combined with the first plate210, the upper surfaces215aof the protrusions215may be located in the cylindrical portions251. That is, the protrusions215occupy some regions of the cylindrical portions251. The protrusions215may have a height h1less than a height h2of the cylindrical portions251. In order to sinter ceramic powder filled in the sintering jig200according to the present embodiment, the manual press190ofFIG.4may be used. Ceramic formed by using the sintering jig200according to the present embodiment may condense during a sintering process, and accordingly, a contact area between the sintered ceramic and the upper surfaces215aof the protrusions215of the first plate210is reduced, and thus, a problem of surface reaction between the first plate210and the sintered ceramic is reduced. FIG.7is a schematic cross-sectional view of a sintering jig300according to another embodiment. Like reference numerals are used to indicate constituent elements that are substantially identical to the constituent elements of the sintering jig100described with reference toFIG.1, and thus, the detailed description thereof will be omitted. Referring toFIG.7, the sintering jig300may include a first plate310. The first plate310may include a plurality of through holes350. The sintering jig300may include bolts370that fill the through holes350. The bolts370may be cylindrical bolts370. A combination of the first plate310and the cylindrical bolts370may be a jig used for sintering ceramic, and may include a material that does not react with the ceramic to sinter at a high temperature. The first plate310and the bolt370may include zirconia. The bolt370has a screw thread377on outer surface. FIG.8is a magnified view of a portion ofFIG.7. Referring toFIGS.7and8, the first plate310may be a flat plate and may include a plurality of the through holes350. The first plate310according to the present embodiment includes six through holes350. The first plate310may include a first surface310aand a second surface310bfacing the first surface310a. The through holes350may include conical portions352formed from the first surface310aand cylindrical portions351formed from the second surface310b. The conical portions352and the cylindrical portions351may be connected to each other. The first plate310includes a first portion311forming the cylindrical portion351and a second portion319forming the conical portion352. A screw groove312and a rim317may be formed inside the first portion311. The screw groove312combines with the screw thread377of the bolt370to form a screw-coupling. The rim317may be formed between the screw thread312and the second portion319. The rim317protrude inwardly along a circumference of the first portion311. When the bolt370combines with the screw groove312of the first plate310, an upper surface317aof the rim317and an upper surface370aof the bolt370may form a coplanar surface. There is a space to form a ceramic pellet between the coplanar surface and the conical portion352. The rim317may reduce a contact area between the upper surface370aof the bolt370and the ceramic pellet. The rim317may support the ceramic pellet or a sintered ceramic thereon in a state when the bolt370is removed. The upper surface370aof the bolt370may have a low surface roughness to reduce a reaction with ceramic thereon. The upper surface370aof the bolt370may have a surface roughness of 0.2 μm or less. Due to the polished cylindrical bolt370of the sintering jig300according to the present embodiment, a surface reaction between the sintering jig300and the ceramic pellets is reduced, and thus, sintered ceramic may efficiently discharged from the through hole350. FIG.9is a schematic perspective view of a sintering jig400according to another embodiment.FIG.10is a cross-sectional view taken along line B-B ofFIG.9, andFIG.11is an exploded view of the cross-sectional view ofFIG.10. Like reference numerals are used to indicate constituent elements that are substantially identical to the constituent elements of the sintering jig100described with reference toFIG.1, and thus, the detailed description thereof will be omitted. Referring toFIGS.9through11, the sintering jig400may include a first plate410and a second plate420. The second plate420may be stacked on the first plate410. The first plate410may be referred to as a lower plate, and the second plate420may be referred to as an upper plate. The second plate420may include a plurality of through holes425. The first plate410and the second plate420may include zirconia. An upper surface410aof the first plate410may have a low surface roughness to reduce a surface reaction with ceramic powder thereon to be sintered. For example, the upper surface410aof the first plate410may have a surface roughness of 0.2 μm or less. The second plate420according to the present embodiment includes six through holes425. A hollow guide mold440may be arranged in each of the through holes425. The hollow guide mold440may contact the upper surface410aof the first plate410. An inner diameter of the hollow guide mold440may define an external diameter of ceramic pellet to be formed. A handle portion442protruding outwards may be formed on an upper part of the hollow guide mold440. The hollow guide mold440may include plastic, for example, PEEK. A press490for forming ceramic pellet may include a cylindrical portion491. A handle portion492may be formed on an upper part of the cylindrical portion491. In the present embodiment, the presses490are separately formed, but the present embodiment is not limited thereto. For example, as depicted inFIG.4, a plurality of the cylindrical portions491may extend from a single plate (not shown). A method of using the sintering jig400according to the present embodiment will be described. First, the second plate420is arranged on the first plate410. Next, the hollow guide molds440are arranged in the through holes425of the second plate420. After filling ceramic powder in the hollow guide molds440, ceramic pellets are formed by molding and pressing the ceramic powder using the presses490. After sequentially removing the presses490and the hollow guide molds440from the second plate420, then the second plate is removed, and sintered ceramics may be formed through a sintering process. In the molding process of the ceramic powder, after removing the hollow guide molds440by pulling the handle portions442in a state that the presses490are pressed, the presses490may be removed first and then the guide molds440and the second plate420may be removed sequentially. Afterwards, a sintering process may be performed. In the sintering jig400according to the present embodiment, a contact between the molded ceramic pellets and the second plate420may be prevented by using the hollow guide molds440, and thus, a reaction of the ceramic pellets with the second plate420may be prevented in a sintering process. Also, due to the polished surface of the first plate410, a reaction of a surface of the first plate410with the ceramic pellets may be reduced. While one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims. | 16,049 |
11858861 | DETAILED DESCRIPTION This disclosure presents a method of applying a polyvinyl butyral (PVB)-based tackifier to ceramic intermediate components/build material (e.g., sheets, tubes, preforms, etc.) of a CMC. The tackifier can be applied to the ceramic material during CMC manufacture by spraying or other local application techniques. Such techniques allow for the incorporation of the tackifier into more complex parts or features and those not easily formed from material pre-impregnated with the tackifier. FIG.1is a flowchart illustrating method10of facilitating formation of a CMC using a tackifier on ceramic build material. To provide the desired level of tack and stabilization to the underlying ceramic material, the tackifier can be a mixture of PVB and ethanol. The amount of PVB in the tackifier compound can range from 3% to 12% in an exemplary embodiment. A range of 3% to 15% PVB is further contemplated herein. As used herein, a percentage of PVB should be understood as a percentage by weight (wt %). The remainder of the compound can be ethanol, or in some embodiments a combination of ethanol and inorganic particles such as silicon carbide particles. The relatively high ratio of ethanol to PVB provides a viscosity suitable for various localized application techniques, discussed in greater detail herein. At step12, the PVB-based tackifier can be applied to ceramic material used to form a CMC. This can occur prior to and/or during preforming as is discussed in greater detail below. In one embodiment, the ceramic material can be a sheet of ceramic fabric formed from, for example, tows of silicon carbide (e.g., Hi-Nicalon™) or other suitable ceramics in various woven architectures. The fabric can be dry or a pre-preg material. The tackifier can be applied to the sheet by spraying, pipetting, or painting, to name a few non-limiting examples. It can be desirable to slow or prevent evaporation of the ethanol within the tackifier after application using backing layers, films, bags, encapsulation, etc. If not already in trimmed to the desired dimensions, the sheet can be cut into multiple plies to be laid up in a preform structure. The PVB-based tackifier helps stabilize the underlying woven fabric when the sheet is being cut such that there is little to no sheet distortion or fiber fraying. The plies cut from one or more sheets can be laid up in a an end-to-end and/or layer-by-layer fashion to form a multidimensional preform structure. In many cases, the preform structure can be supported by one or more sets of rigid tooling, formed from materials such as plastic, steel, aluminum, and or graphite. The tackifier gives each ply a reversible adhesive quality such that any ply can adhere to an underlying tooling surface or ply without shifting its position, while still allowing the ply to be removed and repositioned, if desired, without damaging the repositioned ply or any underlying plies. Similarly, in cases where one or more plies are bent or folded over to form a region of curvature or other complex geometry, the tackifier can cause areas where applied to remain in a bent or folded state and preforming operations can proceed with a reduced risk of needing to rework portions of the part. In an alternative embodiment, the ceramic material being treated at step12can be a biaxial or triaxial braided ceramic (e.g., silicon carbide) material, such as a braided tube on a mandrel. Other three-dimensional structures are contemplated herein. Similar to the ceramic sheet, the tackifier can be applied to all or a portion of the braided material by any of spraying, pipetting, or painting during or after braiding. This allows for the initial formation of the braided architecture with a non-tackified ceramic material, preferable during the braiding process, and the subsequent reinforcement with the tackifier to facilitate handling. More specifically, the braided tube with applied tackifier can be incorporated into a preform structure with other tackified or non-tackified tubes and/or plies with the ability to be handled and modified with less likelihood of damage or distortion. In yet another alternative embodiment, the ceramic material being treated at step12can be a preform structure in the nominal shape of the final component formed from one or more ceramic plies, braided tubes, etc. In such an embodiment, the tackifier can be applied locally by spraying, pipetting, or painting, or the preform structure and any underlying tooling can be immersed in a bath of the PVB -based tackifier. However carried out, the tackifier need not be applied to the entire preform structure. It should be noted that immersion can be used in other embodiments to treat sheets and/or braided tubes without departing from the scope of the invention. A preform treated in this manner can be, for example 3% to 15% PVB. It is further possible for the PVB-based tackifier to be applied to the ceramic build materials during preforming. More specifically, the tackifier can be applied in any manner discussed above to plies and/or three-dimensional structures (e.g., tubes) as they are being incorporated into the preform. As with the previously-discussed embodiments, the tackifier can be broadly or selectively applied to areas requiring additional tack to become or remain adhered to another structure and/or to retain a certain shape during preforming. Such application of the tackifier also applies to materials previously treated (e.g., by local application or as a pre-preg) with the PVB-based or other tackifier if the solvent evaporates prematurely. In such cases, the PVB-based tackifier, preferably with a higher ethanol content (e.g., >95%), can be used to help restore the properties of the resin system. For all embodiments, at step14, the ethanol within the tackifier can be removed using one or a combination of heat and a vacuum, using, for example, a vacuum oven or other suitable equipment. After the ethanol has been removed, the PVB binds the various ceramic layers together and stabilizes/rigidizes the underlying structure. More specifically, when vacuum pressure and/or heat is no longer applied, the remaining PVB can help the underlying structure retain a compressed state. Step14can be carried out after preforming is complete, or in stages during preforming (e.g., in an embodiment with tackified plies). At step16, the PVB can be removed from the preform structure. In one embodiment, removal can constitute burning off/thermally decomposing the PVB by placing the preform in a nitrogen-rich (N2) environment and exposing the preform to a temperature ranging from 500° F. (260° C.) to 1350° F. (732.2° C.), and in an exemplary embodiment, between 800° F. (426.7° C.) to 1150° F. (621.1° C.). In an alternative embodiment, the environment can include a mixture of nitrogen (N2) and hydrogen (H2) gases. The PVB burns off fairly cleanly, meaning that only insignificant amounts of ash from PVB, if any, remains after step16. In an embodiment in which the tackifier includes inorganic (e.g., silicon carbide) particles, such particles remain incorporated into the preform structure after removal of the ethanol and PVB, and can facilitate matrix formation and densification. In another alternative embodiment, the PVB can be removed through other means by washing with ethanol or other suitable solvent without departing from the scope of the invention. At step18, the preform structure can undergo matrix formation and densification using one or a combination of chemical vapor infiltration or chemical vapor deposition (CVI or CVD). During densification, the plies are infiltrated by reactant vapors, and a gaseous precursor deposits on the fibers. The matrix material can be a silicon carbide or other suitable ceramic material. Densification is carried out until the resulting CMC has reached the desired residual porosity. In an alternative embodiment, densification can include other methodologies including, but not limited to, melt infiltration and polymer infiltration and pyrolysis (PIP). At step20, various post-processing steps can be performed, such as the application of one or more protective coatings (e.g., environmental and/or thermal barrier coatings). A bond coat can also be applied to facilitate bonding between the CMC and a protective coating. Other protective coatings, especially those suitable for use in a gas turbine engine environment, are contemplated herein. The resulting CMC formed with the tackified ceramic can be incorporated into aerospace, maritime, or industrial equipment, to name a few, non-limiting examples. Discussion of Possible Embodiments The following are non-exclusive descriptions of possible embodiments of the present invention. A method of forming a ceramic matrix composite includes applying a tackifier of ethanol and 3% to 12% polyvinyl butyral to a ceramic material, removing the ethanol from the ceramic material, and burning off the polyvinyl butyral. The step of applying the tackifier includes one of a spraying, pipetting, painting, and immersing technique. The method of the preceding paragraph can optionally include, additionally and/or alternatively, any one or more of the following features, configurations and/or additional components: In the above method, the ceramic material can include a sheet of woven ceramic fabric, and the step of applying the tackifier can include one of spraying, pipetting, and painting. Any of the above methods can further include forming a plurality of plies from the ceramic fabric sheet, and laying up the plurality of plies into a preform structure. In any of the above methods, the step of removing the ethanol can include one or a combination of a heating the plurality of plies and applying a vacuum to the plurality of plies. In any of the above methods, the step of removing the polyvinyl butyral can include one of burning off the polyvinyl butyral and washing the polyvinyl butyral with a solvent. In any of the above methods, the step of burning off the polyvinyl butyral can include heating the preform structure to a temperature ranging from 500° F. to 1350° F. and placing the preform structure in a nitrogen-rich environment. Any of the above methods can further include densifying the preform structure using one or a combination of chemical vapor infiltration, chemical vapor deposition, polymer infiltration and pyrolysis, and melt infiltration. In any of the above methods, the ceramic material can include a braided ceramic material, and the step of applying the tackifier can include one of spraying, pipetting, and painting. Any of the above methods can further include incorporating the braided ceramic material into a preform structure. In any of the above methods, the step of removing the ethanol can include one or a combination of a heating the plurality of plies and applying a vacuum to the plurality of plies. In any of the above methods, the step of removing the polyvinyl butyral can include one of burning off the polyvinyl butyral and washing the polyvinyl butyral with a solvent. In any of the above methods, the step of burning off the polyvinyl butyral can include heating the preform structure to a temperature ranging from 500° F. to 1350° F. and placing the preform structure in a nitrogen-rich environment. Any of the above methods can further include densifying the preform structure using one or a combination of chemical vapor infiltration, chemical vapor deposition, polymer infiltration and pyrolysis, and melt infiltration. In any of the above methods, the ceramic material can include a ceramic preform structure, and the step of applying the tackifier can include one of spraying, pipetting, painting, and immersing. In any of the above methods, the step of removing the ethanol can include one or a combination of a heating the plurality of plies and applying a vacuum to the plurality of plies. In any of the above methods, the step of removing the polyvinyl butyral can include one of burning off the polyvinyl butyral and washing the polyvinyl butyral with a solvent. In any of the above methods, the step of burning off the polyvinyl butyral can include heating the preform structure to a temperature ranging from 500° F. to 1350° F. and placing the preform structure in a nitrogen-rich environment. Any of the above methods can further include densifying the preform structure using one or a combination of chemical vapor infiltration, chemical vapor deposition, polymer infiltration and pyrolysis, and melt infiltration. In any of the above methods, the tackifier can further include inorganic particles. An intermediate ceramic material for use in a ceramic matrix composite includes silicon carbide with 3% to 15% polyvinyl butyral. While the invention has been described with reference to an exemplary embodiment(s), it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment(s) disclosed, but that the invention will include all embodiments falling within the scope of the appended claims. | 13,445 |
11858862 | DETAILED DESCRIPTION Methods of producing a ceramic matrix composite part are provided. A ceramic fiber preform may be provided, the ceramic fiber preform including a three-dimensional framework of a plurality of ceramic fibers. Prior to melt infiltration, a layer of machinable stock may be added to a target area of the ceramic fiber preform. Melt infiltration may be performed on the ceramic fiber preform. The ceramic matrix composite part may be formed by cooling the melt infiltrated ceramic fiber preform. The part may be machined in the target area where the machinable stock is located. One interesting feature of the systems and methods described below may be that the machinable stock may protect the fiber and fiber coatings of the ceramic matrix preform from exposure to environmental risks, therefore increasing the life of the ceramic composite part. Alternatively, or in addition, an interesting feature of the systems and methods described below may be that use of the machinable stock may prevent the need for an environmental barrier coating (EBC) to protect the ceramic matrix composite part, which may be costly and time-consuming to apply. Alternatively, or in addition, an interesting feature of the systems and methods described below may be that use of the machinable stock may eliminate the need for a second machining process. Alternatively or in addition, the machinable stock may allow for improved dimensional tolerance of the part, better surface finishing, reduced porosity on seal surfaces, and/or a thinner coating on flow paths of the part without intentionally or inadvertently machining into the fibers of the preform. FIG.1illustrates a flow diagram of a method100to produce a ceramic matrix composite. As further explained below, ceramic fibers, which are in a ceramic fiber preform may be arranged in fiber tows or, additionally or alternatively, may not be arranged in tows and may be arranged as individual fibers. The ceramic fiber preform (or simply “preform”) may comprise a three-dimensional framework of, for example, continuous ceramic fibers. The ceramic fiber preform may have the approximate shape of a ceramic matrix composite component being produced. Examples of the ceramic fibers may include carbon (C), silicon carbide (SIC), alumina (Al2O3) and mullite (Al2O3-SiO2) fibers. In the context of this disclosure, carbon and carbon fibers may be considered ceramic material even if carbon and carbon fibers are not generally considered ceramic material. Referring again toFIG.1, the method100may begin by providing (102) the fiber preform202(shown inFIGS.2-5). In some examples, the preform may be formed by laying up plies comprising fibers or tows of fibers204(shown inFIGS.2-5) arranged in a two- or three-dimensional weave. The two- or three-dimensional weave for each of the plies may be formed by weaving the fibers or tows together. Alternatively, the entire preform may be formed by weaving a three-dimensional weave. In still other examples, the preform may be formed by laying up tape that includes the fibers and/or tows of fibers. Any other method of forming the fiber preform may be used as long as the fiber preform includes one or more fibers or fiber tows. The method may further comprise, before or after forming the framework, forming an interface coating on the ceramic fibers to provide a weak fiber-matrix interface once the CMC is formed, which can be beneficial for fracture toughness. Typically, the interface coating includes one or more layers comprising boron nitride and/or silicon-doped boron nitride, The matrix material is typically deposited after the interface coating. The method may also include forming a rigidized fiber preform by depositing a matrix material such as silicon carbide on the fiber preform via chemical vapor infiltration or another deposition process known in the art. The fiber preform, which may be a rigidized fiber preform as described above, may be infiltrated with a slurry comprising ceramic particles and optionally reactive elements/particles to form an impregnated fiber preform, i.e., a fiber preform loaded with particulate matter (ceramic and optionally other particles), prior to application of the slurry layer, as discussed above. Typically, the impregnated fiber preform comprises a loading level of particulate matter from about 40 vol.% to about 60 vol.%, with the remainder being porosity. In addition, the method may further comprise, after applying the heat and pressure to form the protective surface layer116, melt infiltrating the fiber preform102followed by cooling, thereby forming a ceramic matrix composite122that has the protective surface layer116. hi embodiments where the particulate layer104is formed on a fiber preform102comprising a melt-infiltrated preform, as discussed above, the ceramic matrix composite122is already present during the formation of the protective surface layer116. Still referring toFIG.1, the method may continue by infiltrating the fiber preform with a matrix material. Infiltrating the fiber preform with the matrix material may, for example, comprise slurry infiltration. During slurry infiltration, the rigidized fiber preform may be infiltrated with a slurry comprising ceramic particles and optionally reactive elements/particles to form an impregnated fiber preform or “green body,” in other words, a fiber preform loaded with particulate matter. Typically, the impregnated fiber preform comprises a loading level of particulate matter from about 40 vol.% to about 60 vol.%, with the remainder being porous. After slurry infiltration, a machinable stock206,402(shown inFIGS.2-5) may be added (104) to target areas of the ceramic preform202(shown inFIGS.2-5). Additionally or alternatively, the machinable stock206,402may be applied to the preform202during, or simultaneously with, the slurry infiltration. Adding the machinable stock may comprise the application of layers of ceramic slurry206(shown inFIGS.2-5) and/or ceramic tape402(shown inFIGS.2-5) and/or combination of both. For example, one or more layers of ceramic slurry206may be added to the surface of the of the fiber preform202. The slurry206may comprise ceramic particles in a carrier liquid. The slurry206may be, for example, sprayed on to the surface of the preform202. The slurry206may be applied at room temperate, may have relatively low viscosity and, for example, may be water based. The slurry206may be dried after application to remove the water. The slurry206may, for example, be sanded after application to even out or flatten the surface of the preform202after application of the slurry206. The application of the multiple slurry layers may comprise spraying, dip-coating, spin-coating and/or another deposition method. Typically, application of the slurry layers122is carried out under ambient conditions, such as at atmospheric pressure, in air, and/or at room temperature (20-25° C.). Active drying to remove the carrier liquid may be carried out at room temperature or at an elevated temperature (e.g., from about 30° C. to about 200° C.) in ambient conditions or in a controlled environment, such as under vacuum or in an inert gas atmosphere; passive drying may occur by evaporation during or after application of the slurry layers. A typical time duration for drying is from about two hours to about 24 hours. Additionally or alternatively, the machinable stock206,402may be added (104) to target areas of the ceramic preform202by applying one or more layers of ceramic tape402to the surface of the fiber preform202. Such an application of ceramic tape and/or slurry, for example, may be described in U.S. Pat. No. 11,186,525 and U.S. Patent Application Publication 2022/0169574, both of which are incorporated by reference. The ceramic tape402may comprise ceramic particles in a polymeric binder. The ceramic tape402may be prepared by tape casting a typically water-based slurry comprising the ceramic particles and the polymeric binder onto a flexible polymeric sheet, followed by drying of the slurry and separation of the ceramic tape from the polymeric sheet. The ceramic tape402may have a thickness in a range from about 50 μm to about 250 μm (about 2-10 mils). Additionally or alternative, up to 1.2 mm of ceramic tape may be applied402, for example, by layering 6×0.2 mm pieces of ceramic tape402, or, additionally or alternatively, by using a single piece of tape4021.2-2 mm of maximum thickness. The ceramic particles may comprise silicon carbide particles, silicon nitride particles, and/or silicon nitrocarbide particles. The polymeric binder may comprise polyethylene glycol, an acrylate co-polymer, a latex co-polymer, and/or polyvinyl butyral. In addition to the ceramic particles and polymeric binder, the ceramic tape may further include a dispersant, such as ammonium polyacrylate, polyvinyl butyral, a phosphate ester, polyethylene imine, and/or BYK®110(Byk USA, Wallingford, CT), and/or a plasticizer. Like the inner and outer slurry layers discussed above, the ceramic tape may further comprise other particulate solids in addition to the ceramic particles, such as silicon particles, carbon particles and/or other types of reactive particles. The ceramic and other optional particulate solids employed for the inner and outer tape layers typically have an average width or diameter in a range from about 0.5 micron to about 20 microns. Prior to applying the tape402, an adhesive may be deposited (e.g., by spraying) to promote attachment of the ceramic tape. The adhesive may comprise the polymeric binder used in the ceramic tape402. Typically, application of the tape402layers is carried out under ambient conditions, such as at atmospheric pressure, in air, and/or at room temperature (20-25° C.). After application the layers of ceramic slurry and/or layer of ceramic tape may be laminated together and/or to the surface to form the porous ceramic multilayer. Lamination may comprise, for example, vacuum bagging. Lamination may comprise applying pressure and heat to the tape, for example, pressure of approximately −20 to −30 inHg at 90-120° C. for 30 minutes to 2 hours. During lamination, tooling may be applied to the preform202, slurry206, and/or tape402assembly, for example, to apply pressures and/or impart a shape onto the surface of the preform202. After lamination, the preform202may be cooled to room temperature and the tooling removed. Still referring toFIG.1, the method may continue by infiltrating (106) the fiber preform202with a matrix material aging. Infiltrating (106) the fiber preform with the matrix material may, for example, include melt infiltration. During melt infiltration, a molten material may be infiltrated into the fiber preform202(which may be a rigidized and/or impregnated fiber preform as described above). The molten material may, for example, consist essentially of silicon (e.g., elemental silicon and any incidental impurities) or may comprise a silicon-rich alloy. Alternatively, the molten material may comprise any other molten matrix material. Melt infiltration may be carried out at a temperature at or above the melting temperature of silicon or the silicon alloy which is infiltrated. Thus, the temperature for melt infiltration is typically in a range from about 1400° C. to about 1500° C. A suitable time duration for melt infiltration may be from 15 minutes to four hours, depending in part on the size and complexity of the ceramic matrix composite to be formed. However, other durations may be possible. A ceramic matrix is formed from ceramic particles as well as ceramic reaction products created from the reaction between the molten material and any other reactive particles (e.g., carbon particles, refractory metal particles) in the fiber preform. Typically, the ceramic matrix comprises silicon carbide, but may also or alternatively comprise silicon oxycarbide, silicon nitride, alumina, aluminosilicate, and/or boron carbide or another refractory carbide. Cooling (108) may follow melt infiltration, thereby forming a densified ceramic matrix composite. The surface of the preform202, with the added machinable stock206,402, may then be machined (110) as desired to meet any dimensional tolerances in any target areas of the ceramic matrix composite part600(shown inFIGS.6A-Band7-8). The machinable stock added may have a thickness of 200-2000 μm, particularly a thickness of 300-1200 μm. For example, the ceramic matrix composite part600may be a part of a turbine engine, such as a blade, vane, or seal segment. Specific areas of the ceramic matric composite part600may require precision machining to meet necessary dimensional tolerances and/or surface quality standards. A precision machined surface feature is defined as any surface feature with a profile tolerance of 0.25 mm, For example, such target areas may be seal lands, flow paths, and/or datum surfaces. In some examples, the machinable stock206,402may be added only to critical areas of the part600. For example, target areas of the part600may require a profile tolerance of 0.10 mm on sealing surfaces,0.20mm on coating substrate surfaces, and/or flatness of 0.050 mm for datum surfaces. FIGS.2-5illustrate a cross-sectional view of an example of a ceramic matrix composite part being formed using a method of forming a ceramic matric composite with a machinable stock, for example, the method shown inFIG.1.FIGS.2-5illustrate an example target area200of a ceramic matrix composite part.FIG.2illustrates the fiber preform202comprising fibers or tows of fibers204after slurry infiltration, InFIG.2, a first layer206of the machinable stock is shown applied to the surface of the preform202. The first layer206may, for example, be a layer of ceramic slurry sprayed onto the preform202. Additionally or alternatively, the first layer206may be ceramic tape. FIG.3illustrates the sanding of the first layer206of the machinable stock to even or level the surface of the preform202. For example, a sanded down layer of ceramic slurry.FIG.4illustrates the application of a second layer402of machinable stock. The second layer402may comprise, for example, a layer of ceramic slurry applied (such as sprayed) onto the preform202. Additionally or alternatively, the second layer402, may comprise ceramic tape applied on top of the first layer206of the machinable stock. Each layer206,402may comprise multiple additional layers, such that the machinable stock is built up to be a thick as needed to accommodate the needed machined surface features and/or tolerances.FIG.5illustrates a machined machinable stock layer206,402, machined to a specified dimensional tolerance of the target area200. FIGS.6A-Band7-8illustrate an example of a ceramic matrix composite part600with target areas200, such as the target areas200shown inFIGS.2-5and formed using the method shown inFIG.1.FIGS.6A-Band7illustrate a high-pressure seal segment600of a turbine engine, but the ceramic matrix composite part may, for example, be a different turbine component, such as a blade or vane. In the example shown inFIGS.6A-Band7, the target areas200may be, for example, seal lands and/or the ends of the part where an exact size specification is needed. Machinable stock206,402may be built up in the target areas200of the ceramic matrix composite part600on areas of the part600that require precision machine features or specific dimensional tolerances. The machinable stock206,402may only be applied to the critical target areas200, leaving the remaining surface of the part600untreated. InFIGS.6A-Band7, the smooth, machined surface of the machinable stock on the target areas200is represented by the areas with sporadic, spaced out tic marks or dashes. Rough, regular as-formed areas602without machining are represented by a dotted surface. Machined CMC surfaces without machinable stock604, where there exposed fibers, are represented by cross-hating. The method illustrated inFIG.1may include additional, different, or fewer operations than illustrated. For example, although infiltrating the fiber preform with the matrix material includes slurry infiltration and melt infiltration in the example described above, infiltrating the fiber preform may include additional, fewer, or different infiltration processes, for example, such as chemical vapor infiltration. As another example, the method may further comprise, before or after forming the framework, forming an interface coating on the fibers to provide a weak fiber-matrix interface once the CMC is formed, which can be beneficial for fracture toughness. Typically, the interface coating includes one or more layers comprising boron nitride and/or silicon-doped boron nitride. The CVI SIC matrix material is typically deposited after the interface coating. As still another example, the method may further comprise applying further treatments such as applying a coating. An example of such a coating is an environmental barrier coating. An environmental barrier coating (EBC) may be applied to the CMC by depositing the EBC on the fully processed CMC part after the machining step. Additionally or alternatively, the applying EBC may be followed by additional machining. The fibers204that serve as the framework of the fiber preform typically comprise silicon carbide, but may also or alternatively comprise another ceramic, such as silicon nitride, alumina, or aluminosilicate, or carbon. In some examples, the ceramic matrix composite may be referred to as a SiC/SiC composite. The ceramic matrix composite produced may form part or all of a component of a gas turbine engine, such as a blade or vane. To clarify the use of and to hereby provide notice to the public, the phrases “at least one of <A>, <B>, and <N>” or “at least one of <A>, <B>, . . . <N>, or combinations thereof” or “<A>, <B>, . . . and/or <N>” are defined by the Applicant in the broadest sense, superseding any other implied definitions hereinbefore or hereinafter unless expressly asserted by the Applicant to the contrary, to mean one or more elements selected from the group comprising A, B, . . . and N. In other words, the phrases mean any combination of one or more of the elements A, B, . . . or N including any one element alone or the one element in combination with one or more of the other elements which may also include, in combination, additional elements not listed. Unless otherwise indicated or the context suggests otherwise, as used herein, “a” or “an” means “at least one” or “one or more.” While various embodiments have been described, it will be apparent to those of ordinary skill in the art that many more embodiments and implementations are possible. Accordingly, the embodiments described herein are examples, not the only possible embodiments and implementations. The subject-matter of the disclosure may also relate, among others, to the following aspects: A first aspect relates to a method to produce a ceramic matrix composite part, the method comprising: providing a ceramic fiber preform, the ceramic fiber preform including a three-dimensional framework of a plurality of ceramic fibers; prior to melt infiltration, adding a layer of machinable stock to a target area of the ceramic fiber preform; melt infiltrating the ceramic fiber preform; forming the ceramic matrix composite part by cooling the melt infiltrated ceramic fiber preform; and machining the part in the target area where the machinable stock is located. A second aspect relates to the method of aspect1wherein the machinable stock comprises a layer of ceramic tape. A third aspect relates to the method of any preceding aspect wherein he machinable stock comprises a layer of ceramic slurry. A fourth aspect relates to the method of any preceding aspect wherein the machinable stock is sprayed onto the fiber preform. A fifth aspect relates to the method of any preceding aspect wherein the machinable stock is water based. A sixth aspect relates to the method of any preceding aspect wherein the machinable stock comprises ceramic slurry and ceramic tape. A seventh aspect relates to the method of any preceding aspect wherein the target area of the ceramic fiber preform is an area of the ceramic matrix composite part with a precision machined surface feature. An eighth aspect relates to the method of any preceding aspect wherein the machining the part comprises precision machining the part to meet dimensional tolerance requirements, A ninth aspect relates to the method of claim any preceding aspect wherein the machinable stock is between 0.3 to 1.2 mm thick. A tenth aspect relates to the method of any preceding aspect wherein the ceramic matrix composite part is a vane or blade. An eleventh aspect relates to the method of any preceding aspect wherein the machinable stock is applied to the preform at room temperature A twelfth aspect relates to the method of any preceding aspect wherein the ceramic matrix composite is a seal segment. A thirteenth aspect relates to the method of any preceding aspect wherein the target area comprises a seal land, A fourteenth aspect relates to the method of any preceding aspect wherein the target area comprises a datum surface. A fifteenth aspect relates to the method of any preceding aspect wherein the target area comprises a flow path area of a turbine. A sixteenth aspect relates to the method of any preceding aspect further comprising slurry infiltrating the ceramic fiber preform before the layer of machinable stock is added. A seventeenth aspect relates to a method to produce a ceramic matrix composite part, the method comprising: providing a ceramic fiber preform, the ceramic fiber preform including a three-dimensional framework of a plurality of ceramic fibers; slurry infiltrating the ceramic fiber preform adding a layer of ceramic machinable stock to a target area of the ceramic fiber preform, wherein the target area is an area of the ceramic matrix composite part with precision machined surface features; melt infiltrating the ceramic fiber preform; forming the ceramic matrix composite part by cooling the melt infiltrated ceramic fiber preform; and machining the part in the target area where the machinable stock is located. An eighteenth aspect relates to the method of aspect 17 wherein the ceramic matrix composite part is a turbine engine component. A nineteenth aspect relates to the method of any preceding aspect wherein the target area is a flow path of a turbine, A twentieth aspect relates to the method of any preceding aspect wherein the target area is a datum surface. In addition to the features mentioned in each of the independent aspects enumerated above, some examples may show, alone or in combination, the optional features mentioned in the dependent aspects and/or as disclosed in the description above and shown in the figures. | 22,881 |
11858863 | DETAILED DESCRIPTION For the purposes of promoting an understanding of the principles of the claimed technology and presenting its currently understood best mode of operation, reference will now be made to the embodiments illustrated in the drawings and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the claimed technology is thereby intended, with such alterations and further modifications in the illustrated device and such further applications of the principles of the claimed technology as illustrated therein being contemplated as would normally occur to one skilled in the art to which the claimed technology relates. As shown inFIGS.1A-2B, the present novel technology relates to a perfectly wetting surface with a substrate having a predetermined fixed geometric shape, as well as the method for producing the same. The wetting surface can be obtained by creating a rigid, inorganic but porous substrate that can be filled, for example by infiltration into the porous geometric substrate, with the fluid material intended to wet. If this fluid is a molten and or near/molten metal, upon melting the metal volume expands (with only one commonly known exception, silicon metal), exudes from the pores onto the substrate surface, and provides a thin layer of liquid that matches the molten metal intended to wet. On cooling the molten metal volume decreases as it eventually solidifies. The density increase on solidification substantially reduces the volume, causing the metal to retreat into the pore structure where it resides until the system is heated again. The next time the system is heated the metal melts to become a fluid that expands and exudes out of the pores to the surface again providing a perfectly wetting surface. The process can be repeatable over multiple cycles. The metal may be an elemental metal, such as aluminum, silver, copper, or the like, or may be an alloy, such as solder (lead-tin, tin-silver-copper or the like), bronze, or the like. It may be advantageous to use an alloy to infiltrate the pores if the wetting metal is likewise an alloy of the same metals or one of the metals in the alloy. One embodiment of this invention includes the fabrication of a porous substrate having a predetermined geometric shape and comprising a monolithic ceramic in which the pores can be filled with a given liquid such as a molten metal. For purposes of this description a given ceramic is to be considered as a non-metallic material including, but not limited to, oxide, carbide, nitride, and/or boride bodies that exhibit ionic or covalent bonding. The porous substrate can be a ceramic with a continuous pore structure and can be prepared by powder processing followed by sintering to a point where there is a continuous pore structure and where the sintered substrate exhibits sufficient strength for a given application. It is anticipated that the sintering temperature will typically be greater than the melting point of the metal intended to wet the surface. Applicants appreciate that if the sintering temperature were to be less than the melting point of the metal, the pore structure would likely continue to decrease with time leading to dimensional instability and eventual failure. Applicants appreciate that a given infiltrated fluid can be similar or identical to the liquid desired for wetting upon the outer surface of the substrate. The fluid is provided by heating the solid above the infiltrated metal's melting point. Some candidate metals are listed in Table I. These examples are listed for descriptive purposes and this invention is in no way intended to be limited in this regard. Except for silicon, all the metals possess a solids density that is greater than the liquid density. Therefore, on melting a given non-silicon metal, the volume of the resulting fluid is greater than that of the initial solid metal. Typically, at least a five-percent increase in volume is required to provide a surface coating of liquid metal in the application. There does not appear to be an upper limit for the application regarding the volume increase on melting. TABLE IList of potential elemental metals that could be used to fill the pore structure. Inthis list there is only one metal that will not work for this application (silicon, left in forcontrast purposes) because the density of the molten metal is greater than the density ofthe solid so on melting the volume decreases. Other metallic elements, alloys, orcompounds could likewise potentially work to create perfectly wetting surfaces.MoltenSolid(liquid)DensityVolumeAtomicdensitydensityDecrease ondifferenceElementName#TM(° C.)(g/cm3)(g/cm3)Melting*(%)MgMagnesium126501.7381.5840.1549.7%AlAluminum136602.72.3750.32513.7%SiSilicon1414142.332.58−0.25−9.7%SSulfur161151.961.8190.1417.8%TiTitanium2216684.5064.110.3969.6%MnManganese2512467.475.951.5225.5%FeIron2615387.876.980.8912.8%CoCobalt2714958.97.751.1514.8%NiNickel2814558.9087.811.09814.1%CuCopper2910858.967.8981.06213.4%ZnZinc304207.136.570.568.5%MoMolybdenum42262310.289.330.9510.2%AgSilver4796210.499.3461.14412.2%SnTin502327.316.990.324.6%AuGold79106419.3217.312.0111.6%PbLead8232711.3610.680.686.4%*A negative value indicates that the solid density is less than the molten density and therefore the metal will expand during solidification. A sintered ceramic may be prepared and provided as an initial step. While not wishing to be limited in this respect, it has been demonstrated that that a small and uniform pore size tends to be generally desirable, for example with a mean pore diameter not larger than 20 microns, and more typically the pore diameter is in the range of 5-10 microns. Typically, a uniform pore structure will tend to provide for a more uniform liquid metal coating of the substrate. In some embodiments the porous substrate can be machined to the proper shape either before or after sintering, depending on the application. Once the sintered substrate has been prepared the sintered substrate may be placed into a vacuum furnace in contact with the metal intended to be used to fill the pore. The furnace chamber, and the porous body, are evacuated to remove air from the pore structure. Once evacuated the furnace can be heated to sufficient temperature to melt the metal and the metal is then introduced by infusion to the compact. There are generally two cases: (1) the metal wets the substrate; and (2) the metal does not wet the substrate.(1) The metal wets the substrate: The sintered substrate is placed in a crucible containing solid metal particles or chunks. The sample is evacuated by way of vacuum, the metal melts and wets, and because it is wetting, it infiltrates the pore structure by capillary action. Once the infiltration process is complete the furnace is cooled, and the metal allowed to solidify within the substrate. It is possible that a post-infiltration machining step (or similar step such as grinding or bead blasting) can be advantageous for example to remove excess metal from the surface of the infiltrated substrate composite.(2) The metal does not wet the substrate: The sintered compact is placed in a crucible and evacuated. A greater amount of metal is necessary in this case, as the substrate must be submerged in the liquid metal pool after melting. In most cases the molten metal fluid will have a higher density that the porous substrate. This can cause the substrate to float in the molten metal pool, such that the substrate may be held below the surface of the molten metal pool to effect complete and prolonged submersion of the substrate in the liquid metal. Once the metal is melted and the surface of the substrate is covered with molten metal, the furnace is pressurized to force the metal into the substrate pore structure. The amount of pressure required to force liquid metal into the substrate pore structure depends on the degree of non-wetting of the metal and the substrate pore size. Once the pore structure is filled, the furnace can be cooled to solidify the metal. The applied pressure in the furnace can be decreased after the metal has solidified. As with Case 1 above, a post-infiltration machining step (or similar step such as grinding or bead blasting) can be advantageous for example to remove excess metal from the infiltrated substrate composite. The metal-infiltrated porous substrate is now ready for use for example in applications where it is desired to coat, by way of wetting, an identical and/or similar fluid onto the substrate surface. When heated above the melting point of the metal, the molten metal forms an identical and/or similar fluid that coats the exterior surface of the substrate. Since the coating fluid matches the chemistry of the infiltrated fluid, a perfectly wetting surface is created and there is the potential for the coating fluid to some extent mix with the liquid that fills the pores. Even if the metal is non-wetting, such infiltrated metal tends not to leave the pore structure on re-melting. When the application is completed, the substrate can be cooled, and the metal can be expected to retract back into the pore structure during solidification as described above. The substrate can be prepared from various ceramic materials including but not limited to alumina, mullite, spinel, magnesia, refractory cements, zirconia, glass, silicon carbide, silicon nitride, combinations thereof, and the like. The choice of the substrate tends to be influenced by the melting point of the metal (as stated previously the sintering temperature of the substrate should generally be greater than the melting point of the metal) and by the relative stability of the oxide or carbide with respect to the molten metal. If, for example, the metal is more energetically favorable to form an oxide than the substrate material, the molten metal will scavenge oxygen from the oxide substrate and the substrate will be destroyed in use. The metal oxide stability can be predicted by using an Ellingham Diagram. An example of a potential problem would be the use of an alumina (Al2O3) as a substrate for magnesium metal (Mg). MgO is thermodynamically favored to form and the molten Mg will scavenge oxygen from the alumina substrate to create MgO. Similarly, a silicate-based substrate, such as a glass will generally be incompatible with aluminum metal as the Al tends to strip oxygen from the silicate to form alumina. The stability of these three oxides, from highest to lowest, is MgO>Al2O3>SiO2. A similar argument can be made for selecting carbides, but in this case the molten metal would prefer to form the carbide by stripping carbon from the carbide. This is less likely to be a concern but may become so if some of the high melting point refractory metals are used to create a wetting surface. For example, a SiC substrate could be used with molten aluminum because aluminum carbide (Al4C3) is less stable than SiC. As a demonstration, a uniform pore structure SiC monolith was created as described below. Preparation of Sintered Porous Silicon Carbide Porous Body In one embodiment fine alumina (D50=0.3 μm) and colloidal silica (D50=50 nm) powders were added to the silicon carbide as sintering agents. The addition was conducted via a heterocoagulation process to adhere to the surface of SiC particles controlled amounts of alumina and silica. Two abrasive grade SiC powders were evaluated: 240 grit (coarse) and 1200 grit (fine). An example of the coated SiC surface is presented inFIG.1. The heterocoagulation process was conducted in an aqueous medium. A series of blends of coarse and fine SiC powders were prepared to control the pore size and pore volume. It is well known that particle packing can be altered by blending particle sizes and that the pore volume decreases with better packing efficiency. In addition, the finer particle size controls the pore size. After coating, the coated SiC powders were re-suspended and slip cast into pellets using Lexan dies on gypsum molds. The slip cast pellets were dried then heat treated to various temperatures to determine a reasonable heat treatment cycle necessary to provide sufficient strength. The pellets exhibited limited shrinkage. The experimental matrix consisted of 9 batches with three powder blends heat treated at three temperatures with a hold time of 0.3 hours in air (Table II). TABLE IExperimental matrix including 9 samples1200 Grit SiC Addition (%)Temperature (° C.)5075100155012316004561650789 All the sintered substrates possessed continuous open pore channels. The most uniform continuous pore channels were obtained from the fine SiC powders (1200 grit) alone, without coarse powder additions. All three heat treatment temperatures produced specimens with excellent mechanical integrity and continuous pore structures. At the higher sintering temperatures, however, (1600 or 1650° C.) the pore structure became well defined, with the pore channels developing a more cylindrical cross section and a narrower pore size distribution. Examples of fracture surfaces showing this difference are presented inFIG.2. From a microstructure perspective, it appears that the microstructure on the left (sintered at 1650° C.) has a more uniform pore structure and that the pores remain continuous. The microstructure on the right is less well defined but is still continuous. Example: A ceramic monolith was formed and sintered to create a continuous pore structure with uniformly spaced pores with a diameter less than 20 microns, and typically between 5-10 microns. This pore structure was infiltrated with molten metal and then cooled to solidify the metal. On re-heating to the melting point, the volume of the metal increases and the metal exudes from the pore structure to form a liquid metal coating on the surface of the substrate. Since the molten metal exuding from the pores is identical in composition to the metal intended to wet, the surface becomes perfectly wetting to the liquid metal. On cooling the metal retracts into the pore structure, solidifies, and is stored in the pore structure. Upon re-heating, the process is repeated, and the molten metal exudes from the pore structure to recreate the wetting surface. In general, the substrate should be compatible with the molten metal, i.e., metals that are thermodynamically favored to form oxides should not be used with an oxide that is less stable. In other words, the substrate is not decomposed by the first and/or second metals. Carbides likely provide a ready material for the substrate. A specific example is a SiC monolith with a uniform continuous pore structure that can be filled with Al metal. When heated this system forms a perfectly wetting surface for molten aluminum metal. While the claimed technology has been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive in character. It is understood that the embodiments have been shown and described in the foregoing specification in satisfaction of the best mode and enablement requirements. It is understood that one of ordinary skill in the art could readily make a nigh-infinite number of insubstantial changes and modifications to the above-described embodiments and that it would be impractical to attempt to describe all such embodiment variations in the present specification. Accordingly, it is understood that all changes and modifications that come within the spirit of the claimed technology are desired to be protected. | 15,603 |
11858864 | DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S) As noted in the background, slurry and foam should be mixed together as homogenously as possible in order to produce a gypsum board (or plasterboard) product of high quality (i.e., a finished gypsum board product that lacks blisters, blows, voids, and poor core formation). It is generally known that pushing slurry or liquids through a pipe or hose will create vortexes, eddies, and turbulence that promote the mixing of materials. If two materials (e.g., gypsum and foam) of different densities are both injected into a hose or pipe of adequate length, a slurry of a different density (the average of the two originals) is produced. In order to better blend the gypsum slurry and foam together in a more homogeneous fashion, and result in a better product, this disclosure aims to take advantage of blending properties of a hose, along with a canister and funnel. In addition, using a hose in the herein disclosed manner allows for flexibility in the movement and positioning of the mixer relative to other parts of the system, among other benefits, discussed later. Throughout this disclosure, reference to a “slurry mixture” refers to a mixture of at least slurry and (aqueous) foam. Also, the terms “approximately,” “substantially,” “about,” and similar terms generally refer to values and/or ranges that include the identified value within a margin of 10%, and any values therebetween. In addition, reference to a “product” refers to a formed gypsum board and is not intended to be limited with regards to size or dimension. Discussion with regards to ½ inch and ⅝ inch products refers to a thickness of the product/formed gypsum board and such thicknesses are exemplary. FIG.1illustrates a schematic representation of a system100, in accordance with an embodiment of this disclosure, that utilizes an elongated hose and an optional adapter to deposit a slurry mixture and for making gypsum board. Generally, the system100ofFIG.1includes a mixer102, a foam injector104, a canister106, an elongated hose108, an adapter110, an optional mixer boot112, and a board, surface, or table with a conveyor114(e.g., in the form of a belt) with paper that is moved or run therealong and a mixture is deposited to form gypsum board. The mixer102is constructed and arranged to mix gypsum slurry to a first flow rate. Although not shown or described in great detail herein, one of ordinary skill in the art should understand that the mixer102includes at least a mixing chamber, a rotor, and an outlet, as well as a material supply (e.g., calcium sulphate hemi-hydrate) and a water supply (or other liquid or fluid) associated therewith, and any number of orifices or nozzles. The mixer may be designed such that dead zones are limited in the mixing chamber so that risk of clogging the mixer is reduced or eliminated. A tubular element and a collecting element may connect to an outlet orifice in the mixer, and a pressure regulating element and transport element may be provided on the mixer. The mixed slurry is directed from the mixer102to an exit gate105. A foam injector104injects foam into the mixed slurry to form a slurry mixture. The foam injector is constructed and arranged to inject the foam into the mixed slurry at a point between the mixer102and the canister106, into the canister106, and/or into the elongated hose108. In one embodiment, foam is injected by injector104in the exit gate105or to the exit gate passageway to form the slurry mixture. In another embodiment, foam may be injected by injector104into the canister106, e.g., into or through a side or a top of the canister106, in either one or two locations (e.g., seeFIG.2), via foam injection slot(s) or through a grid of smaller holes (e.g., that are covered with an injection manifold) or through a tube or pipe. In yet another embodiment, foam may be injected into both (alternatively or simultaneously) the exit gate105or exit gate passageway and the canister106. From the exit gate105, the slurry mixture may be directed to the canister106. The canister106is connected to the mixer102(see, e.g.,FIG.2,FIG.3). The canister106induces a swirl to the slurry mixture. In an embodiment, the mixer102is constructed and arranged to mix slurry to a first flow rate. The mixture may optionally flow at a second flow rate after being introduced into the canister106. In an embodiment, the canister106is constructed and arranged to reduce the flow of the slurry mixture, such that the second flow rate (e.g., out of the canister106) is lower than the first flow rate (at which it is mixed and output by mixer102). In some cases, the slurry mixture flows at the same flow rate. From the canister106, the slurry mixture is directed to elongated hose108. The elongated hose108may be connected to the canister106at a first end124, as shown inFIG.10(as illustrated here, an optional elbow connector118is attached to and in between the canister106and end124of hose108). In one embodiment, the end124of the hose108is directly connected to the canister106. In other embodiments, the end124of the hose108may be connected to the canister106using a hose barb121, elbow connector118, and/or other connection device(s) (e.g., seeFIGS.4-7). The slurry mixture is further blended (e.g., with the injected foam) as it moves at a flow rate through the elongated hose108such that a well-blended mixture exits a second end126of the hose. In an embodiment, the slurry mixture enters the hose108at first end124at a first flow rate and exits the hose108at second end126at a second flow rate. In one embodiment, the first flow rate and second flow rate relating to the hose108are substantially equal or the same rate. In another embodiment, the second flow rate out of the hose108is lower than the first flow rate. In yet another embodiment, the second flow rate of the hose108is higher than the first flow rate. The second end126of the hose108may be optionally attached to a receiving inlet109of the adapter110constructed and arranged to receive the slurry mixture, for communicating the slurry mixture from the canister106to the adapter110. Accordingly, the slurry mixture may be directable from the canister106, through the elongated hose108, and into the receiving inlet109of the adapter110. The adapter110has a deposit outlet111through which the slurry mixture exits and is deposited onto paper moving on the board or conveyor114to form the gypsum board. In accordance with some embodiments, use of the adapter110is optional; instead, the second end126of the hose108may be positioned to deposit slurry mixture directly onto paper on conveyor114, for example. Generally, the canister106has a body that includes an inlet for receiving the slurry mixture and an outlet for outputting the slurry mixture. In one embodiment, the canister106includes one or more baffles therein to promote blending and/or mixing of the slurry mixture (e.g., with foam). Similarly, grooves or steps may be formed in a body of the canister to promote blending and/or mixing. Structural features of the canister106are generally known, and thus not further explained herein. In an embodiment, a mixer boot112is optionally provided in the system100and receives the slurry mixture exiting from hose108or the outlet111of the adapter110, such as shown inFIG.2or3, for example. The mixer boot112may slow or reduce a speed of the slurry mixture and may be positioned or configured to deposit the slurry mixture onto (or in between) paper that is being conveyed by conveyor114, to make the gypsum board. The mixer boot112has an inlet for receiving the slurry mixture, a body that directs the slurry mixture (e.g., in a downward and a lateral or parallel direction to the moving paper), and an outlet for depositing the slurry mixture, e.g., onto the paper. Structural features of such a mixer boot112are generally known, and thus not further explained herein. In accordance with an embodiment, at least a size of the inlet of the mixer boot112matches or is similar to the size/diameter of the elongated hose108. In one embodiment, the size and dimensions of the mixer boot112may be dependent an amount or desire at which to slow/reduce a speed of the slurry mixture that is received from the hose108, before depositing the slurry mixture onto the paper (i.e., the speed at which the slurry mixture enters the inlet of the mixer boot may be greater than the speed at which the slurry mixture exits the outlet for depositing onto the paper). In an embodiment, the mixer boot112may be attached, connected, or coupled to a second end (outlet) of the elongated hose108. In one embodiment, the mixer boot112is attached directly to the hose108. An outlet of the mixer boot112may be positioned to deposit the slurry mixture in substantially parallel manner to the paper on conveyor114, in accordance with an embodiment. In an embodiment, the outlet of the mixer boot112is parallel to the paper. Once the slurry mixture is deposited onto the paper on the conveyor114(via hose108, adapter110, or mixer boot112), as generally understood by one of ordinary skill in the art, a top sheet of paper may be applied on top of the slurry mixture deposited onto the moving paper of the conveyor114, to sandwich the mixture therebetween. The sandwiched slurry mixture may run through a forming system which may include a forming plate115, a forming lane, and/or forming board section. The forming plate115may include one or more surfaces, rollers, or plates positioned in relation to the moving paper(s) and slurry mixture, and is designed to apply an amount of pressure to the sandwiched product to form a gypsum board (or product) of desired thickness. Then, as generally known in the art, the formed board may be subject to one or more of: finishing (e.g., on its edges), cutting (e.g., into panels), and/or drying, e.g., via a drying system (e.g., an oven or hot air distribution system). The elongated hose108has a length that is sufficient to impart the slurry mixture with a substantially laminar flow between its first end and its second end, in accordance with an embodiment. Producing a substantially laminar flow of the slurry mixture via the hose108reduces turbulence within the flowing slurry mixture that is received from the canister, while still allowing for flow at a desired flow rate or velocity and further blending as it moves through the hose length (e.g., curved inner sides of the hose may impart smaller vortexes, eddies, and/or the like to the slurry mixture as it moves through to the second end). The elongated hose108thus also promotes better mixing and blending of the gypsum slurry mixture and foam together in a more homogeneous fashion. In one embodiment, the length of the elongated hose108is such that the laminar flow of the slurry mixture is maintained from at least a mid-length of the elongated hose to the second end of the elongated hose. In one embodiment, the length of the elongated hose108is at least 3 m. In another embodiment, the length of the elongated hose108is less than 6 m. In an embodiment, the length of the elongated hose108is approximately 2 m to approximately 6 m (both inclusive). In an embodiment, the elongated hose108is made of a substantially kink-free, flexible material. An inner diameter D of the hose108may vary. In accordance with an embodiment, inner diameter D of the hose108is in a range from approximately 2 inches to approximately 4 inches. In an embodiment, the elongated hose108and the receiving inlet109of the adapter110have a substantially similar inner diameter. In an embodiment, the receiving inlet109may have a diameter AD or width in a range from approximately 2 inches to approximately 4 inches. In addition, in accordance with an embodiment, the canister106, hose barb121, elbow connector118, and/or other connection device(s) used to connect the first end124of the hose108may have a similar diameter or width as the inner diameter of the elongated hose108. A position or an arrangement of the length of the hose108between its first and second ends124,126is not intended to be limited. The elongated hose may be positioned in the system100and/or dimensioned to direct the slurry mixture in at least two different directions between the first end124and the second end126. In one embodiment, the at least two different directions are opposite or perpendicular directions. In an embodiment, a portion of the elongated hose108is positioned and/or dimensioned to direct the slurry mixture vertically and away from a plane formed by the paper. In accordance with an embodiment, a portion of the length of the hose108is positioned in a loop. In one embodiment, schematically shown inFIG.3, for example, the loop of the hose108is configured such that the flow of slurry mixture is directed from the canister106horizontally, upwardly, and then downward (vertically) again within the hose108. In another embodiment, for example, the loop of the hose108is configured such that the flow of slurry mixture is directed substantially horizontally and away from the canister106and then around in a horizontally configured loop before directed outwardly to the paper on the conveyor114. In yet another embodiment, the length of the hose108includes at least one portion that may be positioned substantially vertically. In another embodiment, the length of the hose includes at least one portion that may be positioned substantially horizontally, e.g., relative to the paper. In yet another embodiment, the hose108has a length wherein at least a first portion that may be positioned in a substantially vertical direction and a second portion that may be positioned in a substantially horizontal direction. A second end126of the hose108may be positioned substantially parallel to the paper on conveyor114, in accordance with an embodiment. The positioning and configuration of the hose108may be adjusted in any number of ways, and is not intended to be limiting. As discussed throughout this disclosure, the hose108provides flexibility with regards to its positioning and direction, e.g., to affect the movement of the slurry, as well as flexibility with regards to positioning of other parts of the system100. It should be understood that the length of the hose108may be angled, looped, or positioned in a number of different directions, with at least a portion of the hose108positioned such that the slurry mixture flows in a substantially laminar direction. The flexibility of the elongated hose108with regards to its and positioning in the system100accordingly provides the ability to position the mixer102offline from the other system components, such that it may be positioned substantially adjacent to the plate, board or conveyor114that positions the paper for receipt of the slurry mixture. An example of the positioning of mixer102relative to the plate, board or conveyor114is shown inFIG.1. As explained in greater detail below, in accordance with an embodiment, the canister106may include a funnel body116therein to further induce a swirl into the slurry mixture as it flows therethrough.FIGS.2and3illustrate embodiments of system100with a funnel body116connected to the canister106. The entire canister assembly, including its funnel (if used), is stationary within the system. The height H between a top of the canister106and an inlet15of the funnel body116may be approximately 7.0 inches. In accordance with one embodiment, the height H is approximately 6 inches to approximately 8 inches. FIGS.4-5illustrate views of the funnel body116that may be connected to or contained within the canister106for inducing turbulence into a slurry mixture, in accordance with this disclosure. The funnel body116has a body portion12that may be formed as a separate and distinct structure that is connected to and/or inserted into the body of the canister106, e.g., near or at its outlet. In another embodiment, the body portion12is formed with the canister106. The funnel body116and canister106may be integrally formed. The body portion12(or body12) of funnel body116has an inner wall14, an outer wall16, an inlet opening15, and an outlet opening30. The inner wall14is generally spaced from the outer wall16and provided at an angle relative to a longitudinal axis Y (described further later) to direct the slurry mixture poured into the inlet15towards the outlet30. The inlet opening15is provided at a top portion18of the body portion12for receiving the slurry mixture from the canister106, and an outlet opening30may be provided at or near a bottom portion20of the body12. The inner wall14may extend between the inlet opening15at the top portion18of the body12and the outlet opening30near a bottom portion20. In an embodiment, the outlet opening30has a cross-section that is smaller than a cross-section of the funnel inlet opening15. In one embodiment, the outlet opening30has a smaller diameter than a diameter of the funnel inlet opening15. In use, the slurry mixture is introduced into the funnel body116via the inlet opening15from the body of the canister10, and, since the inner wall14extending between the inlet15and the outlet30is angled, it generally swirls the flowing slurry mixture within the body12downwardly towards the outlet opening30. The body portion12may have an overall height DH (seeFIG.4) of approximately 2.75 inches. In accordance with an embodiment, the overall height DH may be approximately 2.5 inches to approximately 4 inches (both inclusive). The outlet opening30of funnel body116may be provided at an outlet height OH (seeFIG.5) measured from a top edge of the body12to an edge of the outlet opening30. The outlet height OH may be approximately 2.5 inches. In accordance with an embodiment, the outlet height OH may be approximately 2.0 inches to approximately 3.75 inches (both inclusive). In another embodiment, the outlet opening30is provided at the bottom20of the body12, and the outlet height OH may be approximately 2.75 inches. As shown inFIG.4, the top edge of the funnel body12has a top dimension DT (e.g., width). The inlet opening15has an opening dimension DT2at the top18of the body12. In an embodiment, the opening dimension DT2of the inlet opening15is slightly smaller than the top dimension DT of the top edge. In an embodiment, the top dimension DT is approximately 7 inches. In accordance with an embodiment, the top dimension DT is approximately 6 inches to approximately 8 inches (both inclusive). In an embodiment, the opening dimension DT2is approximately 6.7 inches to approximately 6.85 inches (both inclusive). In accordance with an embodiment, the opening dimension DT2is approximately 6.5 inches to approximately 7 inches. In another embodiment, DT and DT2may be equal or substantially equal. Of course, any dimensions noted above may be adjusted based on the system or apparatus being used, as well as the desired dimension of the outlet opening30(discussed below). The inner wall14of the funnel body116may be provided at an acute angle relative to a longitudinal axis Y that extends through a center of the outlet opening30, for example. In an embodiment, the inner wall14has a slope of approximately 45 degrees relative to the longitudinal axis Y. In another embodiment, as shown inFIG.5, for example, the inner wall14may be provided at an acute angle A1relative to a plane that extends across the inlet opening15(or a top18) of the funnel body12. In an embodiment, the angle A1of the inner wall14may be within a range between approximately 40 degrees (inclusive) and approximately 60 degrees (inclusive). In an embodiment, the angle A1of the inner wall14may be approximately 52 degrees to approximately 58 degrees. In other embodiments, the angle or slope of the inner wall14may vary, for example, based on the size of the outlet opening30and/or the inlet opening15. The inner wall14may also have a length L that extends between the top edge of the inlet opening15and an edge of the outlet opening30, as shown inFIG.5, for example. In accordance with an embodiment, the length L is approximately 3 inches long. However, it should be understood that the length of the inner wall14may vary based on many factors, including, but not limited to, the size or diameter of the donut hole or outlet opening30, the size or diameter of the assembly or funny body12, and/or the angle A1of the sides or inner wall14of the funnel body12. For example, the length L may range from approximately 1.5 inches (inclusive) to approximately 5 inches (inclusive), or more. The outlet opening30has an outlet diameter OD (seeFIG.4). In an embodiment, the size or diameter OD of the outlet opening30may vary from as little as approximately 1 inch (inclusive) to as much as approximately 5 inches (inclusive). In one embodiment, the outlet opening30may have a diameter OD in the range of approximately 3.75 inches (inclusive) to approximately 4 inches (inclusive). The size of the outlet opening30may variably depend on a line speed (speed or rate at which the mixed slurry is being delivered) and the type of product being mixed. The outlet opening30may have an attachment point for the hose108. In one embodiment, the funnel outlet opening30and the elongated hose108have a substantially similar inner diameter. For example, the diameters may be approximately 4 inches. FIG.2shows an example of a system like system100that includes funnel body116at an outlet of the canister106. As previously described, slurry mixture from the mixer102is directed to the canister116and then swirled using funnel body116. The elongated hose108is connected to outlet30of the funnel body116. As the slurry mixture exits the funnel body116, it is communicated and transported through the elongated hose108, in a laminar fashion along a significant length of the elongated hose108, to the receiving inlet109of the adapter110(optional). The slurry mixture exits the deposit outlet111and into mixer boot112(optional) for placement on paper of a conveyor114. It is again noted that use of the adapter110and/or mixer boot112within the system100are optional. For example, in accordance with one embodiment, the slurry mixture may be directed out from the canister106into the first end124of the hose108, through the length of the hose108, and out of the second end126of the hose108onto the paper of conveyor114. In accordance with an embodiment, wherein an adapter110is used in the system100, the adapter may also or alternatively have a funnel body122associated therewith.FIG.3illustrates another embodiment of a system like system100wherein both the canister106and the adapter include funnel-shaped bodies. Exemplary details of such an adapter are further described below with reference toFIGS.8and9. In an embodiment, the adapter110may be used while a mixer boot112is not. As previously noted, in another embodiment, only a mixer boot112is used with the hose108. Alternatively, in an embodiment, both an adapter and a mixer boot may be used. In another embodiment, neither the adapter110nor the mixer boot112are provided in the system100. When an adapter is associated with, adapted to, attached to, or connected to second end126of hose108, its configuration is not intended to be limiting. FIGS.6and7show an example of one embodiment of an adapter110configured for use with the hose108in the system100. The adapter110has a body portion32A with its receiving inlet109and deposit outlet111. In an embodiment, as previously described, the receiving inlet109is configured for attachment or coupling to the second end126of the hose108. In an embodiment, the deposit outlet111may be positioned relative to paper on a conveyor114or plate. For example, the adapter110ofFIGS.6and7may be attached to an end126of the elongated hose108when no mixer boot112is used in the system. Alternatively, in accordance with another embodiment, the outlet111of the adapter110may be attached or coupled to an opening of the mixer boot112. The adapter110has an overall height AH, shown inFIG.6, and a wall thickness AT, an inner diameter AD, and an outer diameter OD, shown inFIG.7. The inner diameter AD of the adapter110may be consistent or the same from the receiving inlet109through to the deposit outlet111. A thickness AT of the wall of the adapter110(AT=AD2minus AD) may also be consistent between the inlet109and outlet111. Ends of the adapter110at the inlet109and/or outlet111may each include an angled portion, lip, or edge to assist in connection of the adapter to other parts in the system. The lip(s) may extend approximately 0.25 inches to approximately 0.5 inches from the corresponding opening. In an embodiment, the adapter110includes a central flange113that extends outwardly relative to a center/axis Y2of the body of the adapter110, shown inFIG.6. The adapter110may include a top flange portion and bottom flange portion that each extend in the longitudinal direction (relative to axis Y2), e.g., away from the central flange113. The top flange portion of adapter110may be used for attaching, connecting, or coupling the adapter110to the second end126of the elongated hose108, while the bottom flange portion remains open or is connected to an optional mixer boot112. The central flange113may, in some cases, be used to assist in connecting the adapter110to the hose108or boot112, for example (e.g., for grasping by a user). In accordance with an embodiment, the adapter110may be formed from stainless steel (e.g., 303 stainless steel). However, in another embodiment, an alternative material, or a mixture of materials, may be used to form the adapter. In accordance with an embodiment, the funnel outlet30of the first funnel body116, the elongated hose108, and the receiving inlet109of the adapter110have a substantially similar inner diameter. In an embodiment, the overall height AH of the adapter includes a height FH of the central flange113plus the heights of the top and bottom flanges (i.e., each of the distances measured from the central flange to either the receiving opening109or the deposit outlet111). In one embodiment, the overall height AH of the adapter is between approximately 4.0 inches to approximately 6.0 inches (both inclusive). In another embodiment, the overall height AH of the adapter110is approximately 5.0 inches (inclusive) to approximately 5.5 inches (inclusive). In an embodiment, the flange113may have a height FH of approximately 1.0 inches and a width FW of approximately 1.75 inches extending from the outer diameter AD2, for example. However, the height FH and width FW of the flange113may vary. In an embodiment, the outside diameter of the wall, AD2is approximately 4.1 inches to approximately 4.6 inches (both inclusive). The wall thickness AT of the adapter110may be between approximately 0.2 inches and approximately 0.5 inches, inclusive, in accordance with an embodiment. In one embodiment, the inner diameter AD of the adapter110is substantially similar or equal to the diameter D of the hose108. In an embodiment, the size or diameter AD of the adapter110may vary from as little as approximately 1.0 inches (inclusive) to as much as approximately 5.0 inches (inclusive). The inner diameter AD of the adapter110may be between approximately 2.0 inches and 4.0 inches, inclusive, in accordance with an embodiment. In one embodiment, the diameter AD may be in the range of approximately 3.75 inches (inclusive) to approximately 4.0 inches (inclusive). The size of the inner diameter AD may variably depend on a line speed (speed or rate at which the mixed slurry is being delivered) and the type of product being mixed. In another embodiment, the inner diameter AD of the adapter110is slightly larger than the diameter D of the hose108, e.g., for placement around the end126of the hose108. In yet another embodiment, the inner diameter AD may be slightly smaller than the diameter D of the hose108, e.g., the outer diameter OD may also be smaller than the diameter D, e.g., for insertion of the receiving inlet109into the hose108(e.g., the end126of hose108covers the outer diameter OD of the adapter110and receives a portion of the inlet109therein, so that the end126encloses the inlet109of the adapter110), or just the inner diameter ID may be smaller (e.g., greater wall thickness for the adapter110). In another embodiment, the inner diameter AD is substantially similar or equal to a diameter or width of an opening of the mixer boot (if used). In another embodiment, the inner diameter ID of the adapter110is slightly larger than the opening of the mixer boot. In yet another embodiment, the inner diameter ID may be slightly smaller than the opening of the mixer boot. In one particular embodiment, the outside diameter AD2of the adapter110is approximately 4.25 inches, the inner diameter AD is approximately 4.0 inches, and the wall thickness AT is approximately 0.25 inches. In still yet another embodiment, where a mixer boot112is used, the inner diameters (or widths) of the hose108, adapter110(if used), and opening of the mixer boot112are all substantially the same or equal in dimension. In one embodiment, the adapter110is configured for attachment, connection, or coupling with an elbow connector, e.g., such as one similar to elbow connector118shown inFIGS.4and5, and described in further detail later. In an embodiment, the adapter110has an inner diameter AD that is similar or the same in dimension as an inside diameter ED of the elbow connector118, e.g., approximately 4 inches. In one embodiment, the adapter110has an inner diameter AD that is similar or the same in dimension as both the hose108and an inside diameter ED of the elbow connector118, e.g., approximately 4 inches. FIGS.8and9illustrate views of adapter110having a funnel body122adapted to, connected to, associated with, or contained within the adapter110, in accordance with another embodiment of this disclosure, e.g., such as schematically depicted in the system ofFIG.3. The adapter110has a body portion32with its receiving inlet109and deposit outlet111. As an example, the receiving inlet109of the adapter110ofFIGS.8and9may be attached to an end126of the elongated hose108when the size/diameter of the second end126is smaller than an inlet of a mixer boot112(the outlet111being attached to the inlet). Alternatively, in accordance with another embodiment, the outlet111of the adapter110may be positioned relative to the paper on the conveyor114, without using a mixer boot112. The funnel body122of the adapter110may be formed as a separate and distinct structure that is connected to and/or inserted into the body32of the adapter110, e.g., near or at its outlet. In another embodiment, the funnel body is formed with or within the adapter110. The funnel body122and adapter110may be integrally formed, for example. The body portion of funnel body122has an inner wall34, an outer wall36, a receiving inlet opening35, and the deposit outlet opening111. The inner wall34is generally spaced from the outer wall36and provided at an angle relative to a longitudinal axis Y2(described further later) (and, in some cases, at an angle relative to outer wall36) to direct the slurry mixture poured into the inlets109,35towards the outlet111. As shown inFIG.8, the adapter100may include a top flange portion38that extends in the longitudinal direction (relative to axis Y2) between the inlet109of the adapter and the inlet opening35of the funnel body122. The top flange portion38may be used for attaching, connecting, or coupling to the adapter110to the second end126of the elongated hose108. In an embodiment, the adapter110includes a central flange39that extends outwardly relative to a center/axis Y2of the body of the adapter110, shown inFIG.8. The adapter110may include a bottom flange portion that extends in the longitudinal direction (relative to axis Y2), e.g., downwardly away from the central flange39. The bottom flange portion remains open or is configured to be attached, connected, or coupled to an optional mixer boot112. The central flange39may, in some cases, be used to assist in connecting the adapter110to the hose108or boot112, for example (e.g., for grasping by a user). In accordance with an embodiment, the adapter110may be formed from stainless steel (e.g., 303 stainless steel). However, in another embodiment, an alternative material, or a mixture of materials, may be used to form the adapter. In accordance with an embodiment, the funnel outlet30of the first funnel body116, the elongated hose108, and the receiving inlet109of the adapter110have a substantially similar inner diameter. The inlet opening35of the funnel body122may be provided at, near, or adjacent a mid-portion of the body of adapter110. In another embodiment, the inlet opening35of the funnel body122is provided at or near a top of the body of the adapter110, e.g., top of the flange portion38. The outlet opening111may be provided at or near a bottom portion of the body of the adapter110. The outlet opening of the funnel and adapter may be the same opening. The inner wall34may extend between the inlet opening35of the funnel body122and the outlet opening111of the adapter110. In an embodiment, the cross-section of the receiving inlet109of the adapter is smaller than a cross-section of the deposit outlet111. In an embodiment, the cross-section of the inlet35of the funnel body122is smaller than a cross-section the deposit outlet111. In one embodiment, the receiving inlet109and inlet35have a similar cross-section and/or diameter (or width). In one embodiment, the outlet opening111has a larger diameter than a diameter of the funnel inlet opening35. In use, the slurry mixture is introduced into the funnel body122via the inlet opening35from receiving opening109that is attached to the elongated hose108. The adapter110may have an overall height DH2(seeFIG.8) that includes a height of the funnel FH and a height FH3measured between the receiving inlet109and the inlet opening35(i.e., DH2=FH+FH3). The adapter110may have an overall height DH2of approximately 3.25 inches, in accordance with one embodiment. In one embodiment, the funnel body122may have a funnel height FH between its inlet35and deposit outlet111between approximately 1.5 inches and 3.0 inches (both inclusive). In an embodiment, the funnel height FH is approximately 2.0 inches. The distance FH3between the opening at the receiving inlet109(measured from a top edge of the adapter110) and the funnel inlet35may be between approximately 1.0 inches (inclusive) and approximately 2.0 inches (inclusive). The distance FH3may be approximately 1.25 inches, in accordance with one embodiment. In an embodiment, the flange39may have a height FH2of approximately 1.0 inches (inclusive), but is variable. The inlet opening35has an inlet diameter ID (seeFIG.9). In accordance with an embodiment, the inlet diameter ID and the diameter (AD) of the receiving inlet109are substantially the same or equal. In one embodiment, the inlet diameter ID of the inlet opening35is substantially similar or equal to the diameter D of the hose108. In another embodiment, the inlet diameter ID is slightly larger than the diameter D of the hose108. In yet another embodiment, the inlet diameter ID may be slightly smaller than the diameter D of the hose108. In an embodiment, the size or diameter ID of the inlet opening35may vary from as little as approximately 1.0 inches (inclusive) to as much as approximately 5.0 inches (inclusive). The diameter ID of the inlet opening35may be between approximately 2.0 inches and 4.0 inches, inclusive, in accordance with an embodiment. In one embodiment, the inlet opening35may have a diameter ID in the range of approximately 3.75 inches (inclusive) to approximately 4.0 inches (inclusive). The size of the inlet opening35may variably depend on a line speed (speed or rate at which the mixed slurry is being delivered) and the type of product being mixed. The size of the inlet opening35may be the same or similar size as the receiving inlet109of the adapter110, and/or the inner diameter of the elongated hose108. The inner wall34of the funnel body122may be provided at an obtuse angle A2(seeFIG.8) relative to a plane extending horizontally through the inlet35of the funnel122or the inlet109of the adapter110(the plane being perpendicular to longitudinal axis Y2that extends through a center of the deposit outlet opening111). (Alternatively, it could be said that the inner wall34is provided at an acute angle relative to a longitudinal axis Y2, for example.) The angled, inner wall34of the funnel body122may assist in substantially reducing and/or eliminating any dead space and/or backup in the mixture or material as it is deposited from the deposit outlet opening111. In an embodiment, the angle A2of the inner wall34may be within a range between approximately 100 degrees (inclusive) and approximately 120 degrees (inclusive). In an embodiment, the angle A2of the inner wall34may be approximately 111 degrees. In another embodiment, the inner wall34has a slope of approximately 45 degrees relative to the longitudinal axis Y2. In other embodiments, the angle or slope of the inner wall34may vary, for example, based on the size of the deposit outlet opening111and/or inlet109. The inner wall34may also have a length L2that extends between the edge of the inlet opening35and an edge of the outlet opening111, as shown inFIG.8, for example. In accordance with an embodiment, the length L is approximately 2 inches long. However, it should be understood that the length of the inner wall34may vary based on many factors, including, but not limited to, the size or diameter receiving opening109and/or inlet opening35, and/or the angle A2of the sides or inner wall122of the funnel body12. For example, the length L2may range from approximately 1.5 inches (inclusive) to approximately 5 inches (inclusive), or more. The opening of the deposit outlet111has an outlet diameter OD2(seeFIG.9). In an embodiment, the size or diameter OD2of the outlet opening111may vary from as little as approximately 2 inch (inclusive) to as much as approximately 6 inches (inclusive). In one embodiment, the deposit outlet opening111may have a diameter OD2in the range of approximately 5.0 inches (inclusive) to approximately 6 inches (inclusive). In one embodiment, the diameter OD2of the opening is approximately 5.5 inches. The size of the outlet opening111may variably depend on a line speed (speed or rate at which the mixed slurry is being delivered) and the type of product being mixed. Ends of the adapter110at the inlet109and/or outlet111may each include an angled portion, lip, or edge to assist in connection of the adapter to other parts in the system. The lip(s) may extend approximately 0.25 inches to approximately 0.5 inches from the corresponding opening. In one embodiment, a lip of the deposit outlet111has an outside diameter OD3(seeFIG.9) of approximately 6.0 inches. In one embodiment, the adapter110is configured for attachment, connection, or coupling with an elbow connector, e.g., such as one similar to elbow connector118shown inFIGS.4and5, and described in further detail later. In an embodiment, the outlet diameter OD2of the adapter110is similar or the same in dimension as an inside diameter ED of the elbow connector118, e.g., approximately 4 inches. In an embodiment, the outlet diameter OD2of the adapter110may be similar in size as the opening of a mixer boot112(if used). The wall thickness of the top flange portion38of the adapter110may be between approximately 0.2 inches and approximately 0.5 inches, inclusive, in accordance with an embodiment. The wall thickness around the funnel portion122may vary or may be substantially consistent through its length L2. In one particular embodiment, the diameters AD and ID of the receiving opening109and inlet opening35are approximately 4.0 inches and the outlet diameter of the deposit outlet111is approximately 5.5 inches. In accordance with an embodiment, the system100may include the canister106and the adapter110as shown inFIGS.8-9. In one embodiment, the angle A1of the inner wall14of funnel body116of the canister may be larger or steeper than the angle A2of walls of the inner wall34of funnel body122of adapter110. Again, both angles A1and A2may vary based on any number of factors, including, but not limited to the size of the outlet openings30,111and/or the type of material or product being swirled, induced, and delivered, and/or a line speed, for example. It will be appreciated that, any dimensions noted above may be adjusted based on the system or apparatus being used, the product or material, the line speed, as well as relatively adjusted based on a desired dimension of the elongated hose108attached to the canister106. The deposit outlet111may have an attachment point for the mixer boot112. The mixer boot112may be positioned around or over the deposit outlet111of the adapter110. In one embodiment, the outlet111and the inlet of the mixer boot112are substantially similar in size or dimension. In one embodiment, the mixer boot112may include 2.25×7 inch outlet with approximately 6.625 inch inlet. The size of the deposit outlet111, lip, or attachment point may be based on a size of inlet of the mixer boot112, in accordance with embodiments herein. Although throughout this disclosure the mixer boot112is generally noted as having a single outlet (or single leg), it should also be understood that more than one outlet may be provided in the mixer boot112. Different boot configurations may be used for mixer boot112to ensure optimal distribution or spread across the table/conveyor114. For example, a multi-legged boot may include two (or more) outlets, while its inlet may be attached to the end126of the elongated hose108or attached to the adapter110. Such a multi-outlet or multi-leg mixer boot112may provide additional control over the slurry mixture to ensure that its deposition across the width of the paper, and thus the volume of the formed board, is substantially full and complete across its entire width. The devices and methods for connecting the ends124,126of the elongated hose108to the canister106and/or adapter110are not limited. In accordance with embodiments herein, one or more elbow connectors118, hose barbs121, and/or connection devices may be attached to one or more end(s)124,126of the elongated hose108for connection to the canister106and/or the inlet109and/or deposit outlet111of the adapter110. As shown inFIGS.4and5, for example, an elbow connector118may be attached near or to the funnel outlet30of the funnel body116within canister106, or to an outlet of a canister106without a funnel body therein.FIG.10shows one embodiment wherein an elbow connector118is attached to the outlet of the canister106and to the first end124of the elongated hose108(via a hose barb121). The elbow connector118may include an inner diameter ED (seeFIG.5) that is similar to the outer diameter OD of the funnel body116, in one embodiment. In an embodiment, elbow connector118may include an inner diameter ED that is similar to the inner diameter ID of the elongated hose108. In yet another embodiment, the inner diameter ED of the elbow connector118is consistent from end-to-end, and thus similar to both the funnel body116and inner diameter of the elongated hose108. In still yet another embodiment, the inner diameter ED of the elbow connector118may vary to accommodate for different sizes of the outlet (OD) and the elongated hose (ID). In one embodiment, the inner diameter ED of the elbow connector is approximately 3.75 inches (inclusive) to approximately 4 inches (inclusive). The elbow connector118may have a radius R (seeFIG.4) of approximately 6 inches. In an embodiment, the system100includes the elongated hose108coming from the elbow connector118connected at the bottom of the canister106, wherein the hose108is configured to feed the slurry mixture from its second126directly onto the paper, without an adapter110or mixer boot112. In one embodiment, a frame or structure may be provided in the system for stabilizing, securing, and/or positioning a length or body of the elongated hose108. For example, the frame or structure may stabilize and position the second end126and outlet of the elongated hose108at a desired height, angle, and/or position relative to the paper and conveyor114, such that the slurry mixture is directed and deposited, as desired, thereon (e.g., in a laminar manner). In another embodiment, multiple frames and/or structures may be used or spaced along the length of the elongated hose108, for positioning and securing the body of the hose108. As previously noted, in another embodiment, an elbow connector like connector118may be attached to an end of the adapter110(not shown) or the inlet of the mixer boot112. In accordance with an embodiment, such as shown inFIG.10, the canister106and adapter110are positioned such that their axes Y and Y2are substantially parallel with one another. In one embodiment, the adapter110may be positioned adjacent to the canister106. In another embodiment, the outlets30and111of the canister106and adapter (respectively) are positioned such that they are within a similar plane and/or adjacent to one another. In order to evaluate and confirm the effect on foam blending into the slurry and resulting gypsum board product, several tests/trials were implemented. Example Test 1 The test was run using a system similar to the system shown inFIG.3; i.e., with funnel body116and an adapter with funnel body122(like adapter110ofFIG.8). One end of an elongated hose (108) was installed onto a canister, like canister106, and the adapter was attached to the opposite end of hose. The tested hose had an inner diameter of approximately four (4) inches, and a four (4) inch elbow connector was also used. Foam was injected into the exit gate for the purposes of the trial. Also, a mixer boot (112) having the same diameter as the hose with a dimensional outlet of seven inches wide by 2.25 inches high (7″W×2.25″H) was utilized at the opposite end of the hose (near the adapter). The hose had a vertically positioned portion. The system and product were observed during processing. The slurry looked very smooth as it was streamed. Also, no blisters were found during the trial. It was also determined that a differential density across the forming table (i.e., across its width, e.g., from right side to left side) decreased by more than fifty percent (50%) as foam weight was lowered for subsequent runs—e.g., from 5-8 grams (prior to the trial) to less than 2 grams during the trial; this means that the system improves foam blending (as designed). Lowering of both the foam weight and soap usage also improved nail pulls. Example Test 2 The test was run using parts from a system similar to the system shown inFIG.2, but with no adapter (110) and no mixer boot (112); i.e., using only funnel body116. One end of an elongated hose (108) was installed onto a canister, like canister106, while the opposite end of hose was positioned relative to the paper on the conveyor and secured using a frame. The tested hose had an inner diameter of approximately four (4) inches, and a four (4) inch elbow connector was also used. Foam was injected into the exit gate for the purposes of the trial. The hose had a horizontally positioned portion. The system and product were observed during processing. There was smooth and laminar slurry flow through the hose, with no spin, but flow from an end of hose (out to the paper) was generally at a higher velocity. These example tests and trial runs, utilizing the system configurations above (each including at least the canister106and elongated hose108) resulted in producing a smoother slurry mixture, of more consistent density, exiting the hose (whether with or without a mixer boot and/or adapter). The hose did not cause the mixer to increase load in any of the tests (in some cases, it actually decreased the load on the mixer). Core splits and blisters in the produced products may be substantially reduced and/or eliminated. Build up on parts (as a result of the flowing slurry) may be minimal, or none at all, depending on the configuration and features of the parts in the system. Also, by implementing use of the elongated hose, no speed restriction (i.e., line speed) is necessary for ⅝ inch products (vs. ½ inch products) (further details are described later, below). Accordingly, as confirmed via results of the tests, the herein disclosed system using at least canister106and the elongated hose108, enhances mixing and forces blending of the slurry with the foam, substantially reducing and/or eliminating the normal liabilities of blisters and deep core splits associated with low density foam and high air usage. More mixing residence time in and through the hose allows the foam to coalesce before forming the board. As a result, the foam formulation added by injector104may be optimized. The resulting optimized foam formulation may be lower in density, with increased foam air and decreased soap, thus creating a more open core (bigger bubbles) that contributes to higher core strength, easier drying, and improved nail pulls (in the finished product). The disclosed system, including the combination of the described canister and elongated hose, eliminates normal issues typically associated with lower density foam and higher air usage that typically make it very difficult to blend to the foam into the slurry because the disclosed system forces blending of the slurry with the foam in a number of locations, e.g., exit gate and/or canister, and elongated hose. It also produces a reduction in the product/gypsum board weight. As such, the combination of using at least the canister106with its funnel body116and the elongated hose108in the disclosed system results in an improved and higher quality formed gypsum board product. The structures of the canister106and funnel body116further induce a swirl into the slurry mixture (as received from the mixer102) as it flows therethrough, and reduces the flow rate of the slurry mixture, to blend the gypsum slurry and foam together. The elongated hose108further blends the gypsum slurry and foam together as the slurry mixture moves along its length and between its ends. Laminar flow imparted to the slurry mixture in the elongated hose108also reduces turbulence while still allowing and forcing blending. Thus, the output or deposited slurry mixture from the hose108(either directly therefrom, or via optional adapter110and/or via optional mixer boot112) is a more homogeneous slurry mixture, having larger air pockets or bubbles therein that are more evenly distributed and consistently incorporated throughout the slurry. As a result, once the gypsum board product is formed and complete (e.g., dried), it has higher strength, with less blistering, core splits, and cracks, thereby improving both performance and aesthetic. FIG.11provides a visual comparison (in the form of photographs) of the enhanced formed product formed as a result of using the herein disclosed system100and method for forming gypsum board vs. standard formed product. A product with a ½ inch core125, formed using a standard, known/prior art system, is shown on top, while another product with a ½ inch core120, formed using the disclosed system100, i.e., formed using at least the canister106and elongated hose108, is shown on bottom. Specifically, the product/core125was formed using a system that had a normal/known mixer gate, a standard (e.g., cylindrical) canister, a donut (e.g., having a top and bottom portion), and a mixer boot attached to the donut, with no hose or attachments provided on the devices or in the canister. The product/core120was formed using a system as described herein: e.g., using a mixer gate, a canister like canister106having funnel body116therein, an integral rigid elbow connector, an elongated hose like hose108, an adapter/reducer like adapter110at the second end of the hose108, and a mixer boot like boot112attached to the adapter110. As compared to the standard core125,FIG.11shows that the core120includes a more open core, i.e., bigger voids (as a result of bubbles from improved distribution of foam throughout the slurry mixture) that are distributed throughout a thickness of the formed core120. Such a core120includes features and advancements over a standard core125, such as those noted above.FIG.13further shows photographic examples (two pieces of a core are shown) of the improvements to the core120of a formed board product using one embodiment of the system100; specifically, as noted above, the core ofFIG.13was formed using a system100including a mixer gate, a canister106having funnel body116therein, an integral rigid elbow connector, an elongated hose108, an adapter110at the second end of the hose108, and a mixer boot112attached to the adapter110. As shown, the formed core ofFIG.13has larger size voids that are more consistent in size and more evenly distributed throughout the core, i.e., across its length and width. However, a core formed using the above noted standard systems and methods—such as the cores shown in the photos ofFIG.12(two pieces of a core are shown) which are similar to core125and were formed using a standard system having a known mixer gate, a standard (e.g., cylindrical) canister, a donut, and a mixer boot attached to the donut, with no hose or attachments provided on the devices or in the canister—has generally smaller voids with random larger sized voids that are inconsistent and sporadically placed throughout the length and width of the core. In addition, the disclosed configuration improves runability of the system for an extended period of time. The disclosed system provides the ability to run smaller slumps, resulting in improved calipers, improved edge formation, and improved face appearance in the gypsum board product. There may also be a reduction in evaporation and resulting gas usage savings. Moreover, as shown inFIG.1, for example, the use of the elongated hose and adapter provide the ability to move the mixer “offline” relative to the plate, board or a conveyor that positions the paper for receipt of the slurry mixture. The mixer may be provided adjacent to or beside the board, for example, instead of above or behind the board or conveyor, as is typically known. This helps decrease paper breaks (e.g., from falling mixer debris onto the paper, which typically can create breaks in the conveyed paper), for example. Also, moving the mixer offline allows for easier addition of additives because there may be more room outside in the environment around the mixer as compared to when the mixer is positioned in line with the conveyor and provided in a fixed space or area. Additionally, moving the mixer offline also results in less operational downtime and more flexibility with product scheduling; the mixer change out time could be decreased dramatically (e.g., from about 45 minutes to 15 minutes) by being positioned offline. It provides in easier access for operators to clean the machinery as well as provide safer conditions for tending to problems. Further, by moving the mixer offline, the mixer boot may also be moved further back from the forming station (since the mixer is no longer constraining the location of the boot attachment, and is no longer in the way). Moving the mixer boot back allows for more effective forming table/board/conveyor length (i.e., its lengthens the table, since the boot is limited with regards to covering a portion of the table), and also gives more time to spread the slurry, which could allow line speed increases—thus avoiding a traditional bottleneck for certain line speeds, and more time for the table vibrators to agitate the slurry to remove large, unwanted bubbles, thereby helping to eliminate voids. Furthermore, flexibility in the position or arrangement of the length of the hose108provides improvements with regards to space considerations and/or limitations. Note that the features (e.g., measurements such as length) and position or arrangement of the length of the elongated hose108between its ends (i.e., from the canister to the paper) is not intended to be limited. Depending upon the features and a position of the elongate hose and its output end (second end)—e.g., relative to the paper/board—placement of the elongated hose in the system may reduce and/or eliminate potential issues related to too much coalescence residence time and/or separation of dense slurry and light foam in the mixed slurry that is deposited onto the paper/board, for example. Also, use of the canister and elongated hose with the optional mixer boot and/or optional adapter may result in less mixer build up and formation of lumps in the deposited slurry mixture. Moreover, using at least the mixer boot at the second end of the hose may further improve the system such that it: induces further blending of the slurry and foam, allows for expansion of the slurry mixture as it moves out of the hose, allows density across the slurry mixture to equalize, reduces splatter onto the paper as the slurry mixture exits the hose, as well as reduce and/or eliminate core splits in the formed board/product. An additional benefit of the herein disclosed system100, as briefly mentioned above, is the ability to better match mixer set up to different density and different speed products; e.g., ⅝ inch products may be run without being restricted on line speed. Historically, mixer set up has been a compromise between optimization for slower, denser products and faster, low density products. What works best for ½″ products and its needs of good foam blending, good mixer fill, and lump prevention, has not necessarily worked best for ⅝″ products and its needs, e.g., its need of high mixer throughput. The capability to produce both products with the same mixer results in compromises. Most frequently, the mixer is biased for ½″ production, which results in speed losses for ⅝″ products. In accordance with an embodiment, optimization for ½″ products may be accomplished in system100by fitting a smaller, narrower exit gate105to the mixer102. In addition, the gate105may typically be the area where foam is injected from injector104into the slurry stream. Using a smaller exit gate105helps ensure the passageway is completely filled, which ensures that the foam is homogenously blended into the slurry. However, using a smaller exit gate105may also unfortunately force a reduction in throughput on ⅝″ products, since the amount of flow through such a smaller exit gate105may be limited by its smaller (outlet) size. Nonetheless, the disclosed system100with its elongated hose108largely reduces and/or substantially eliminates compromises with regards to the exit gate105size. That is, the disclosed system allows for any sized gate—including a larger, funnel-type mixer gate—to be used for both ⅝″ and ½″ products, in accordance with an embodiment, if so desired. Generally, a larger gate could have compromised foam blending in the past (e.g., for reasons noted above). However, because foam is further blended in the slurry mixture as it moves through the elongated hose108of system100, the system100does not rely solely on the exit gate105for foam blending (as in traditional configurations). Thus, the mixer can be optimized for ½″ products without compromising the throughput and line speed of ⅝″ products (e.g., by using a larger exit gate or funneled exit gate (that has a wider or larger gate outlet)). It should be understood, based on the disclosure above, that this disclosure further provides a method for mixing a slurry mixture for making gypsum board. The method as disclosed herein may utilize a system as shown inFIG.1, for example, including the mixer, the foam injector, the canister and its funnel body, and the elongated hose. The method may include, for example, mixing the slurry at a first flow rate; injecting foam into the mixed slurry to form the slurry mixture (at one or a number of places previously described); inducing a swirl to the slurry mixture using the canister; and depositing the slurry mixture via the deposit outlet of the adapter onto paper to form the gypsum board. The slurry mixture is directed from the canister and through the elongated hose, before the depositing onto the paper. In one embodiment, an adapter is provided, and the slurry mixture is directed from the elongated hose into the receiving inlet of the adapter, before being deposited onto the paper. In an embodiment wherein the system includes a mixer boot, the method may include receiving, in the mixer boot, the slurry mixture from the hose or the adapter (if provided); and depositing the slurry mixture from the mixer boot onto paper to make gypsum board. The method of manufacturing and materials used to form the disclosed system10are not intended to be limited. In an embodiment, the funnel body116and/or122may be formed from stainless steel and chrome plated or coated on at least the inner walls therein. In another embodiment, one or more parts of the system10may be formed from plastic. For example, the funnel body116and/or122may be formed from plastic. Although not described in great detail herein, it should be understood by one of ordinary skill in the art that the materials mixed and used in the system100are not intended to be limited. For example, the gypsum may be a calcined gypsum or hydrated calcium sulphate (e.g., semi-hydrate calcium sulphate, calcium sulfate hemihydrate or anhydrite, anhydrous calcium sulphate or anhydrite (type II or type III), or CaSO4.2(H20), CaSO4.0.5H20, or CaSO4) and is not limited to such. Accordingly, a calcined gypsum slurry may be mixed and flow induced therein. Further, it should be understood that reference to the “slurry mixture” is not limited to just slurry and foam, and that such a “slurry mixture” may also include products or additives to the mixture such as accelerators, retarders, fillers, binders, etc. Also, the parts of the system100as illustrated are not intended to be limiting. Alternate and/or additional parts may be provided as part of system100that utilizes the elongated hose108, adapter110, and/or funnel bodies116and/or122as disclosed herein. Further, although described herein as being used with a gypsum slurry to produce a gypsum board (or plasterboard) with a gypsum core covered with sheet(s) of paper, it should be understood that the herein disclosed apparatus may be provided in alternate systems or assemblies and/or may be used with other aqueous slurries or solutions, for example, that are mixed or poured and dispensed or output using an outlet to form other products, and thus are not just limited to systems for mixing and depositing gypsum slurry to form gypsum boards. Moreover, although specific dimensions and ranges have been noted in this disclosure for different parts of the system, these dimensions and ranges are not intended to be limiting in any way. The sizes and geometries of one part may be adjusted based on sizes and geometries of another part to which it is attached, connected, or coupled to. For example, diameters of the elongated hose, adapter, and/or mixer boot openings (inlet and outlet(s)) may be altered for velocity and/or product changes. Also, the positioning of the parts of the system are not intended to be limited to the schematic drawings provided herewith. While the principles of the disclosure have been made clear in the illustrative embodiments set forth above, it will be apparent to those skilled in the art that various modifications may be made to the structure, arrangement, proportion, elements, materials, and components used in the practice of the disclosure. For example, in accordance with some embodiments, the funnel body116and/or canister106may include one or more baffles provided on its inner walls. In an embodiment, baffles such as those described in U.S. application Ser. No. 15/142,090, filed Apr. 29, 2016 and which is incorporated by reference in its entirety herein, may be provided on the inner wall14of the funnel body116. In an embodiment, baffles like those in the incorporated '090 application may be provided in the canister106. In another embodiment, the funnel body116may include one or more features described in the incorporated '090 application that are related to its funnel body, including, but not limited to: an angle and/or a slope of the inner wall, size or diameter of the inlet opening and/or outlet opening, and/or outlet height. It will thus be seen that the features of this disclosure have been fully and effectively accomplished. It will be realized, however, that the foregoing preferred specific embodiments have been shown and described for the purpose of illustrating the functional and structural principles of this disclosure and are subject to change without departure from such principles. Therefore, this disclosure includes all modifications encompassed within the spirit and scope of the following claims. | 65,132 |
11858865 | DETAILED DESCRIPTION Embodiments of this disclosure are directed to compositions and methods of carbonation processing for the fabrication of cementitious materials and concrete products that meet design criteria of compressive strength and CO2uptake. Compressive strength is a design criterion that indicates the mechanical performance of concrete materials and pre-fabricated concrete products (e.g., concrete masonry units, beams, slabs, and so forth). The CO2uptake (quantified as a mass of CO2incorporated into solid products per mass of initial solid material) describes the material's efficiency in sequestering gaseous CO2into stable solids. Enhancing CO2uptake reduces a material's embodied CO2emissions footprint, and allows impactful removal of gaseous CO2from industrial emissions sources. Together, these metrics describe the fundamental design criteria for producing construction products with carbonate-based binders that incorporate alkaline solid wastes and flue gas CO2streams. In an aspect according to some embodiments, a manufacturing process of a low-carbon concrete product includes: (1) forming a cementitious slurry including portlandite; (2) shaping the cementitious slurry into a structural component; and (3) exposing the structural component to a CO2waste stream, such as a post-combustion or post-calcination flue gas stream containing carbon dioxide, thereby enabling manufacture of the low-carbon concrete product. It is understood that, in some embodiments, the amount of carbon dioxide in the CO2waste stream (e.g., post-combustion or post-calcination flue gas stream) is greater than concentration of carbon dioxide typically in the atmosphere. In some embodiments, the process operates, effectively, at ambient pressure and/or gas temperatures. For example, in come embodiments, step (3) is performed at an ambient pressure. In some embodiments, the pressure is about 0.5 to about 10 atm, e.g., about 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 3, 4, 5, 6, 7, 8, 9 or 10 atm. In some embodiments, step (3) is performed at an ambient temperature. in some embodiments, the temperature is about 15° C. to about to about 80° C., e.g., about 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 or 80° C. In some embodiments, forming the cementitious slurry includes combining water and a binder including the portlandite, and optionally cement and coal combustion residuals (e.g. fly ash) at a water-to-binder mass ratio (w/b) of about 0.5 or less, about 0.45 or less, about 0.4 or less, about 0.35 or less, or about 0.3 or less, and down to about 0.25 or less. The term coal combustion residuals has its typical meaning in the art. Coal combustion residuals can include coal ash, and can include components such as those residuals produced when coal is burned by power plants. Coal ash can include one or more of fly ash, bottom ash, and boiler slag. Fly ash is generally composed mostly of silica and can be made from the burning finely ground coal. A post-combustion or post-calcination flue gas stream can be produced from coal fired power plants, and can include, e.g., 12.7% CO2, 2.5% O2, 66.7% N2+Ar, 18.1% H2O, 23 ppm SO2, and 28 ppm NOx. Furthermore, the portlandite carbonation and CO2mineralization reaction is insensitive to the presence of acid gases (e.g., SOxand NOx) that may be contained in flue gas streams. In some embodiments, the post-combustion or post-calcination flue gas stream can be simulated flue gas, e.g., a gas stream that is the same or similar to a post-combustion or post-calcination flue gas stream from an industrial process, such as from coal fired power plants. In some embodiments, the post-combustion or post-calcination flue gas stream includes carbon dioxide in an amount of about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, up to 50%. In some embodiments, the CO2waste stream, such as the post-combustion or post-calcination flue gas stream, is diluted. For example, the stream may be diluted by 10, 20, 30, 40, 50, 60, 70, 80, or 90 percent from its original concentration. In some embodiments, the CO2waste stream, such as the post-combustion or post-calcination flue gas stream, is enriched. For example, the stream may be enriched by 10, 20, 30, 40, 50, 60, 70, 80, or 90 percent from its original concentration In some embodiments, forming the cementitious slurry includes combining water and a binder including a cement, portlandite, and coal combustion residuals at a mass percentage of the cement in the binder of about 25% or greater, about 30% or greater, about 35% or greater, about 40% or greater, or about 45% or greater, and up to about 50%. In some embodiments, the manufacturing process includes drying the structural component prior to exposing the structural component to carbon dioxide. In some embodiments, drying the structural component includes reducing a fraction of pore volume that is saturated with liquid water (Sw) to less than 1, such as about 0.9 or less, about 0.8 or less, about 0.7 or less, about 0.6 or less, about 0.5 or less, or about 0.4 or less, and down to about 0.1. In some embodiments, drying the structural component includes reducing Swto a range of about 0.1 to about 0.7, about 0.2 to about 0.6, about 0.2 to about 0.5, or about 0.2 to about 0.4. In some embodiments, drying the structural component is performed at a temperature in a range of about 20° C. to about 85° C., about 30° C. to about 65° C., or about 35° C. to about 55° C., for a time duration in a range of 1 h to about 72 h. In some embodiments, shaping the cementitious slurry includes compacting the cementitious slurry to form the structural component. For example, in some embodiments, shaping the cementitious slurry includes either compacting the cementitious slurry (dry-casting) or pouring the slurry in to a mold (wet-casting) to form the structural component. In some embodiments, compacting the cementitious slurry includes reducing a degree of pore water saturation (Sw) to less than 1, such as about 0.9 or less, about 0.8 or less, about 0.7 or less, about 0.6 or less, about 0.5 or less, or about 0.4 or less, and down to about 0.1. In some embodiments, compacting the cementitious slurry includes reducing Swto a range of about 0.1 to about 0.7, about 0.2 to about 0.6, about 0.2 to about 0.5, or about 0.2 to about 0.4. In some embodiments, compacting the cementitious slurry is performed at a pressure in a range of about 0.5 MPa to about 50 MPa, e.g., about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 30, 35, 40, 45, or 50 MPa. In some embodiments, exposing the structural component to carbon dioxide is performed at a temperature in a range of about 20° C. to about 85° C., about 30° C. to about 75° C., about 35° C. to about 70° C., or about 40° C. to about 65° C. In some embodiments, the low-carbon concrete product have up to 75% lower carbon intensity than a traditional cement-based concrete product. In some embodiments, the lower carbon intensity is due to (a) partial substitution of cement with portlandite and fly ash and/or (b) CO2uptake during manufacturing. As understood by the skilled artisan, a traditional cement-based concrete product can have a carbon intensity of about 0.5 to about 1.5 tons of CO2per ton of OPC used in concrete products, e.g., about 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, or 1.5 tons of CO2per ton of OPC used in concrete products. For example, a traditional cement-based concrete, and its products can have a carbon intensity of about 195 to about 771 kg CO2e per m3. It will be understood that in some embodiments other benefits or aspects disclosed more specifically below are also applicable to the above-disclosed embodiments. In another aspect according to some embodiments, a manufacturing process of a low-carbon concrete product includes: (1) providing a target compressive strength of the concrete product; (2) providing a prediction model relating carbon dioxide uptake to compressive strength; (3) forming a cementitious slurry including portlandite; (4) forming the cementitious slurry into a structural component; and (5) exposing the structural component to carbon dioxide, thereby forming the low-carbon concrete product, wherein exposing the structural component to carbon dioxide includes monitoring carbon dioxide uptake of the structural component, and exposing the structural component to carbon dioxide is performed at least until the carbon dioxide uptake of the structural component is indicative of meeting the target compressive strength according to the prediction model. In some embodiments, the carbon dioxide is contained within a CO2waste stream, such as a post-combustion or post-calcination flue gas stream, such as those described elsewhere herein. Specific Embodiments and Examples The following embodiments and examples describes specific aspects of some embodiments of this disclosure to illustrate and provide a description for those of ordinary skill in the art. These embodiments and examples should not be construed as limiting this disclosure, as the embodiments and examples merely provides specific methodology useful in understanding and practicing some embodiments of this disclosure. Overview In certain embodiments, a cementation solution is mineral carbonation (CO2mineralization), which is the reaction of CO2with inorganic precursors to produce stable carbonate solids. Such reactions can be exploited to produce cement-replacement materials while sequestering CO2from industrial emissions streams. To achieve cementation by carbonation, a shape-stabilized “green-body” (e.g., block, slab, beam, and so forth) is exposed to fluid CO2(e.g., gas or liquid). Such in situ CO2mineralization is a multi-stage process that typically proceeds via dissolution-precipitation (rather than direct solid-gas reaction), namely in some embodiments, the multi-stage process can proceed via the following stages (for calcium-bearing reactants):1) Dissolution of reactants to yield Ca2+within liquid water in pore network/water films at reactant surfaces,2) Transport of CO2through the green body's pore network towards pore water,3) Dissolution of CO2in pore water and speciation to HCO3−or CO32−, and4) Reaction of dissolved species to precipitate mineral carbonates (e.g., CaCO3). In addition to CO2sequestered into solid products, the embodied CO2emissions of carbonating binders may be reduced vis-à-vis OPC by diminishing production and use of OPC. This is because the reactants can be industrial wastes (e.g., coal fly ash) and/or phases produced via lower-temperature routes (e.g., portlandite or Ca(OH)2). CO2mineralization of portlandite with flue gas is thermodynamically favored at near-ambient temperatures. The final carbonation conversion of portlandite particulates is found to be controlled by the relative humidity RH of the contacting gas stream—i.e., independent of temperature T and CO2concentration [CO2] (FIG.1). The weak dependence of portlandite particulate carbonation to CO2concentration suggests that substantially enhancement of the CO2concentration beyond that typical to flue gases, e.g., by membrane enrichment, is unlikely to yield proportional increases in the reaction kinetics of portlandite particles. This finding highlights the suitability of portlandite carbonation within process cycles that use (un-enriched) post-combustion gas streams, which may be secured from natural gas or coal-fired power generation systems. For readily-dissolved reactants such as portlandite, a constraint on carbonation rates is CO2transport, which depends, in part, on the presence of liquid water in the green body. Liquid water in pore networks retards CO2transport by physical hindrance, since CO2diffusion in water is about 105times slower than in air. The strengthening of binders containing rapidly dissolved Ca-bearing phases along with fly ash and OPC is a complex process, as strengthening is induced by precipitation of both carbonates and of C-S-H (formed by OPC hydration and pozzolanic reactions of Ca(OH)2with aluminosilicate sources such as fly ash). Carbonation of Wet-Cast Compositions: Investigation is made of the carbonation kinetics of mortars containing portlandite-enriched binders in contact with flue gas simulating that from a coal fired power plant (about 12% CO2). A representative binder composition includes about 42 mass % portlandite, about 25 mass % ASTM C618-compliant Class F fly ash (FA), and about 33 mass % OPC. This binder is mixed with fine aggregate (sand) and water to form a mortar. The carbonation kinetics of these mortars is investigated as a function of their initial pore saturation with water (Sw), which is controlled by drying prior to carbonation (FIG.2A). The extent of CO2uptake achievable within feasible processing durations increases significantly as Swis reduced, until saturation is reduced below a critical value (Sw,c). The value of Sw,cis between about 0.13 and about 0.07 for wet-cast compositions, indicating that this suppression of CO2uptake is due to the reduction of water below the intrinsic level for Ca(OH)2dissolution and carbonation product precipitation. Until this point, carbonation kinetics are hastened by the reduction of pore saturation, and are sufficiently rapid, even in direct exposure to diluted gas streams, to render sufficient CO2uptake within a feasible processing duration. The strengthening resulting from carbonation (e.g., per unit CO2uptake) is described inFIG.2B. Despite their varying CO2uptake, all compositions demonstrated broadly corresponding compressive strength development, which is comparable or superior to that achieved solely by cement hydration (e.g., sealed curing) by the end of the processing period. Concrete mixtures are typically specified to achieve design compressive strength criteria at an age of 28 days after casting. To evaluate the continued strength development (and progress of hydration and pozzolanic reactions) in carbonated portlandite-enriched binders, mortar specimens are cured in saturated limewater following carbonation, and their compressive strengths are measured (FIG.3A). As a point of reference, similar evaluations are performed for non-carbonated specimens, and specimens featuring a portlandite-free binder (about 75% OPC and about 25% Class F fly ash). Despite its initially lower strength development, the carbonated portlandite-enriched binder achieved corresponding compressive strength to that of the carbonated mixtures without portlandite, while achieving over about 4× greater CO2uptake. The continued strength development is attributed to the continued progress of pozzolanic reactions (e.g., between residual calcium hydroxide and silica-rich fly ash) and cement hydration during limewater curing.FIG.3Bdisplays the mass fraction of calcium hydroxide in each specimen as a function of specimen age, as assessed by thermogravimetric analysis. The initially elevated calcium hydroxide content of the portlandite-enriched binder is rapidly decreased with carbonation, and then shows a continual reduction due to consumption by pozzolanic reactions, at a higher rate than the reference binder. The pozzolanic reaction manifested in the continued development of C-S-H, as indicated by the non-evaporable water (wn) evolution, which was normalized by the OPC mass fraction (FIG.3C). This figure indicates that carbonated portlandite-enriched binders show a similar evolution of hydrated phases to the non-carbonated reference OPC binders. This trend ensures that unlike the carbonated OPC binder which demonstrates suppressed hydration/pozzolanic reactions in time, carbonated portlandite-enriched compositions continue to gain strength at a higher rate due to formation of hydrated phases. Carbonation of Dry-Cast Compositions: Mortar formulations containing the same portlandite-enriched binder composition, but with elevated sand content and reduced water content are also developed. Rather than being poured into a mold, these specimens are “dry-cast” into a mold and compacted using a hydraulic press to become shape-stable, as for concrete masonry products.FIG.4Acompares the CO2uptake of both wet-cast and dry-cast compositions as a function of their saturation. While dry-cast components exhibit higher specific CO2uptake than wet-cast specimens, both formulations exhibit similar trends with respect to pore saturation. The critical saturation Sw,cis similar between the two formulations within the experimental resolution. This trend is also observed in dry-cast pellets composed of solely portlandite (FIG.4B), indicating that the Sw,creflects the intrinsic sensitivity of Ca(OH)2carbonation to proximate relative humidity (RH). The strengthening of dry-cast specimens with increasing carbonation durations is illustrated inFIG.5A, which plots compressive strength as a function of the relative density, a measure of the volume fraction of porosity within the specimens. Carbonation significantly elevates compressive strength relative to non-carbonated samples, and is the dominant contribution to strength development, for all relative densities. At either duration of carbonation, the increase in strength due to carbonation is also approximately constant regardless of the relative density. This finding allows the carbonated strength to be predicted from early age measurements of compressive strength of non-carbonated specimens. The influences of reaction temperature on the carbonation kinetics and strength development of dry-cast binders are also of note. Given that increasing temperature accelerates both the rate of drying and rate of carbonation, the effects of carbonation temperature on dry-cast mortar specimens are evaluated as a function of the reaction temperature, without drying prior to CO2exposure (FIG.5B). Increasing the reaction temperature up to about 65° C. increased both the CO2uptake and 24-h compressive strength substantially. However, further increasing the temperature to about 85° C. diminished both CO2uptake and strength gain on account of the insufficient availability of water (Sw=0.06 following CO2exposure at about 85° C. for about 12 h) to support carbonation reactions. This information indicates that carbonation processing may be applied without pre-drying, which allows enhanced process flexibility and increased throughput of CO2utilization. The critical saturation Sw,cobserved previously (in cases in which drying did not appreciably reduce the saturation during carbonation) also holds when carbonation processing conditions yield simultaneous drying (saturation reduction). CO2Uptake—Strength Correlations: To provide unifying guidelines describing the effect of carbonation on strength development,FIG.6shows the carbonation strengthening factor (the ratio between carbonated and non-carbonated specimens) as a function of CO2uptake. Both wet-cast and dry-cast compositions follow a linear trend of increasing carbonation strengthening with CO2uptake, up to a value of about 3.75. This allows forecasting of compressive strength development resulting from various compositions and processing, provided that the CO2uptake is determined. This is important, as the CO2uptake can be assessed in real-time during carbonation, using on-line instrumentation to quantify reductions in gaseous CO2concentrations (e.g., nondispersive infrared (NDIR) sensor or gas chromatography). Fulfillment of Strength Criteria: Fulfilling design strength criteria (typically 1 day and 28-day strengths) may be achieved via three primary levers: (1) changing the water-to-binder mass ratio (w/b), (2) adjusting the mass proportions of a ternary blend of portlandite-fly ash-OPC in the binder, and (3) altering the processing conditions. A strategy for fulfilling performance criteria (e.g., strength) involves (i) implementing drying prior to carbonation to adjust liquid water saturation in pores, (ii) elevating the temperature used during carbonation processing to simultaneously enhance reaction kinetics and CO2transport properties (e.g., up to about 65° C.), (iii) reducing the water-to-binder mass ratio (w/b) to reduce volume of porosity, and (iv) increasing OPC content in binder system (e.g., at most ≤about 50 mass % of OPC). As an example inFIG.7, it is highlighted that processing of a wet-cast mortar by drying at T=about 45° C. for about 12 h resulted in a higher CO2uptake after carbonation for about 24 h, and also in a greater strength as compared to a similar mortar that was directly carbonated (without an initial drying stage) for a longer duration of about 36 h. After carbonation, the strength continued to increase during limewater curing at which strength on the order of about 35 MPa was produced at 28 days. Furthermore, by comparing strength results betweenFIG.3AandFIG.7, for a similar processing condition, reducing w/b from about 0.45 to about 0.40 and increasing OPC content from about 35% to about 50% enhanced the 28-day strength from about 25 MPa to about 35 MPa. These findings demonstrate that adjustment of processing conditions and mixture proportioning can be implemented to develop carbonate-cemented solids that take up CO2and provide strengths sufficient to fulfill structural construction criteria (e.g., ≥about 30 MPa as per ACI 318; and ≥about 15 MPa as per ASTM C90 for concrete masonry units), as indicated inFIG.5BandFIG.7. Example Carbonation Processing and Strength Evolution of Portlandite-Based Cementing Binders Overview Binders containing portlandite (Ca(OH)2) can take up carbon dioxide (CO2) from dilute flue gas streams (<15% CO2, v/v) thereby forming carbonate compounds with binding attributes. While the carbonation of portlandite particulates is straightforward, it remains unclear how CO2transport into monoliths is affected by microstructure and pore moisture content. Therefore, this study elucidates the influences of pore saturation and CO2diffusivity on the carbonation kinetics and strength evolution of portlandite-enriched composites (“mortars”). To assess the influences of microstructure, composites hydrated to different extents and conditioned to different pore saturation levels (Sw) were exposed to dilute CO2. First, reducing saturation increases the gas diffusivity, and carbonation kinetics, so long as saturation exceeds a critical value (Sw,c≈0.10); independent of microstructural attributes. Second, careful analysis reveals that both traditional cement hydration and carbonation offer similar levels of strengthening, the magnitude of which can be estimated from the extent of each reaction. As a result, portlandite-enriched binders offer cementation performance that is similar to traditional materials while offering an embodied CO2footprint that is more than 50% smaller. These insights are foundational to create new “low-CO2” cementation agents via in situ CO2mineralization (utilization) using dilute CO2waste streams. Cementation enabled by in situ carbonation is a promising alternative to conventional concrete that relies upon the reaction of CO2with alkaline inorganic precursors to precipitate carbonate solids. In this method, a shape-stabilized green body (e.g., block, slab, beam) is exposed to CO2, e.g., in the gas, liquid, or supercritical states, which may be sourced from CO2waste streams. Here, green bodies may be produced by either wet-casting (wherein a slurry is poured into a mold until it hardens and becomes self-supporting) or dry-casting (in which components having very low water contents are mechanically compacted until they are self-supporting). In the absence of water, the carbonation of mineral reactants such as portlandite (Ca(OH)2) may proceed via gas-solid reaction. However, faster rates and greater extents of portlandite conversion and CO2mineralization are realized when the presence of liquid water promotes a dissolution-precipitation mechanism of carbonation, which entails the following steps for green bodies composed of calcium-bearing reactants:The dissolution of the reactants releases Ca2+species within the pore liquid,The dissolution and transport of CO2(i.e., as a gas/vapor or dissolved carbonate ions) occurs from the outside environment through the green body's pore network, and,The reaction of dissolved species precipitates carbonate minerals (e.g., CaCO3). The embodied CO2intensity of the resulting carbonated binder may be substantially reduced vis-à-vis OPC depending on the nature of reactants used. This is attributed to: (i) the direct sequestration of CO2from an emissions stream which fulfills the premise of CO2utilization, and (ii) the CO2avoidance associated with the substitution of OPC by industrial wastes (e.g., coal fly ash) or alkaline solids that may be produced by a low-temperature pathway, e.g., portlandite. In green bodies composed using readily-dissolving reactants such as portlandite, CO2transport through the body is often the rate limiting step in carbonation. In the absence of significant pressure gradients, CO2transport is dominated by diffusion. As the diffusivity of dissolved CO2through water is ≈104times lower than that of gaseous CO2in air, the provision of air-filled porosity within green bodies is critical to accelerating the rate of carbonation. The effective diffusivity of partially saturated pore networks is inversely proportional to the microstructural resistance factor f(Sw, ϕ). The microstructural resistance to diffusion increases as the total porosity, ϕ, is reduced and as the volume fraction of porosity that is saturated with liquid water, Sw, is increased. The total porosity of portlandite-enriched composites is a function of their composition (e.g., water-to-binder mass ratio, aggregate content), method of forming (e.g., wet-cast vs. dry-cast, and degree of consolidation), and the extent of hydration and carbonation reactions that may have occurred. On the other hand, Swcan be reduced by using dry-cast mixtures with low water contents, or by drying before (or during) CO2exposure. However, large reductions in Swmay depress the internal relative humidity (RH) within the green body's pores; a relationship which is described by the material's water vapor sorption isotherms. This is significant, as the RH of the CO2-containing gas stream (“reaction environment”) that is contacting portlandite has been noted to significantly impact its carbonation behavior. For example, portlandite's carbonation in dry conditions (RH≈0%) is hindered (e.g., less than 10% conversion), due to surface passivation associated with gas-solid carbonation. Increasing the RH is noted to promote a dissolution-precipitation pathway, which enables near complete conversion (e.g., in excess of 80%). Although the important of the reaction environment's RH on the carbonation of portlandite particulates is recognized, the effect of pore saturation on the carbonation of portlandite-based monoliths remains unclear. The fabrication of carbonated wet-cast or dry-cast structural concrete components that fulfill specific engineering performance criteria requires a detailed understanding of the mechanisms of cementation (strengthening) therein. Although it is known that the products of carbonation, OPC hydration, and pozzolanic reactions can adhere proximate surfaces and induce reductions in porosity, the contributions of these reactions to strength gain, especially in carbonated composites, remain unclear. For example, during CO2exposure, these reactions occur concurrently, making it difficult to isolate the contributions of each reaction to strength gain. Furthermore, C-S-H precipitation on reactant surfaces and within pore spaces, prior to carbonation, may limit strengthening by hindering CO2diffusion and reducing the availability of exposed reactant (portlandite) surfaces. Finally, it is unknown whether conventional relationships between the extent of hydration and strength hold true during CO2exposure, as processing conditions that may favor carbonation (e.g., decreasing Swby drying) may suppress OPC hydration and pozzolanic reactions due to the consumption of portlandite. To overcome gaps in knowledge to implement carbonation-based cementation, this example primarily aims to elucidate the influences of microstructure on the carbonation kinetics of portlandite-enriched cementing composites (“mortars”). The premise of using portlandite is straightforward for a multiplicity of reasons including:Making use of existing facilities: Portlandite can be produced using limestone as a precursor using existing OPC kilns and features a cost that is essentially similar to OPC,Lower processing temperature: Portlandite's production, by the decarbonation of limestone around 800° C. (at ambient pressure, in air), followed by the hydration of lime requires a processing temperature that is nearly 700° C. lower than OPC production,Straightforward carbonation: Unlike OPC and other potential alkaline precursors, portlandite carbonation is only slightly affected by temperature and CO2partial pressure for conditions relevant to flue gas exposure (≈4-15% CO2, v/v), provided that the RH of the contacting gas is sufficient to promote liquid water-mediated carbonation, and,Highest CO2uptake: Due to its substantial calcium content, portlandite features among the highest potential CO2uptake (59 mass %) of mineral reactants that may be achieved in contact with flue gases. For example, although Mg(OH)2has a higher potential CO2uptake (75 mass %), it requires a greatly elevated temperature and pressure to achieve similar carbonation kinetics (rates) as portlandite. Taken together, the findings highlight that portlandite-enriched binders can serve as a viable functional replacement for OPC-based cementation agents, and offer new insights to design concrete construction components that are cemented via in situ CO2mineralization. Materials and Methods: Materials and Sample Preparation Portlandite-enriched binders were composed of: 42 mass % portlandite, 33 mass % ASTM C150-compliant ordinary portland cement (Type II/V OPC) and 25 mass % ASTM C618-compliant Class F fly ash (FA). OPC was incorporated to provide green strength and to facilitate handling prior to drying and carbonation, whereas FA served as a source of aluminosilicates to promote pozzolanic reactions. A portlandite-free reference binder (i.e., 75 mass % OPC and 25 mass % FA) was also formulated to isolate portlandite's influences on reactions and strength evolution. The portlandite (Mississippi Lime) used featured a purity of 94%±2% (by mass) with the remainder being composed of CaCO3as determined by thermogravimetric analysis (TGA). The median particle diameters (d50) of portlandite, FA, and OPC were 3.8 μm, 8.9 μm, and 17.2 μm, respectively, as determined using static light scattering (SLS; LS13-320, Beckman Coulter). Further details on the chemical composition and particle size distributions of binder solids are reported in the Supporting Information (SI). The binders were combined with ASTM C33 compliant silica sand (fine aggregate) to form composites (“mortars”) as described in ASTM C305. Wet-cast composites were formulated at w/b=0.45 (w/b=water-to-binder mass ratio) and a/b=3.5 (a/b=aggregate-to-binder mass ratio). Dry-cast composites had w/b=0.25 and a/b=7.95. The fine aggregate had a density of 2650 kg/m3and a water absorption of ≤1.0 mass %. A commercially-available polycarboxylate ether (PCE) dispersant was added to enhance the fluidity of the wet-cast composites at a dosage of 0.8% of the binder mass. The wet-cast composites were molded into cylinders (50 mm×100 mm; d×h) and vibrated to remove entrapped air. Dry-cast composites were prepared by compaction using a hydraulic press to form cylindrical specimens (75 mm×40 mm; d×h) that featured a surface area-to-volume ratio (SA/V, mm−1) equivalent to the wet-cast specimens. The compaction pressure was varied between 0.5 MPa and 22.0 MPa to achieve relative densities (ρ/ρs, the ratio of bulk density to skeletal density) ranging between 0.58-to-0.88. Dry-cast portlandite composites with w/b=0.25 and a/b=7.95 as well as neat portlandite pellets (10 mm×8 mm; d×h) with different water-to-solid (i.e., portlandite) mass ratios between 0 and 0.75 were also formed by compaction for comparative analyses. Drying and Carbonation Processing The wet-cast composites were cured under sealed conditions for 6 h at T=22±2° C. to achieve shape stability and a compressive strength σc≈0.5 MPa. The specimens were then either carbonated immediately after forming or dried under exposure to flowing air to achieve different initial Swprior to carbonation. In contrast to the wet-cast composites, the initial Swof the dry-cast composites was altered by applying different compaction pressures. During drying and carbonation, the cylindrical specimens were placed in custom-built reactors with an internal diameter of 100 mm and a length of 150 mm (see schematic,FIG.14in SI). The reactors were placed in an oven for temperature regulation and the flow rate of the inlet gas was controlled by mass-flow controllers. Different drying conditions were implemented by varying the: (i) air temperature (22±0.5° C., 45±0.5° C., and 65±0.5° C.), (ii) air flow rate (0.5 slpm to 40 slpm; standard liters per minute), and, (iii) drying duration (0 to 12 h). Carbonation during air drying was very limited. The average CO2uptake of wet-cast specimens prior to CO2exposure was 0.015±0.005 gCO2/greactants. The dried specimens were then contacted with simulated flue gas at a flow rate of 0.5 slpm for up to 60 h at different isothermal temperatures (22±0.5° C., 45±0.5° C., and 65±0.5° C.). The simulated flue gas was prepared by mixing air and CO2to mimic the exhaust of a coal power plant. The CO2concentration of the gas was 12±0.2% [v/v] as confirmed using gas chromatography (GC; F0818, Inficon). Experimental Methods Time-dependent CO2uptake was quantified using thermogravimetric analysis (TGA: STA 6000, Perkin Elmer). The values reported are the average CO2uptake of three powdered samples taken along the height of the cylindrical specimens. Around 30 mg of each powder was placed in pure aluminum oxide crucibles and heated at a rate of 15° C./min over a temperature range of 35° C. to 975° C. under UHP-N2gas purge at a flow rate of 20 mL/min. The CO2uptake was quantified as the mass loss associated with CaCO3decomposition over the temperature range of 550° C. to 900° C., normalized by the total mass of solids in the binder (i.e., portlandite, fly ash, and OPC). Towards this end, the mass loss associated with CaCO3was initially normalized by the total sample mass (i.e., aggregate+binder solids) in the form of gCO2/gsolid. The results were then normalized by the fraction of binder present in the total solids (i.e., gCO2/gsolid*gsolid/greactants=gCO2/greactants), which was determined from the mixture proportions. It should be noted that the initial CO2content (i.e., carbonate minerals within the aggregates and binder) and the CO2uptake during drying were subtracted from the overall CO2uptake measured during carbonation, to eliminate their influences on the experimental results. The non-evaporable water content (wn, mass %) was calculated as the mass loss over the temperature range of 105° C. to 975° C. excluding the mass loss from the decomposition of CaCO3and Ca(OH)2. The compressive strength of the composites was measured as per ASTM C39. Appropriate strength correction factors were applied in consideration of the specimens' length-to-diameter ratios to allow direct comparisons between the dry-cast and wet-cast specimens, which feature slightly different geometries. The total porosity and pore (moisture) saturation level of the composites before and after carbonation were quantified using a vacuum saturation method. Cross-sectional disks, 25 mm-thick were sectioned from the middle of the cylindrical specimens using a low-speed saw. Isopropanol (IPA) was used as the solvent to arrest hydration. The CO2diffusivity was estimated from the total moisture diffusion coefficient, Dtot(m2/s), (i.e., the sum of liquid water and water vapor diffusion coefficients) of the composites prior to CO2exposure using Fick's 2ndlaw of diffusion, as elaborated in the SI. Results Influences of Saturation on CO2Uptake in Portlandite-Enriched Binders The carbonation kinetics of wet-cast composites pre-dried to different initial Sw(FIG.15in SI) were evaluated.FIG.8Adisplays the time-dependent CO2uptake of each specimen C(t) normalized by the mass of reactants, i.e., portlandite, fly ash, and OPC. The measured data was fitted to an equation of the form C(t)=C (tu) [1−exp ((−kt)/C(tu))] to estimate the apparent carbonation rate constant (k, h−1), and C(tu), the ultimate CO2uptake, where tuis taken as 60 h. Reducing Swfrom 1.00 (complete saturation) to 0.13 for the wet-cast composites increased both the carbonation rate constant and the ultimate CO2uptake by nearly 10× (FIG.8A). The same observation is true for dry-cast composites, demonstrating the significance of Swas a controlling variable on carbonation kinetics across different forming methods and microstructures. But, enhanced levels of CO2uptake were obtained for the dry-cast relative to wet-cast composites at comparable Sw(FIG.8B), as further discussed below. The carbonation of both the wet-cast composites and neat portlandite compacts was nearly fully suppressed when Swwas reduced below a critical value, Sw,c≈0.10 (FIG.8C). It should be clarified that although the trend fitted to the data for dry-cast composites indicates a higher critical saturation Sw,c=0.30 (identified as Swat which there is a maximum in CO2uptake), this estimation resulted from a lack of data corresponding to dry-cast composites within 0.03<Sw<0.30. However, separate data obtained for the neat portlandite compacts (FIG.8C) indicated a critical saturation level, Sw,c=0.14. This value is similar to Sw,c=0.12 that was determined for the wet-cast composites (FIG.8C). This implies that Sw,c≈0.10 is an intrinsic limit on portlandite carbonation, which is sustained for composites prepared by both wet-cast and dry-cast forming methods. Assuming that the water vapor sorption isotherms of portlandite-enriched binders are functionally similar to those of typical cementitious binders, Sw,c≈0.10 corresponds to an internal RH≈10%. These findings broadly agree with the minimum ambient RHc=8% to promote carbonation reactions via a dissolution-precipitation pathway. So long as Sw,cis exceeded, Ca2+species liberated following the dissolution of portlandite and other Ca-bearing reactants (OPC and fly ash) react with dissolved CO2species (i.e., CO32−and HCO3−) to precipitate calcium carbonate. However, below Sw,c, carbonation may be hindered by the reduced mobility and availability of water to support dissolution and precipitation; thus, carbonation should, in some embodiments, proceed by gas-solid reaction, which is limited by surface passivation. This observation suggests that carbonation suppression at low Swmay result from a shift in the reaction mechanism, which is applicable across processing and preparation conditions. Therefore, maintaining Sw>Sw,cis an important requirement in some aspects for the carbonation of portlandite-enriched binders to enhance CO2uptake and the carbonation strengthening. A detailed analysis of the TGA traces of portlandite-enriched composites indicated that Ca(OH)2was rapidly converted upon CO2exposure, and accounted for nearly all of the overall CO2uptake within the first 10 h CO2exposure. As portlandite conversion slowed, the contribution of other solid such as C-S-H became significant. These results suggest that the overall carbonation rate largely corresponded to that of portlandite carbonation initially, with a progressive switchover, in time, to the carbonation of other solid phases which including C-S-H. The contributions of other solid phases to the total CO2uptake of binder for the wet- and dry-cast composites ranged between 2%-15% and 20%-38%, respectively, after 60 h CO2exposure. These results indicate that the overall CO2uptake of portlandite-enriched composites is largely dominated by portlandite carbonation. The differences in the carbonation kinetics between wet-cast and dry-cast composites are on account of the composites' microstructural resistances to CO2diffusion. Here, the CO2diffusivity was indirectly estimated by the total moisture diffusivity, which was measured by one-dimensional drying experiments. Although the mechanisms by which CO2and moisture (i.e., in the form of liquid and vapor phases) diffuse through pore networks may somewhat differ, they are both controlled by the total porosity, tortuosity and saturation level of the pore structure. The total moisture diffusivities of the composites were estimated at the time immediately prior to the initiation of carbonation. At equivalent Sw, the dry-cast composites showed a higher moisture diffusivity than wet-cast composites, due to their lower degree of OPC hydration (FIG.9A). This reinforces the premise that microstructural resistance controls CO2diffusion and carbonation reaction kinetics. The carbonation rate constant of wet-cast and dry-cast composites at varying Swshows a similar logarithmic scaling as a function of the total moisture diffusivity for Sw≥0.13 (FIG.9B). It should be noted, however, that the dry-cast composites showed rate constants that are systematically higher than those of wet-cast composites for equivalent diffusivities. This difference is postulated to result from the different extents of OPC hydration of the two composites, as reflected in their non-evaporable water contents (FIG.9C). Indeed, the CO2uptake of both wet-cast and dry-cast composites decreased at a similar rate with increasing non-evaporable water content. The enhanced carbonation kinetics of the dry-cast composites is therefore consistent with the elevated accessibility of portlandite surfaces therein, due to such surfaces being less occluded by C-S-H precipitates which may impose transport barriers to CO2contact and intrusion. This indicates that if OPC hydration in wet-cast composites was limited to a degree similar to that of the dry-cast composites (while ensuring shape stability) they too may feature enhanced CO2uptake. Carbonation Strengthening of Portlandite-Enriched Binders The compressive strengths of the portlandite-enriched composites increased over the course of CO2exposure due to carbonation and OPC hydration (FIG.10A). Notably, despite their lower extents of OPC hydration (i.e., wn/mOPC), the carbonated composites featured strengths equivalent to or greater than that of a sealed composite, i.e., in which OPC was permitted to hydrate without CO2exposure. Strength slightly increased as the initial Swwas reduced, owing to the increased CO2uptake (FIG.16in SI). However this was so only as long as Sw>Sw,c, because, in general, both carbonation and hydration are suppressed at low internal RH. The critical pore saturation required to sustain OPC hydration is substantially higher than that of carbonation reactions. For instance, the hydration of alite (Ca3SiO5, the major phase in OPC) is suppressed when the internal RH drops below 80%. The dry-cast composites showed a contrasting trend, whereby strength increased with Sw(FIG.10bB). However, this is, in part an artifact resulting from the reduction in total porosity that resulted from the increased levels of compaction that were used to elevate Sw. For example, analytical analysis of particle packing within the dry-cast composites reveals a 4× reduction in the interparticle spacing as the relative density increased from 0.67 to 0.88. Not only does this improve particle-to-particle contacts, but it also permits more effective cohesion in the material by a smaller quantity of cementing agent (carbonate precipitates). Unlike carbonated pastes composed only of fly ash, the strength-CO2uptake curves of portlandite-enriched composites with different initial Swcannot all be fitted by a single linear relation, i.e., with a shared slope m=Δσc/ΔC; MPa/(gCO2/greactant) that remains constant over the course of carbonation (seeFIG.10). Rather, both wet-cast and dry-cast composites demonstrated unique bi-linear trends wherein the secondary slope m2(i.e., between t=6 h and t=60 h) was steeper than the initial slope m1(i.e., between t=0 h and t=6 h); i.e., indicating an increase in the strength gain per unit CO2uptake at later ages after the cementing agent first cohered the solid skeleton together. Interestingly, the later-age slope m2increased exponentially with the normalized non-evaporable water content Δ(wn/mOPC) and eventually sketched a single curve for both wet-cast and dry cast mixtures (FIG.10C). As such, extrapolation to Δ(wn/mOPC)=0 (i.e., when the OPC would remain unreacted during CO2exposure) yields a y-intercept of 14.7 MPa per unit mass CO2uptake (gCO2/greactants). This value reflects the strength gain per unit mass of CO2uptake in the portlandite-enriched binder in the absence of concurrent strengthening by OPC hydration. This level of strengthening is substantially higher than the 3.2 MPa per unit mass of CO2uptake noted for fly ash reactants (gCO2/gfly ash)—an unsurprising outcome given the much higher mobility and availability of Ca-species and greater carbonation reaction rate provisioned by portlandite. Similar analysis of the strength-wn/mOPCrelation over the course of CO2exposure (FIG.10D) indicates that OPC hydration results in strength gain of ≈0.38 MPa per unit of OPC reacted (wn/mOPC). As such, assuming that the binding effects of carbonation and OPC hydration are additive, for processing carried out at 22° C., strength developed can be estimated by an equation of the form σc(t)=A·C(t)+B·wn(t)/mOPCwhere A=14.7 MPa/(gCO2/greactants) and B=0.38 MPa/(wn/mOPC) as determined from the slopes of the strength-CO2uptake and strength-wn/mOPCcurves. Note, the strength gain per degree of OPC hydration estimated above is similar to that observed during sealed curing in the absence of CO2exposure (FIG.16in SI) and to that within portlandite-free composites, indicating that carbonation, and the presence of portlandite as a reactant does not explicitly induce a change in the composition (i.e., Ca/Si, molar ratio) or binding performance of the reaction products that are formed. It should be noted however, that the strength prediction equation noted above offers better estimates for the dry-cast, as opposed to the wet-cast composites. This is on account of the effects of drying (FIG.17in SI). For example, unlike drying at a low flow rate of 0.5 slpm (i.e., similar to that used for carbonation), increasing the flow rate to enhance drying depressed the rate of strength gain per degree of OPC hydration. This may be attributed to the effects of microcracking, and/or heterogeneity in microstructure with respect to the nature of hydration products that may form resulting from the accelerated extraction of water, especially at higher temperatures. Due to the inherently lower water content of the dry-cast composites, and the reduced extent of OPC hydration that results—dry-cast composites are therefore less affected by processing conditions prior to carbonation. Nevertheless, analysis of the carbonation strengthening factor (Fcs, unitless), i.e., the ratio of the strength of carbonated to non-carbonated composites revealed that dry-cast composites composed of neat-portlandite achieved Fcs=3.75 (FIG.11A). This was substantially higher than the strengthening factors achieved for wet-cast composites (Fcs≤2.5) and dry-cast composites (Fcs≤3.25)—and confirms that the strengthening offered by the in situ formation of carbonates is foundational in ensuring cohesion and strength development (FIG.18in SI). Interestingly, Fcsof dry-cast mixtures was inversely correlated to their relative density (ρ/ρs) indicating that the strengthening effect arising from compaction/particle interlock reduces the relative influence of carbonation and the bridging action of cementing precipitates. Sw, can be additionally controlled, especially in dry-cast composites, by changing the temperature, i.e., by imposing drying using a heated gas stream, prior to and during carbonation. As noted inFIG.11B, elevating the reaction temperature substantially enhanced both CO2uptake and strength, resulting in the development of σc≈25 MPa in 24 h. This is attributed to both facilitated CO2transport due to the removal of water by evaporation (increased carbonation reaction rate), and the stimulation of OPC hydration and pozzolanic reactions (as indicated by wn/mOPCinFIG.11B). However, in agreement with the results for drying-induced changes in Sw, a temperature increase is beneficial to a limit—further increasing the temperature to 85° C. diminished both CO2uptake and strength gain on account of the insufficiency of pore water to support both CO2mineralization and OPC hydration reactions. This is attributed to: (a) the exothermic nature of carbonation reactions wherein temperature rise (unless the heat is rapidly dissipated) shifts the reaction equilibrium towards the reactants thereby resulting in a retardation in reaction progress; following Le Chatelier's principle, and (b) the rapid extraction of water, as a result of which carbonation and hydration are both suppressed due to the rapid decrease in the liquid saturation level in the pores. These observations suggest that use of a partially humidified CO2(flue gas) stream could favor carbonation in composites having low water contents (e.g., dry-cast composites) that are processed at higher temperatures. As an example, the flue gas emitted from a coal-fired power plant features temperatures (T) and a water vapor contents (wv, v/v) on the order of 50° C.≤T≤140° C. and 12%≤wv≤16%, respectively. The water (vapor) present in the flue gas could thus compensate for water loss due to evaporation at such temperatures. Long-Term Strength Development of Carbonated Composites The strength evolution of carbonated composites following an initial period of CO2processing is relevant because the compressive strength of cementitious materials at 28 days currently serves as an important criterion/specification/compliance attribute in structural design. Therefore, wet-cast portlandite-enriched composites with Sw=0.65 were either: (a) cured in saturated limewater (Ca(OH)2solution) at 22° C. for up to 28 d, or (b) carbonated for 12 h at 45° C. (in 12% CO2, v/v) before curing in saturated limewater was continued until 28 d. To better assess the effects of portlandite enrichment, the strength evolutions of portlandite-free composites (i.e., where the binder was simply composed of OPC and FA) were also examined. In portlandite-free composites, carbonation induced a small increase in compressive strength and CO2uptake at early ages (≈3% by mass of binder) relative to the portlandite-enriched composites at an equivalent carbonation reaction time of 12 h. However, the rate of strength gain diminished over time (FIG.12A) due to the coverage of reacting particle surfaces by carbonate (and perhaps C-S-H) precipitates, which hinders hydration and pozzolanic reactions relative to non-carbonated, and non-portlandite enriched composites in the longer term, i.e., see reduced non-evaporable water contents as shown inFIG.12B. As a comment of substance: this draws into question the approach of carbonating fresh OPC-based composites with respect to late-age strengthening and durability. For instance, Zhang et al. reported that the carbonation of early-age OPC concrete can result in formation of carbonate precipitates on C3S/C2S particles which can lead to suppression of strength at later ages during post-hydration. Furthermore, it has been noted that the reduced calcium hydroxide content of carbonated OPC-based concretes can increase the risk of corrosion of reinforcing steel. Similar reductions in the reactivity of OPC-based materials following carbonation have often been attributed to the formation of surficial barriers (e.g., as also relevant for prehydrated cements) on anhydrous and/or hydrated OPC phases (C-S-H and Ca(OH)2), and to the consumption of Ca(OH)2during carbonation (seeFIG.12C). In contrast, portlandite-enriched composites exposed to CO2featured strengths that are higher than that of the non-carbonated reference composite not only during CO2exposure but also when cured in limewater, manifesting a strength that is nearly 7 MPa (≈40%) higher after 28 days of aging (Figure A. OPC hydration in the carbonated portlandite-enriched composites, interestingly, was suppressed to only a minor degree relative to its non-carbonated reference (FIG.12B) and was nearly equivalent to that of the hydrated portlandite-free binder. This nature of enhanced later-age strength development of the portlandite-enriched composites suggests that surface localization of carbonation products in the vicinity of the easier to carbonate portlandite grains results in reduced surface obstructions on OPC (and other reactant) particulates in these composites. Moreover, despite the significant consumption of portlandite during carbonation, the progress of pozzolanic reactions of carbonated portlandite-enriched binders proceeded unabated during curing, as represented by the progressive increase in non-evaporable water content (FIG.12B) and the corresponding reduction in portlandite contents (FIG.12C). It is furthermore observed that despite substantial portlandite consumption in the carbonated portlandite-enriched composite, residual portlandite remains that is not converted into CaCO3. While this does suggest the potential to extend the carbonation processing window (i.e., to consume more portlandite), it shows an ability to explicitly control how much residual portlandite remains, e.g., to maintain a sufficient pH buffer to allow for the formation of passivation films on reinforcing steel surfaces as appropriate to hinder corrosion. Notably, the portlandite-enriched composite had an equivalent 28 d strength to the carbonated portlandite-free composite, while containing less than half of the OPC content and while taking up 4.3× more CO2. Admittedly, this strength was around 83% that of the reference (non-carbonated) OPC-FA composite. However, the embodied CO2intensity of the carbonated portlandite-enriched composite is—conservatively, i.e., in spite of incomplete portlandite consumption—more than 50% lower when aspects of both CO2avoidance and uptake are taken into account. Further, by applying a slightly higher temperature as typical for flue gas exhaust, it is noted that portlandite-enriched dry-cast composites were able to deliver the same strength as their wet-cast counterparts (FIG.11)—although in 24 h rather than 28 d, and once again, with a greatly reduced embodied CO2footprint. This example has elucidated the potential of in situ CO2mineralization and the formation of carbonate precipitates as a pathway for: (a) ensuring the cementation of construction relevant components, and (b) as a means for enabling the utilization of dilute CO2waste streams at ambient pressure, and near-ambient temperatures with any need for pre-/post-treatment. The understanding gained offers new means to design low-CO2cementation agents that can serve as a functional replacement to OPC, the very CO2-intensive cementation agent used by the construction sector for over a century. Special focus was paid to elucidate the roles of microstructure and pore (moisture) saturation on affecting CO2transport into 3D-monoliths, and the consequent impacts on the rate and progress of carbonation reactions and strength development. In general, while reducing pore saturation enhances carbonation, this is only true so long as Sw,c>0.10, below which the hindered dissolution of portlandite, in turn, suppresses carbonation. Unsurprisingly, dry-cast composites due to their lower water content, and the reduced surface coverage produced on their reactant surfaces (e.g., due to OPC hydration) are more effectively carbonated. Importantly, it is shown that the formation of carbonate precipitates is able to effectively bind proximate surfaces mineral particle surfaces thereby resulting in the carbonated dry-cast composites that achieve a compressive strength of ≈25 MPa in 24 h. It is furthermore shown that the formation of carbonate precipitates yields strengthening at the level of ≈15 MPa per unit of CO2uptake of reactants. This is substantially higher, e.g., than that noted by Wei et al. in their studies of fly ash carbonation. The outcomes of this work offer guidelines regarding process routes to develop portlandite-enriched cementation agents. This is significant as such novel binders, on account of their CO2uptake and avoidance, feature a CO2intensity that is substantially lower than that of typical OPC-based binders, which are commonly, today, diluted using fly ash. As an example, the global warming potential (GWP; kg CO2e/m3) associated with production of raw materials, transportation, and manufacturing of the concrete masonry units (CMUs) indicate that representative portlandite-enriched CMU formulations feature a GWP that is nearly 58% lower than that of typical OPC-dominant CMU formulations (Table S2 in SI). This GWP reduction is attributed to (i) the substitution of OPC with portlandite and fly ash (CO2avoidance), and (ii) the net negative CO2emissions associated with CO2uptake during manufacturing (CO2utilization). Evidently, the nature of processing conditions discussed herein are well-suited for the precast manner of fabrication. This creates opportunities to utilize portlandite-enriched binders to manufacture both masonry and precast components that can be used for both structural (“load bearing”) and non-structural construction. Supporting Information: (A) Materials The bulk oxide compositions of the ordinary portland cement (OPC) and fly ash as determined using X-ray fluorescence (XRF) are presented in Table S1. The densities of the portlandite, fly ash, and OPC were measured using helium pycnometry (Accupyc II 1340, Micromeritics) as: 2235 kg/m3, 2460 kg/m3, and 3140 kg/m3, respectively. The particle size distributions (PSDs) of the binder solids were measured using static light scattering (SLS; LS13-320, Beckman Coulter; seeFIG.13). TABLE S1Oxide composition (by mass) of the fly ash andOPC as determined by XRF.Mass (%)OxideFly ashType I/II OPCSiO260.8421.21Al2O322.304.16Fe2O34.753.85SO30.622.81CaO6.3865.50Na2O2.070.18MgO1.801.98K2O1.230.32 (B) Drying and Carbonation Processing A schematic of the drying and carbonation reactors and related online instrumentation is illustrated inFIG.14. (C) Experimental Methods Moisture diffusion coefficient: The sides of the cylinders (50 mm×25 mm for wet-cast and 75 mm×25 mm for dry-cast; d×h) were sealed using a silicone sealant and aluminum tape to ensure 1-D diffusion. For this boundary conditions, Fick's 2ndlaw can be expressed analytically using a Taylor expansion of the error function as follows: mtm∞=1-∑n=0n=∞8(2n+1)2π2exp(-Dtot(2n+1)2π2t4L2)Equation(S1) where mt(g) is the mass loss at a given time, m∞(g) is the ultimate mass loss (i.e., at the infinite time; at equilibrium), t (s) is time, and L (m)=0.0125 m is half of the sample thickness. (D) Kinetics of Drying Prior to Carbonation The effects of temperature and air flow rate on the drying kinetics of wet-cast composites (“mortars”) and the reduction in the degree of liquid saturation, Sw, are shown inFIGS.15Aand B. Expectedly, higher temperatures or air flow rates accelerated drying and resulted in a prominent decrease in Sw. Swplateaued over time under all drying conditions, and more rapidly so at higher temperatures. This plateau indicates a progressive transition in the size of pores from which water is removed. Specifically, as the internal RH diminishes, water is first drawn out from larger and percolated pores, and thereafter smaller sub-micron and disconnected pores.FIG.15Cshows the effect of compaction pressure on increasing Swfor dry-cast composites that is induced by decreasing their total porosity. (E) Carbonation Strengthening FIG.16displays the evolution of compressive strength as a function of the non-evaporable water content, wn/mOPC, for wet-cast composites across increasing carbonation durations. Significantly, the compressive strengths developed in carbonated composites are equivalent or superior to the sealed cured composites wherein, in the latter, strength development is simply ensured by the hydration of OPC. FIG.17displays the dependence of slope of strength—wn/mOPCrelation on drying conditions. FIGS.18Aand B compare the microstructure and surface morphology of carbonated wet-cast and dry-cast composites at varying degrees of hydration. The images were acquired using a field emission-scanning electron microscope with an energy dispersive X-ray spectroscopy detector (SEM-EDS; FEI NanoSEM 230). For a given time, cross-sectional disks were taken from the cylinders and immersed in IPA for 7 days to suppress OPC hydration. The disks were then vacuum-dried in a desiccator for 7 days, before small coupons were taken from the disks and impregnated with epoxy, polished, and gold-coated. All SEM micrographs were acquired in secondary electron mode with a spot size of 4.0 nm, at an accelerating voltage of 10 kV, and a working distance between ≈5.5 mm. (F) Representative Sustainability Implications/Assessments The global warming potential (GWP; kg CO2e/m3) of representative portlandite-enriched concrete masonry units (CMUs) has been estimated in line with the Environmental Product Declaration (EPD) methodology and compared with the OPC-based CMUs. For concrete masonry products, this is described by the product category rule (PCR): “ASTM International. ASTM International PCR005: Product Category Rules for Preparing an Environmental Product Declaration for Manufactured Concrete and Concrete Masonry Products, 2014; p 21.” EPDs following this PCR use the product stage as the system boundary, and therefore include three modules: (1) raw materials supply, (2) transport to the manufacturer, and (3) manufacturing. The declared unit is 1 m3of concrete masonry products. Table S2 provides a comparative evaluation of the GWP of each module of a Canadian industry-averaged EPD (representative of conventional OPC-based CMU) against the GWP of a representative portlandite-enriched binder designed for CMU fabrication. This calculation indicates that the portlandite-enriched CMU features a GWP that is ≈58% less than that of conventional OPC-based CMU. This reduction is attributed to (i) the substitution of OPC with portlandite and fly ash (CO2avoidance), and (ii) the net negative CO2emissions associated with CO2uptake during manufacturing (CO2utilization). TABLE S2The comparative global warming potential (GWP, kg CO2e/m3) for portlandite-enriched and OPC-concrete masonry based on a cradle-to-gate analysis. The declared unit is 1m3of concrete formed into masonry units (CMUs) as per applicable product category rules.GWP of OPC-based CMUGWP of Portlandite-(kg CO2e/m3) [sourced fromenriched CMUModuleCCMPA average EPD](kg CO2e/m3)A1: Raw Material Supply170103A2: Transport to Manufacturer2727A3: Manufacturing63−21Total (A1 + A2 + A3)260109 As used herein, the singular terms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to an object can include multiple objects unless the context clearly dictates otherwise. As used herein, the terms “connect,” “connected,” and “connection” refer to an operational coupling or linking. Connected objects can be directly coupled to one another or can be indirectly coupled to one another, such as via one or more other objects. As used herein, the terms “substantially” and “about” are used to describe and account for small variations. When used in conjunction with an event or circumstance, the terms can refer to instances in which the event or circumstance occurs precisely as well as instances in which the event or circumstance occurs to a close approximation. When used in conjunction with a numerical value, the terms can refer to a range of variation of less than or equal to ±10% of that numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%. Additionally, amounts, ratios, and other numerical values are sometimes presented herein in a range format. It is to be understood that such range format is used for convenience and brevity and should be understood flexibly to include numerical values explicitly specified as limits of a range, but also to include all individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly specified. For example, a ratio in the range of about 1 to about 200 should be understood to include the explicitly recited limits of about 1 and about 200, but also to include individual ratios such as about 2, about 3, and about 4, and sub-ranges such as about 10 to about 50, about 20 to about 100, and so forth. While the disclosure has been described with reference to the specific embodiments thereof, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true spirit and scope of the disclosure as defined by the appended claim(s). In addition, many modifications may be made to adapt a particular situation, material, composition of matter, method, operation or operations, to the objective, spirit and scope of the disclosure. All such modifications are intended to be within the scope of the claim(s) appended hereto. In particular, while certain methods may have been described with reference to particular operations performed in a particular order, it will be understood that these operations may be combined, sub-divided, or re-ordered to form an equivalent method without departing from the teachings of the disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the disclosure. | 66,616 |
11858866 | DETAILED DESCRIPTION OF THE INVENTION The following terms and definitions will be used in the context of the present invention: As used in the context of present invention, the singular forms of “a” and “an” also include the respective plurals unless the context clearly dictates otherwise. Thus, the term “a” or “an” is intended to mean “one or more” or “at least one”, unless indicated otherwise. The term “aluminous cement” in the context of the present invention refers to a calcium aluminate cement that consists predominantly of hydraulic active calcium aluminates. Alternative names are “high-alumina cement” or “Ciment fondu” in French. The main active constituent of calcium aluminate cements is monocalcium aluminate (CaAl2O4, CaO·Al2O3, or CA in the cement chemist notation). The term “shelf life” in the context of the present invention refers to the time during which a component stays in the form of a more or less fluid aqueous suspension of solid products, capable of coming back to the aqueous-suspension by mechanical means, without setting or losing its reactivity. The term “initiator” in the context of the present invention refers to a compound or composition that modifies the chemical environment to start a particular chemical reaction. In the present invention the initiator modifies the pH-value of the mortar suspension thereby de-blocking the hydraulic binder in the final mixture. The term “retarder” in the context of the present invention refers to a compound or composition that modifies the chemical environment to delay a particular chemical reaction. In the present invention the retarder modifies the hydration ability of the calcium aluminate cement of the mortar suspension thereby delaying the hydraulic binder action in the final mixture. The term “initial set-time” in the context of the present invention refers to the time at which the mixture of component A and component B starts to set after mixing. During the time period after mixing, the mixture stays in the form of a more or less fluid aqueous suspension or paste of solid products. The present invention pertains to a fire-resistant two-component mortar system for a fire-resistant chemical fastening of anchors and post-installed reinforcing bars in mineral surfaces, comprising a curable aqueous-phase aluminous cement component A and an initiator component B in aqueous-phase for initiating the curing process. In particular, according to the present invention, component A further comprises at least one blocking agent selected from the group consisting of phosphoric acid, metaphosphoric acid, phosphorous acid and phosphonic acids, at least one plasticizer and water, and component B comprises an initiator, at least one retarder, at least one mineral filler and water, wherein the initiator comprises a mixture of alkali and/or alkaline earth metal salts, the at least one retarder is selected from the group consisting of citric acid, tartaric acid, lactic acid, salicylic acid, gluconic acid and mixtures thereof, and the mineral filler is selected from the group consisting of limestone fillers, sand, corundum, dolomite, alkaline-resistant glass, crushed stones, gravels, pebbles and mixtures thereof. Component A according to the present invention is based on an aqueous-phase aluminous cement (CA) or an aqueous-phase calcium sulfoaluminate cement (CAS). The calcium aluminate cement which can be used in the present invention is characterized by rapid set and rapid hardening, rapid drying and shrinkage compensation when mixed with calcium sulfates, excellent resistance to corrosion and shrinkage. Such a calcium aluminate cement suitable to be used in the present invention is for example Ternal® White (Kerneos, France). If component A comprises a mixture of aluminous cement (CAC) and calcium sulfate (CaSO4), rapid ettringite formation takes place during hydration. In concrete chemistry hexacalcium aluminate trisulfate hydrate, represented by the general formula (CaO)6(Al2O3)(SO3)3·32H2O or (CaO)3(Al2O3)(CaSO4)3·32H2O, is formed by the reaction of calcium aluminate with calcium sulfate, resulting in quick setting and hardening as well as in shrinkage compensation or even expansion. With moderate increase of the sulfate content shrinkage compensation can be achieved. Component A of the present invention comprises at least about 40 wt.-%, preferably at least about 50 wt.-%, more preferably at least about 60 wt.-%, most preferably at least about 70 wt.-%, from about 40 wt. % to about 95 wt.-%, preferably from about 50 wt.-% to about 85 wt.-%, more preferably from about 60 wt.-% to about 80 wt.-%, most preferably from about 70 wt.-% to about 75 wt.-% of aluminous cement, based on the total weight of component A. According to an alternative embodiment of the invention, component A comprises at least about 20 wt.-%, preferably at least about 30 wt.-%, more preferably at least about 40 wt.-%, most preferably at least about 50 wt.-%, from about 20 wt.-% to about 80 wt.-%, preferably from about 30 wt.-% to about 70 wt.-%, more preferably from about 35 wt.-% to about 60 wt.-%, most preferably from about 40 wt.-% to about 55 wt.-% of aluminous cement, based on the total weight of component A and at least about 5 wt.-%, preferably at least about 10 wt.-%, more preferably at least about 15 wt.-%, most preferably at least about 20 wt.-%, from about 1 wt.-% to about 50 wt.-%, preferably from about 5 wt.-% to about 40 wt.-%, more preferably from about 10 wt.-% to about 30 wt.-%, most preferably from about 15 wt.-% to about 25 wt.-% of calcium sulfate, preferably calcium sulfate hemihydrate, based on the total weight of component A. In a preferred alternative embodiment of the two-component mortar system of the present invention, the ratio of CaSO4/CAC of component A should be less or equal to 35:65. The blocking agent comprised in component A according to the present invention is selected from the group consisting of phosphoric acid, metaphosphoric acid, phosphorous acid and phosphonic acids, preferably is phosphoric acid or metaphosphoric acid, most preferably is phosphoric acid, in particular an 85% aqueous solution of phosphoric acid. Component A comprises at least about 0.1 wt.-%, preferably at least about 0.3 wt.-%, more preferably at least about 0.4 wt.-%, most preferably at least about 0.5 wt.-%, from about 0.1 wt.-% to about 20 wt.-%, preferably from about 0.1 wt.-% to about 15 wt.-%, more preferably from about 0.1 wt.-% to about 10 wt.-%, most preferably from about 0.3 wt.-% to about 10 wt.-% of said blocking agent, based on the total weight of component A. In a preferred embodiment, component A comprises from about 0.3 wt.-% to about 10 wt.-% of 85% aqueous solution of phosphoric acid, based on the total weight of component A. Preferably, the amounts of aluminous cement and/or calcium sulfoaluminate cement by weight relative to the hydraulic binder total weight are higher than any of the following values: 50%, 60%, 70%, 80%, 90%, 95%, 99% or are 100%. The plasticizer comprised in component A according to the present invention is selected from the group consisting of low molecular weight (LMW) polyacrylic acid polymers, superplasticizers from the family of polyphosphonate polyox and polycarbonate polyox, and ethacryl superplasticizers from the polycarboxylate ether group, and mixtures thereof, for example Ethacryl™ G (Coatex, Arkema Group, France), Acumer™ 1051 (Rohm and Haas, U.K.), or Sika® ViscoCrete®-20 HE (Sika, Germany). Suitable plasticizers are commercially available products. Component A comprises at least about 0.2 wt.-%, preferably at least about 0.3 wt.-%, more preferably at least about 0.4 wt.-%, most preferably at least about 0.5 wt.-%, from about 0.2 wt.-% to about 20 wt,%, preferably from about 0.3 wt.-% to about 15 wt.-%, more preferably from about 0.4 wt.-% to about 10 wt.-%, most preferably from about 0.5 wt.-% to about 5 wt.-% of said plasticizer, based on the total weight of component A. In an advantageous embodiment, component A further comprises the following characteristics, taken alone or in combination. Component A may additionally comprise a thickening agent. The thickening agents which can be used in the present invention may be selected from the group consisting of organic products, such as xanthan gum, welan gum or DIUTAN® gum (CPKelko, USA), starched-derived ethers, guar-derived ethers, polyacrylamide, carrageenan, agar agar, and mineral products, such as clay, and their mixtures. Suitable thickening agents are commercially available products. Component A comprises at least about 0.01 wt.-%, preferably at least about 0.1 wt.-%, more preferably at least about 0.2 wt.-%, most preferably at least about 0.3 wt.-%, from about 0.01 wt.-% to about 10 wt.-%, preferably from about 0.1 wt.-% to about 5 wt.-%, more preferably from about 0.2 wt.-% to about 1 wt.-%, most preferably from about 0.3 wt.-% to about 0.7 wt.-% of said thickening agent, based on the total weight of component A. Component A may further comprise an antibacterial or biocidal agent. The antibacterial or biocidal agents which can be used in the present invention may be selected from the group consisting of compounds of the isothiazolinone family, such as methylisothiazolinone (MIT), octylisothiazolinone (OIT) and benzoisothiazolinone (BIT) and their mixtures. Suitable antibacterial or biocidal agents are commercially available products. Exemplarily mentioned are Ecocide K35R (Progiven, France) and Nuosept OB 03 (Ashland, The Netherlands). Component A comprises at least about 0.001 wt.-%, preferably at least about 0.005 wt.-%, more preferably at least about 0.01 wt.-%, most preferably at least about 0.015 wt.-%, from about 0.001 wt.-% to about 1.5 wt.-%, preferably from about 0.005 wt-% to about 0.1 wt.-%, more preferably from about 0.01 wt.-% to about 0.075 wt.-%, most preferably from about 0.015 wt.-% to about 0.03 wt.-% of said antibacterial or biocidal agent, based on the total weight of component A. In a preferred embodiment, component A comprises from about 0.015 wt.-% to about 0.03 wt.-% of Nuosept OB 03, based on the total weight of component A. In an alternative embodiment, component A comprises at least one filler, in particular an organic or mineral filler. The filler which can be used in the present invention may be selected from the group consisting of quartz powder, preferably quartz powder having an averaged grain size (d50%) of about 16 μm, quartz sand, clay, fly ash, fumed silica, carbonate compounds, pigments, titanium oxides, light fillers, and their mixtures. Suitable mineral fillers are commercially available products. Exemplarily mentioned is quartz powder Millisil W12 or W6 (Quarzwerke GmbH, Germany). Component A comprises at least about 1 wt.-%, preferably at least about 2 wt.-%, more preferably at least about 5 wt.-%, most preferably at least about 8 wt.-%, from about 1 wt.-% to about 50 wt.-%, preferably from about 2 wt.-% to about 40 wt.-%, more preferably from about 5 wt.-% to about 30 wt.-%, most preferably from about 8 wt.-% to about 20 wt.-% of said at least one filler, based on the total weight of component A. The water content comprised in component A is at least about 1 wt.-%, preferably at least about 5 wt.-%, more preferably at least about 10 wt.-%, most preferably at least about 20 wt.-%, from about 1 wt.-% to about 50 wt.-%, preferably from about 5 wt.-% to about 40 wt.-%, more preferably from about 10 wt.-% to about 30 wt.-%, most preferably from about 15 wt.-% to about 25 wt.-%, based on the total weight of component A. The presence of a plasticizer, thickening agent as well as an antibacterial or biocidal agent does not change the overall inorganic nature of the cementitious component A. Component A comprising the aluminous cement or calcium sulfoaluminate cement is present in aqueous-phase, preferably in form of a slurry or paste. Component B of the present invention comprises an initiator, at least one retarder, at least one mineral filler and water. To ensure a sufficient processing time, whereby the initial-set time is at least 5 min or more, at least one retarder, which prevents premature hardening of the mortar composition, is used in a distinct concentration in addition to the initiator component. The initiator present in component B is comprised of an activator component and an accelerator component which comprise a mixture of alkali and/or alkaline earth metal salts. In particular, the activator component is constituted of at least one alkali and/or alkaline earth metal salt selected from the group consisting of hydroxides, chlorides, sulfates, phosphates, monohydrogen phosphates, dihydrogen phosphates, nitrates, carbonates and mixtures thereof, preferably the activator component is an alkali or alkaline earth metal salt, more preferably is a calcium metal salt, such as calcium hydroxide, calcium sulfate, calcium carbonate or calcium phosphate, a sodium metal salt, such as sodium hydroxide, sodium sulfate, sodium carbonate or sodium phosphate, or a lithium metal salt, such as lithium hydroxide, lithium sulfate, lithium carbonate or lithium phosphate, most preferably is lithium hydroxide. In one preferred embodiment the lithium hydroxide used in component B is a 10% aqueous solution of lithium hydroxide. Component B comprises at least about 0.01 wt.-%, preferably at least about 0.02 wt.-%, more preferably at least about 0.05 wt.-%, most preferably at least about 1 wt.-%, from about 0.01 wt.-% to about 40 wt.-%, preferably from about 0.02 wt.-% to about 35 wt.-%, more preferably from about 0.05 wt.-% to about 30 wt.-%, most preferably from about 1 wt-% to about 25 wt.-% of said activator, based on the total weight of component B. In a particular preferred embodiment, the activator is comprised of water and lithium hydroxide. The water content comprised in component B is at least about 1 wt.-%, preferably at least about 5 wt.-%, more preferably at least about 10 wt.-%, most preferably at least about 20 wt.-%, from about 1 wt.-% to about 60 wt.-%, preferably from about 5 wt.-% to about 50 wt.-%, more preferably from about 10 wt.-% to about 40 wt.-%, most preferably from about 15 wt.-% to about 30 wt.-%, based on the total weight of component B. The lithium hydroxide content comprised in component B is at least about 0.1 wt.-%, preferably at least about 0.5 wt.-%, more preferably at least about 1.0 wt.-%, most preferably at least about 1.5 wt.-%, from about 0.1 wt.-% to about 5 wt.-%, preferably from about 0.5 wt.-% to about 4 wt.-%, more preferably from about 1.0 wt.-% to about 3 wt.-%, most preferably from about 1.5 wt.-% to about 2.5 wt.-%, based on the total weight of component B. In a most preferred embodiment, component B comprises from about 2.0 wt.-% to about 20 wt.-% of a 10% aqueous solution of lithium hydroxide, based on the total weight of component B. The accelerator component is constituted of at least one alkali and/or earth alkaline metal salt selected from the group consisting of hydroxides, chlorides, sulfates, phosphates, monohydrogen phosphates, dihydrogen phosphates, nitrates, carbonates and mixtures thereof, preferably the accelerator component is an alkali or earth alkaline metal salt, still preferably is a water-soluble alkali or earth alkaline metal salt, more preferably is a calcium metal salt, such as calcium hydroxide, calcium sulfate, calcium carbonate, calcium chloride, calcium formate or calcium phosphate, a sodium metal salt, such as sodium hydroxide, sodium sulfate, sodium carbonate, sodium chloride, sodium formate or sodium phosphate, or a lithium metal salt, such as lithium hydroxide, lithium sulfate, lithium sulfate monohydrate, lithium carbonate, lithium chloride, lithium formate or lithium phosphate, most preferably is lithium sulfate or lithium sulfate monohydrate. Component B comprises at least about 0.01 wt.-%, preferably at least about 0.05 wt.-%, more preferably at least about 0.1 wt.-%, most preferably at least about 1.0 wt.-%, from about 0.01 wt.-% to about 25 wt.-%, preferably from about 0.05 wt.-% to about 20 wt.-%, more preferably from about 0.1 wt.-% to about 15 wt.-%, most preferably from about 1.0 wt.-% to about 10 wt.-% of said accelerator, based on the total weight of component B. In a particular preferred embodiment of component B of the present invention, the ratio of 10% aqueous solution of lithium hydroxide/lithium sulfate or lithium sulfate monohydrate is 7/1 or 6/1. The at least one retarder comprised in component B according to the present invention is selected from the group consisting of citric acid, tartaric acid, lactic acid, salicylic acid, gluconic acid and mixtures thereof, preferably is a mixture of citric acid and tartaric acid. Component B comprises at least about 0.1 wt.-%, preferably at least about 0.2 wt.-%, more preferably at least about 0.5 wt.-%, most preferably at least about 1.0 wt.-%, from about 0.1 wt.-% to about 25 wt.-%, preferably from about 0.2 wt.-% to about 15 wt.-%, more preferably from about 0.5 wt.-% to about 15 wt.-%, most preferably from about 1.0 wt.-% to about 10 wt.-% of said retarder, based on the total weight of component B. In a particular preferred embodiment of component B of the present invention, the ratio of citric acid/tartaric acid is 1.6/1. The at least one mineral filler comprised in component B according to the present invention is selected from the group consisting of limestone fillers, sand, crushed stones, gravels, pebbles and mixtures thereof, preferred are limestone fillers, such as various calcium carbonates. The at least one mineral filler is preferably selected from the group consisting of limestone fillers or quartz fillers, such as quartz powder Millisil W12 or W6 (Quarzwerke GmbH, Germany) and quartz sand. The at least one mineral filler of component B is most preferably a calcium carbonate or a mixture of calcium carbonates. Component B comprises at least about 30 wt.-%, preferably at least about 40 wt.-%, more preferably at least about 50 wt.-%, still more preferably at least about 60 wt.-%, most preferably at least about 70 wt.-%, from about 30 wt.-% to about 95 wt.-%, preferably from about 35 wt.-% to about 90 wt.-%, more preferably from about 40 wt.-% to about 85 wt.-%, still more preferably from about 45 wt.-% to about 80 wt.-%, most preferably from about 50 wt.-% to about 75 wt.-% of at least one mineral filler, based on the total weight of component B. The at least one mineral filler is chosen to obtain a particle size complementary to that of the aluminous cement. It is preferred that the at least one mineral filler has an average particle size of not more than 500 μm, more preferably of not more than 400 μm, most preferably not more than 350 μm. In a particular preferred embodiment of the present invention, the at least one mineral filler comprised in component B is mixture of three different calcium carbonates, i.e. calcium carbonate fines, such as different Omyacarb® types (Omya International AG, Germany). Most preferably, the first calcium carbonate has an average particle size (d50%) of about 3.2 μm and a residue of 0.05% on a 45 μm sieve (determined according to ISO 787/7). The second calcium carbonate has an average particle size (d50%) of about 7.3 μm and a residue of 0.5% on a 140 μm sieve (determined according to ISO 787/7). The third calcium carbonate has an average particle size (d50%) of about 83 μm and a residue of 1.0/6 on a 315 μm sieve (determined according to ISO 787/7). In a particular preferred embodiment of component B of the present invention, the ratio of first calcium carbonate/second calcium carbonate/third calcium carbonate is 1/1.5/2 or 1/1.4/2.2. In a particular preferred alternative embodiment of the present invention, the at least one mineral filler comprised in component B is mixture of three different quartz fillers. Most preferably, the first quartz filler is a quartz sand having an average particle size (d50%) of about 240 μm. The second quartz filler is a quartz powder having an average grain size (d50%) of about 40 μm. The third quartz filler is a quartz powder having an average grain size (d50%) of about 15 μm. In a particular preferred embodiment of component B of the present invention, the ratio of first quartz filler/second quartz filler/third quartz filler is 3/2/1. In an advantageous embodiment, component B further comprises the following characteristics, taken alone or in combination. Component B may additionally comprise a thickening agent. The thickening agent to be used in the present invention may be selected from the group consisting of bentonite, silicon dioxide, quartz, thickening agents based on acrylate, such as alkali-soluble or alkali-swellable emulsions, fumed silica, clay and titanate chelating agents. Exemplarily mentioned are polyvinyl alcohol (PVA), hydrophobically modified alkali soluble emulsions (HASE), hydrophobically modified ethylene oxide urethane polymers known in the art as HEUR, and cellulosic thickeners such as hydroxymethyl cellulose (HMC), hydroxyethyl cellulose (HEC), hydrophobically-modified hydroxy ethyl cellulose (HMHEC), sodium carboxymethyl cellulose (SCMC), sodium carboxymethyl 2-hydroxyethyl cellulose,2-hydroxypropyl methyl cellulose, 2-hydroxyethyl methyl cellulose, 2-hydroxybutyl methyl cellulose, 2-hydroxyethyl ethyl cellulose, 2-hydoxypropyl cellulose, attapulgite clay, and mixtures thereof. Suitable thickening agents are commercially available products, such as Optigel WX (BYK-Chemie GmbH, Germany), Rheolate 1 (Elementis GmbH, Germany) and Acrysol ASE-60 (The Dow Chemical Company). Component B comprises at least about 0.01 wt.-%, preferably at least about 0.05 wt.-%, more preferably at least about 0.1 wt.-%, most preferably at least about 0.3 wt.-%, from about 0.01 wt.-% to about 15 wt.-%, preferably from about 0.05 wt.-% to about 10 wt.-%, more preferably from about 0.1 wt.-% to about 5 wt.-%, most preferably from about 0.3 wt.-% to about 1 wt.-% of said thickening agent, based on the total weight of component B. The presence of a retarder and thickening agent does not change the overall inorganic nature of the cementitious component B. Component B comprising the initiator and retarder is present in aqueous-phase, preferably in form of a slurry or paste. It is preferred that the pH-value of component B is above 10, more preferably above 11 and most preferably is above 12, in particular in the range between 10 and 14, preferably between 11 and 13. It is particular preferred that the proportions of water in the two components, namely component A and component B, are chosen so that the water to aluminous cement ratio (W/CAC) or water to calcium sulfoaluminate cement (W/CAS), in the product obtained by mixing components A and B is lower than 1.5, preferably between 0.3 and 1.2, most preferably between 0.4 and 1.0. Moreover, it is particular preferred that the proportion of lithium in component B is chosen so that the lithium to aluminous cement ratio (Li/CAC) and lithium to calcium sulfoaluminate cement (L/CAS), in the product obtained by mixing components A and B is lower than 0.05, preferably between 0.001 and 0.05, most preferably between 0.005 and 0.01. Moreover, it is particular preferred that the proportion of retarder in component B is chosen so that the citric acid/tartaric acid to aluminous cement ratio and citric acid/tartaric acid to calcium sulfoaluminate cement, in the product obtained by mixing components A and B is lower than 0.5 preferably between 0.01 and 0.4, most preferably between 0.1 and 0.2. In a most preferred embodiment, component A comprises or consists of the following components:70 to 80 wt.-% of aluminous cement, alternatively 40 to 60 wt.-% aluminous cement and 15 to 25 wt.-% calcium sulfate,0.5 to 1.5 wt.-% of phosphoric acid,0.5 to 1.5 wt.-% of plasticizer,0.001 to 0.05 wt.-% of an antimicrobial or biocidal agent,optionally 5 to 20 wt.-% of mineral fillers, and15 to 25 wt.-% of water. In a preferred embodiment, component B comprises or consists of the following components:0.1 wt.-% to 4 wt.-% of lithium hydroxide,0.1 wt.-% to 5 wt.-% of lithium sulfate or lithium sulfate monohydrate,0.05 wt.-% to 5 wt.-% of citric acid,0.05 wt.-% to 4 wt.-% of tartaric acid,35 wt.-% to 45 wt.-% of a first mineral filler,15 wt.-% to 25 wt.-% of a second mineral filler,10 wt.-% to 20 wt.-% of a third mineral filler,0.01 wt.-% to 0.5 wt.-% of a thickening agent, and15 wt.-% to 25 wt.-% of water. In a most preferred embodiment, component B comprises or consists of the following components:1.5 wt.-% to 2.5 wt.-% of lithium hydroxide,1 wt.-% to 4 wt.-% of lithium sulfate or lithium sulfate monohydrate,1 wt.-% to 3 wt.-% of citric acid,0.5 wt.-% to 2 wt.-% of tartaric acid,35 wt.-% to 45 wt.-% of a first mineral filler,15 wt.-% to 25 wt.-% of a second mineral filler,10 wt.-% to 20 wt.-% of a third mineral filler,0.01 wt.-% to 0.5 wt.-% of a thickening agent, and15 wt.-% to 25 wt.-% of water. In a most preferred alternative embodiment, component B comprises or consists of the following components:3 wt.-% to 4 wt.-% of lithium hydroxide,1 wt.-% to 10 wt.-% of lithium sulfate or lithium sulfate monohydrate,1 wt.-% to 5 wt.-% of citric acid,1 wt.-% to 3 wt.-% of tartaric acid,25 wt.-% to 35 wt.-% of a first mineral filler,15 wt.-% to 25 wt.-% of a second mineral filler,10 wt.-% to 20 wt.-% of a third mineral filler,0.01 wt.-% to 0.5 wt.-% of a thickening agent, and30 wt.-% to 40 wt.-% of water. In another most preferred embodiment, component B comprises or consists of the following components:0.2 wt.-% to 1.5 wt.-% of lithium hydroxide,0.1 wt.-% to 1.0 wt.-% of lithium sulfate or lithium sulfate monohydrate,0.1 wt.-% to 1.0 wt.-% of citric acid,0.1 wt.-% to 0.5 wt.-% of tartaric acid,35 wt.-% to 45 wt.-% of a first mineral filler,15 wt.-% to 25 wt.-% of a second mineral filler,10 wt.-% to 20 wt.-% of a third mineral filler,0.01 wt.-% to 0.5 wt.-% of a thickening agent, and15 wt.-% to 25 wt.-% of water. Component A of the present invention may be prepared as follows: The phosphor-containing blocking agent is mixed with water, so that the pH-value of the resulting mixture is about 2. Plasticizer is added and the mixture homogenized. Aluminous cement, optionally calcium sulfate, and optionally mineral filler are premixed and added stepwise to the mixture whilst increasing the stirring speed, so that the pH-value of the resulting mixture is about 4. Finally, thickening agent and antibacterial/biocidal agent are added and mixed until complete homogenization of the mixture. Component B of the present invention may be prepared as follows: The accelerator is dissolved in an aqueous solution of an activator, followed by subsequent addition of retarder and homogenization of the mixture. The filler(s) is/are added stepwise whilst increasing the stirring speed until the mixture homogenizes. Finally, the thickening agent is added until complete homogenization of the mixture. Component A and B are present in aqueous phase, preferably in form of a slurry or paste. In particular, components A and B have a pasty to fluid aspect according to their respective compositions. In one preferred embodiment, component A and component B are in paste form thereby preventing sagging at the time of mixing the two components. The weight ratio between component A and component B (A/B) is preferentially comprised between 7/1 and 1/3, preferably is 3/1. Preferably, the composition of the mixture comprises 75 wt.-% of component A and 25 wt.-% of component B. In an alternative embodiment, the composition of the mixture comprises 25 wt.-% of component A and 75 wt.-% of component B. The fire-resistant two-component system is of mineral nature, which is not affected by the presences of additional thickening agents of other agents. The shelf life of the fire-resistant two-component system depends on the individual shelf life of each of the respective components, in particular component A as well as component B has a shelf life of at least six months at ambient temperature so as to protect the system from the storing and supply delays. Most preferably, component A and B are individually stable for at least six months. The component A and B were stored in tightly closed containers to avoid evaporation of water at 40° C. and checked for any changes in fluidity, homogeneity, whether sedimentation occurs, and pH-value after several time intervals. The properties of all components remained unaffected after 6 months, thus the shelf life is at least 6 months at 40° C. It is preferred that the fire-resistant two-component mortar system has an initial set-time of at least 5 min, preferably of at least 10 min, more preferably of at least 15 min, most preferably of at least 20 min, in particular in the range of from about 5 to 25 min, preferably in the range of about 10 to 20 min, after mixing of the two components A and B. In the fire-resistant multi-component mortar system, especially the fire-resistant two-component mortar system, the volume ratio of cementitious component A to initiator component B is 1:1 to 7:1, preferably is 3:1. In an alternative embodiment, the volume ratio of cementitious component A to initiator component B is 1:3 to 1:2. After being produced separately, component A and component B are introduced into separate containers, from which they are ejected by means of mechanical devices and are guided through a mixing device. The fire-resistant two-component mortar system of the present invention is preferably a ready-for-use system, whereby component A and B are separately arranged from each other in a multi-chamber device, such as a multi-chamber cartridge and/or a multi-chamber cylinder or in two-component capsules, preferably in a two-chamber cartridge or in two-component capsules. The multi-chamber system preferably includes two or more foil bags for separating curable component A and initiator component B. The contents of the chambers or bags which are mixed together by a mixing device, preferably via a static mixer, can be injected into a borehole. The assembly in multiple chamber cartridges or pails or sets of buckets is also possible. The hardening aluminous cement composition existing from the static mixer is inserted directly into the borehole, which is required accordingly for fastening the anchors and post-installed reinforcing bars, and has been initially introduced into the mineral surface, during the chemical fastening of anchors and post-installed reinforcing bars, whereupon the construction element to be fastened, such as an anchor or post-installed reinforcing bar, is inserted and adjusted, whereupon the mortar composition sets and hardens. In particular, the fire-resistant two-component system of the present invention is to be considered as a fire-resistant chemical anchor for fastening anchors and post-installed reinforcing bars. Without being bound by theory, the blocking agent present in component A inhibits the solubilization of the calcium aluminate(s) in water, thereby stopping cement hydration which leads to the curing of the mixture. Upon adding the initiator component B, the pH-value is changed and the cementitious component A is unblocked and hydration reaction of the calcium aluminate(s) is released. As this hydration reaction is catalyzed and accelerated by the presence of alkali metals salts, in particular lithium salts, it has an initial set-time of shorter than 5 min. In order to retard the fast curing time (initial-set time), it is preferred that the at least one retarder comprised in component B according to the present invention is so chosen to obtain an initial set-time of at least 5 min, preferably of at least 10 min, more preferably of at least 15 min, most preferably of at least 20 min, in particular in the range of from about 5 to 25 min, preferably in the range of about 10 to 20 min, after mixing of the two components A and B. The role of mineral fillers, in particular in component B, is to adjust the final performance with regard to mechanical strength and performance as well as long term durability. By optimizing the fillers, it is possible to optimize the water/aluminous cement ratio which allows for an efficient and fast hydration of the aluminous cement. The fire-resistant two-component mortar system of the present invention can be used for a fire-resistant chemical fastening of anchors and post-installed reinforcing bars into mineral surfaces, such as structures made of brickwork, concrete, pervious concrete or natural stone. In particular, the fire-resistant two-component mortar system of the present invention can be used for a fire-resistant chemical fastening of anchors and post-installed reinforcing bars in boreholes. It can be used for anchoring purposes encompassing an increase in the load capacity at elevated temperatures, such as 250° C. An increased temperature resistance results in a better operational capability for anchoring purposes at higher temperatures, such as temperatures being present in the area of a borehole of facade anchorages, which are exposed to strong sunlight or otherwise elevated temperatures, such as fire. In particular, the fire-resistant two-component mortar system of the present invention has load values that do not decrease at higher temperatures, they even increase at higher temperatures such as 250° C. when compared to the known systems, to guarantee a sufficient anchoring at elevated temperatures which is necessary when fastening anchors and post-installed reinforcing bars. Moreover, the fire-resistant two-component mortar system of the present invention may be used for the fire-resistant attachment of fibers, scrims, fabrics or composites, in particular of high-modulus fibers, preferably of carbon fibers, in particular for the reinforcement of building structures, for example walls or ceilings or floors, or further for mounting components, such as plates or blocks, e.g. made of stone, glass or plastic, on buildings or structural elements. However, in particular it is used for a fire-resistant fastening of anchors and post-installed reinforcing bars into recesses, such as boreholes, in mineral surfaces, such as structures made of brickwork, concrete, pervious concrete or natural stone, whereby the components of the fire-resistant two-component mortar system of the present invention are prior mixed, for example by means of a static mixer or by destroying a cartridge or a plastic bag, or by mixing components of a multi-chamber pails or sets of buckets. The following example illustrates the invention without thereby limiting it. EXAMPLES 1. Preparation of the Comparative Inorganic Mortar Systems 1.1 Comparative Example 1—Inorganic Mortar System “Cemeforce” The commercially available one-component cartridge Cemeforce (Sumitomo Osaka Cement Co. Ltd., Japan) containing the binder as dry powder is opened and its contents mixed with a separate bottle of water according to the instructions ready for introducing into the borehole using a dispenser. 1.2 Comparative Examples 2a and 2b—Inorganic Mortar System “Ambex Capsules” The commercially available one-component Ambex Anchoring Capsules AAC (comparative example 2a) and ARC-E (comparative example 2b) (Ambex Concrete Repair Solutions, Canada) ware immersed into water according to the instructions ready for manually insertion into the borehole. 2. Preparation of the Inventive Inorganic Mortar System (Inventive Example 3) The cementitious component A as well as the initiator component B of the inventive example 3 are initially produced by mixing the constituents specified in Tables 1 and 2, respectively. The proportions that are given are expressed in wt.-%. A typical mixing protocol for component A is as follows: weighting out the necessary quantity of water, introducing the water into a mixing bowl and slowly adding phosphoric acid thereto under stirring until a pH-value of about 2 is obtained; adding plasticizer and homogenizing at 100 to 200 rpm for 2 minutes; pre-mixing Ternal White® and filler in a big bucket and adding this mixture step by step whilst slowly stirring at 200 rpm to avoid lump formation, increasing stirring speed to 4000 rpm; pH-value obtained should be about 4; adding slowly thickening agent and finally antibacterial or biocidal agent and homogenizing at 5000 rpm it for 5 min. TABLE 1Composition of component A.CompoundFunctionADeionized water19.995Phosphoric acid 85%blocking agent0.910Ternal Whitealuminate cement77.981Ethacryl™Gplasticizer0.600Xanthan Gumthickening agent0.500Nuosept OB 03biocidal agent0.015Phosphoric acid 85% marketed by Sigma-Aldrich Chemie GmbH, GermanyTernal White®marketed by Kerneos S.A., FranceEthacryl™G marketed by Coatex, Arkema Group, FranceXanthan Gum marketed by Colltec GmbH & CO. KG, GermanyNuosept OB 03 marketed by Ashland Nederland B.V., The Netherlands A typical mixing protocol for component B is as follows: dissolving lithium sulfate monohydrate together with water in a 10% aqueous solution of lithium hydroxide followed by dissolving the carboxylic acids in this mixture and fully homogenizing it at 500 rpm for at least for 30 min; adding stepwise filler or filler mixture while increasing stirring speed to 2000 rpm over a time period of 5 min and continuing homogenizing it at 2000 rpm for about 10 min; finally adding thickening agent whilst stirring, and increasing stirring speed to 2500 rpm over a time period of 3 min; finally continuing homogenizing for 5 min. TABLE 2Composition of component B.CompoundFunctionBWater0.426LiOH 10% (water)activator18.412Li2SO4•H2Oaccelerator3.217Citric acidretarder2.108Tartaric acidretarder1.317Filler 1filler35.4291Filler 2filler22.3122Filler 3filler16.3833Optigel WXthickening agent0.396LiOH 10% (water) marketed by Bern Kraft GmbH, GermanyLi2SO4•H2O marketed by Sigma-Aldrich Chemie GmbH, GermanyCitric acid marketed by Sigma-Aldrich Chemie GmbH, GermanyTartaric acid marketed by Sigma-Aldrich Chemie GmbH, Germany1Omyacarb 130-Al marketed by Omya International AG, Germany2Omyacarb 15-H Al marketed by Omya International AG, Germany3Omyacarb 2-Al marketed by Omya International AG, GermanyOptigel WX marketed by Rockwood Clay Additives GmbH, Germany 3. Determination of Mechanical Performance at 250° C.—Resistance to Fire The tests were performed in uncracked concrete C20/25. The concrete used for testing complies with EN 206 and meets the requirements of ETAG 001 Annex A. For installation purposes the borehole was drilled (borehole diameter 16 mm) and cleaned, the mortar injected and the reinforcement bar injected at normal ambient temperature in accordance with the MPII. Comparative example 1 was introduced into the borehole using a dispenser. Comparative examples 2a and 2b were manually inserted into the borehole. After being produced separately, the cementitious component A and initiator component B of the inventive example was mixed in a speed mixer in a volume ratio of 3:1 and were introduced into the borehole. The diameter of the rebar was equal to 10 mm. The embedment depth of the rebar was equal to 120 mm. In the test, the curing time of the samples at room temperature was 24 hours and then the concrete block with the reinforcement bars was placed in an oven and heated to 250° C. Pull-out tests were performed at 250° C. after 3 days of maintaining said temperature. The average failure load is determined by centrally pulling out the rebar with tight support using high-strength steel rods using a hydraulic tool. Three reinforcement bars are doweled in place in each case and their load values are determined after curing for 3 days at 250° C. as mean value. Ultimate failure loads are calculated as bond strengths and given in N/mm2in Table 3. TABLE 3Bond strengths in N/mm2.Inventive example3 (mixture ofComparativeComparativeComparativecomponentexample 1example 2aexample 2bA and B)250° C. in10.25.91.913.7servicetem-perature As it can be seen from Table 3, the inventive system shows considerable bond strengths after 3 days at 250° C. Further, all three prior art one-component systems show a reduced bond strength at 250° C. of about 2-4 N/mm when compared to the bond strength achieved after 24 h at ambient temperature. The inventive system exhibits an increased bond strength at 250° C. of 2 N/mm2when compared to the bond strength achieved after 24 h at ambient temperature indicating a desired post-cure effect instead of weakening the binder matrix by the elevated temperature. Furthermore, this variant has been tested for fire performance according to EAD (EAD #330087-00-0601, European Assessment Document von EOTA, 2015) in a temperature range of from 23° C. to 450° C. (bond strength value of 14.5 N/mm2). Further, in comparison to injection mortars based on organic resins, their bond strength at elevated temperatures show significant, non-acceptable decrease in load values, at 250° C. sometimes close to zero in the organic systems, whereas the inventive examples increase in their bond strengths. As it has been shown above, the fire-resistant two-component mortar system of the present invention provides mechanical strength comparable to those of the organic systems, but the essentially mineral composition thereof makes it far less toxic and very little polluting for the environment as well as allows for a more cost-effective production than of the known system of the prior art. Further, it has been shown, that the fire-resistant multiple-component system, in particular a fire-resistant two-component mortar system, overcomes the disadvantages of the prior art systems. In particular, the fire-resistant two-component mortar system that is ready-for-use, is handled easily and is eco-friendly, can be stably stored for a certain period of time prior to use, exhibits a good balance between setting and hardening and still has an excellent mechanical performance when it comes to a fire-resistant chemical fastening of anchors and post-installed reinforcing bars, even under the influence of elevated temperatures, such as fire. Moreover, fire-resistant multiple-component anchoring system has load values that increase at higher temperatures such as 250° C. to guarantee a sufficient anchoring at elevated temperatures which is necessary when fastening anchors and post-installed reinforcing bars. | 42,542 |
11858867 | DETAILED DESCRIPTION 1. The first step of treating dental zirconia in the present disclosure is to solve the contradiction between the translucency and masking property of the zirconia base, which is specifically implemented as follows. The present disclosure provides a product for improving/balancing the translucency and masking property of dental zirconia ceramics (hereinafter referred to as color masking liquid), which has a formula comprising, in mass percentages, 95-98% of a mother liquor, 1.3-1.6% of an alcohol (e.g., a C1-C4alkanol such as methanol or ethanol, or a C2-C4alkanediol such as ethylene glycol or propylene glycol), 0.03-3.40% of potassium nitrate, 0.1-0.3% of yttrium chloride and 0.3-0.4% of citric acid. The formula of the mother liquor comprises, in mass percentages, 18-23% of ethylene glycol, 1-5% of gluconic acid, 1-3% of citric acid, 1-3% of praseodymium nitrate, and water. For example, the balance of the mother liquor (e.g., other than the ethylene glycol, the gluconic acid, the citric acid, and the praseodymium nitrate) may comprise of consist essentially of water, which may be distilled and/or deionized water. Among them, the potassium nitrate can make the zirconia base and/or the masking layer have a milky color after sintering, so as to achieve the color masking effect. As the concentration of potassium nitrate increases, generally speaking, the masking effect will also enhance. The alcohol acts as a dispersant because of its good compatibility. The yttrium chloride acts as a catalyst. All components of the color masking liquid except the mother liquor are accurately weighed, and preliminarily mixed at room temperature. Then, the mother liquor is added thereto, the mixture is well stirred to dissolve the components and obtain the desired color masking liquid. To prepare the zirconia ceramic, pressing and pre-sintering are carried out first for preliminary forming and preliminary crystallization, and then secondary sintering is carried out to improve the density and mechanical strength of the zirconia ceramic. The preliminary pressing, pre-sintering and other processes can be carried out conventionally. The color masking liquid is used in the secondary sintering after the pre-sintering. Specifically, the color masking liquid is painted on or over the surface of the pre-sintered zirconia ceramics. The amount of the color masking liquid on or over the surface of a single denture (e.g., a single tooth) is less than or equal to 0.001 g, and in practice, a little color masking liquid is taken by dipping to paint the zirconia without repeating the painting step. The painting may be repeated up to two times. Then, the zirconia ceramics are put into an oven for drying at 90° C., and half an hour later, taken out and put into a crucible with zirconium beads. The crucible is then put into a sintering furnace, the temperature curve of the sintering furnace is set, and the crucible is then kept at 1530° C. for 2 h to allow the color masking liquid and zirconia ceramics to undergo secondary sintering together. Before the zirconia base is preliminarily formed (pre-sintering is completed, but secondary sintering has not yet been performed), the color masking liquid is painted on or over the zirconia base, which is then subjected to the secondary sintering process, so that the color masking liquid reacts and crystallizes with the zirconia base, and the zirconia base is directly colored by the color masking liquid, making the color masking layer become a part of the zirconia base and constitute a built-in color of the base. The color masking layer is closely bound to the base after reaction, which does not increase the volume of the base. The present disclosure will be further explained with specific examples below. Example 1: Effect of Formula of Color Masking Liquid 1. Nine groups of color masking liquids were prepared by the above method, wherein the formula of these group of color masking liquids comprises 96.83% of a mother liquor, 1.52% of ethanol, 1.1% of potassium nitrate, 0.2% of yttrium chloride and 0.35% of citric acid. The formula of the mother liquor is shown in Table 1, wherein the numerals in the table indicate the mass percentages of the corresponding components in the color masking liquid, and the balance is deionized water, with the sum of all the components being 100%. The zirconia powder used in this example was purchased from Shanghai Linghao Metal Material Co., Ltd., with an article number of ZR-2. The zirconia powder was isostatically pressed at 150 MPa for 10 min (e.g., to form a pressed or “green” zirconia pre-ceramic). Then, it was pre-sintered at 1050° C. for 2 h. Thereafter, the pre-sintered zirconia ceramics were taken out, equal amounts of color masking liquids from each group were painted on or over the surface of the zirconia ceramics respectively, which was repeated twice. Then, the zirconia ceramics were put into an oven for drying at 90° C., and half an hour later, taken out, put into a crucible with zirconium beads, put into a sintering furnace, and heated at 1530° C. for 2 hours to complete secondary sintering. At the same time, a control group was provided, where the pre-sintered zirconia ceramics were directly heated at 1530° C. for 2 h without prior painting with the color masking liquid. TABLE 1Formula of mother liquor used in individual groupsEthyleneGluconicCitricPraseodymiumGroupglycolacidacidnitrateGroup 118%3%2%2%Group 220%3%2%2%Group 323%3%2%2%Group 420%1%2%2%Group 520%5%2%2%Group 620%3%1%2%Group 720%3%3%2%Group 820%3%2%1%Group 920%3%2%3% 2. Light transmittance test, three-point bending strength test, thickness test and color masking test were carried out for each group of zirconia bases. Among them, the thickness test is carried out as follows: the thickness of the zirconia bases in each group is measured at three points (the positions of the three points selected are the same for all the bases) respectively, and compared with that in the blank control group to obtain three groups of difference ratios which are then averaged. Thickness difference ratio lower than 1/10,000 is regarded as no difference. The color masking test comprises the following steps: the zirconia bases prepared in each group are fit onto the same metal abutments, and observed for whether the zirconia bases are transparent to color or not with naked eyes under a typical daily illumination condition, and observed for translucency and aesthetic quality. The results of these tests are shown in Table 2. TABLE 2Results for zirconium dioxide bases in individual groupsLightBendingTransparenttransmit-strengthThicknessto colorGrouptance (%)(MPa)differenceor notTranslucencyGroup 121.2%1201NoNoExcellentdifferenceGroup 215.3%1215NoNoExcellentdifferenceGroup 319.2%1209NoNoExcellentdifferenceGroup 419.6%1190NoNoExcellentdifferenceGroup 521.5%1196NoNoExcellentdifferenceGroup 625.2%1193NoNoExcellentdifferenceGroup 720.5%1201NoNoExcellentdifferenceGroup 826.4%1203NoNoExcellentdifferenceGroup 931.5%1207NoNoExcellentdifferenceControl42.1%1205N/AYesExcellentgroup 3. A mother liquor was prepared with the formula of the mother liquor in group 2 in step 1, and then 14 groups of color masking liquids (group 10-group 23) were prepared with the mother liquor, wherein the formulas of these groups of color masking liquids are shown in Table 3, and the numerals in the following Table indicate the mass percentages of the corresponding components in the color masking liquid. The color masking liquid was used in the same way as above. TABLE 3Formula of color masking liquid used incolor masking liquid in individual groupsMotherPotassiumYttriumCitricGroupliquorAlcoholAmountnitratechlorideacidGroup95.00%Ethanol4.15%0.30%0.20%0.35%10Group96.63%Ethanol2.52%0.30%0.20%0.35%11Group96.83%Ethanol1.52%0.30%0.20%0.35%12Group97.88%Ethanol1.27%0.30%0.20%0.35%13Group95.00%Ethanol1.52%2.93%0.20%0.35%14Group96.63%Ethanol1.52%1.30%0.20%0.35%15Group96.83%Ethanol1.52%1.10%0.20%0.35%16Group97.88%Ethanol1.52%0.05%0.20%0.35%17Group96.93%Ethanol1.52%1.10%0.10%0.35%18Group96.93%Ethanol1.52%1.10%0.30%0.35%19Group96.93%Ethanol1.52%1.10%0.20%0.20%20Group96.93%Ethanol1.52%1.10%0.20%0.40%21Group96.83%Ethylene1.52%1.10%0.20%0.35%22glycolGroup96.83%Methanol1.52%1.10%0.20%0.35%23 4. Light transmittance test, three-point bending strength test, thickness test and color masking test were carried out on each group of zirconia bases. Among them, the thickness test is carried out as follows: the thickness of the zirconia bases in each group is measured at three points (the positions of the three points selected are the same for all the bases) respectively, and compared with that in the blank control group to obtain three groups of difference ratios which are then averaged. The color masking test comprises the following steps: the zirconia bases prepared in each group are fit onto the same metal abutments, and observed for whether the zirconia bases are transparent to color or not with naked eyes under a typical daily illumination condition. The results of these tests are shown in Table 4. TABLE 4Results for zirconium dioxide bases in individual groupsLightBendingTransparenttransmit-strengthThicknessto colorGrouptance (%)(MPa)differenceor notTranslucencyGroup 1026.5%1209NoNoExcellentdifferenceGroup 1123.2%1210NoNoExcellentdifferenceGroup 1228.4%1210NoNoExcellentdifferenceGroup 1331.2%1213NoNoExcellentdifferenceGroup 1417.2%1198NoNoExcellentdifferenceGroup 1516.3%1203NoNoExcellentdifferenceGroup 1615.2%1217NoNoExcellentdifferenceGroup 1733.6%1209NoNoExcellentdifferenceGroup 1819.2%1213NoNoExcellentdifferenceGroup 1920.0%1213NoNoExcellentdifferenceGroup 2016.3%1208NoNoExcellentdifferenceGroup 2117.6%1206NoNoExcellentdifferenceGroup 2216.1%1213NoNoExcellentdifferenceGroup 2315.9%1211NoNoExcellentdifference Example 2: Effect of Methods for Applying Color Masking Liquids 1. Eight groups of color masking liquids were prepared using the formula of group 16 in Example 1, and then applied by different methods. Specifically, the treatment methods for these groups are shown in Table 5. TABLE 5Comparison of methods for applying color masking liquids in individual groupsStage in Method at whichNo. of times that zirconiazirconia bases are paintedbases are painted withDriedDryingGroupwith color masking liquidcolor masking liquidor not?temperatureGroup 1Before secondary sintering of2Yes90° C.zirconia baseGroup 2After secondary sintering of2Yes90° C.zirconia baseGroup 3Before secondary sintering of1Yes90° C.zirconia baseGroup 4Before secondary sintering of4Yes90° C.zirconia baseGroup 5Before secondary sintering of2NoN/Azirconia baseGroup 6Before secondary sintering of2Yes30° C.zirconia baseGroup 7Before secondary sintering of2Yes60° C.zirconia baseGroup 8Before secondary sintering of2Yes120° C.zirconia base 2. A group of zirconia bases were prepared separately without painting with the masking liquid, and other preparation and sintering conditions were completely the same, which served as the blank control group. The results of these groups are shown in Table 6. Among them, “not dried” means the bases are directly sintered without drying. TABLE 6Results for zirconia bases in all groupsLightBendingtransmit-strengthThicknessTransparent toGrouptance (%)(MPa)differencecolor or not?TranslucencyGroup 115.6%1213NoNoExcellentdifferenceGroup 233.7%1203+3‰NoGoodGroup 329.3%1207NoYesExcellentdifferenceGroup 410.5%1210NoNoGooddifferenceGroup 528.6%1198NoNoGooddifferenceGroup 623.6%1203NoNoExcellentdifferenceGroup 721.3%1205NoNoExcellentdifferenceGroup 819.1%1210NoNoExcellentdifferenceBlank43.2%1207/YesExcellentcontrolgroup Zirconia bases were obtained with the formula of group 16 in Example 1 using the method of group 1 in Example 2. Then, the zirconia base was colored. Of course, the zirconia base can be colored directly without being treated with the color masking liquid. In the latter case, the translucency and color masking property of the zirconia base may be inferior. The present disclosure provides the following two coloring methods. Method 1 involves preparing a first coloring liquid, roughening the surface of the zirconia base, soaking the zirconia base in the first coloring liquid for more than 15 s, then taking out the zirconia base, and subjecting the zirconia base to surface protection treatment using the adhesive solution. The advantage of Method 1 is that the coloring speed is fast, and the coloring depth does not change after a certain time (15 s), which is convenient for dentists to operate. Method 2 involves preparing a second coloring liquid, preparing an adhesive solution, mixing the second coloring liquid and the adhesive solution, painting the mixed solution on or over the surface of the zirconia base, or soaking the zirconia base in the mixed solution, then crystallizing at a high temperature, and finally painting a layer of silane coupling agent on or over the surface of the zirconia base for protection. The advantage of Method 2 is that the coloring process is simple, and a protective film will be formed on or over the surface of the zirconia base after coloring, thus prolonging the service life of the base. Method 1 and Method 2 are described in detail below. Method 1: 1. The first coloring liquid comprises a first coloring agent, a first dispersant and a first solvent which are, in mass percentages, 0.01-26%, 0.2-35% and 60-97% of the first coloring liquid respectively. The first coloring agent is at least one of erbium chloride, ferric chloride and manganese nitrate. Preferably, the coloring agent includes each of erbium chloride, ferric chloride and manganese nitrate in mass percentages of 0.5-13% of erbium chloride, 0.5-6% of ferric chloride, and 0.01-6% of manganese nitrate by weight of the coloring liquid. The first dispersant is polyethylene glycol; and the first solvent is deionized water. The method for preparing the first coloring liquid comprises the following steps: weighing raw materials according to the above-mentioned mass percentages, adding erbium chloride, ferric chloride, manganese nitrate and polyethylene glycol into the deionized water, stirring them uniformly, and sub-packaging the mixture for later use. 2. The method for coloring the zirconia base specifically comprises the following steps.(1) Surface roughening treatment is carried out on the zirconia base. Specifically, surface sandblasting treatment and hot acid treatment are carried out on the zirconia denture to control the surface roughness of the zirconia denture. The sandblasting treatment involves sandblasting the zirconia denture with 30-60 μm zirconia powder under a pressure of 0.2-0.3 MPa for 5-10 s. The hot acid treatment involves mixing hydrochloric acid and nitric acid thoroughly, heating them to 70-80° C. to obtain a mixed acid solution, and soaking the zirconia denture with sandblasted surface in 15-30 ml of the mixed acid solution (e.g., at 70-80° C.) for 10-15 min. The concentration of hydrochloric acid is 1-2 mol/L, the concentration of nitric acid is 1-2 mol/L, and the volume ratio of hydrochloric acid to nitric acid is 1:2-3.(2) The roughened zirconia base is washed 3-5 times with deionized water, and then the zirconia base is soaked with the first coloring liquid for more than 15 s. After 15 s, the color of the colored zirconia base will not deepen with prolonged soaking times (i.e., soaking times longer than 15 seconds).(3) The colored zirconia base is put into a denture sintering furnace, where the base is heated to 1530° C. at a rate of 5° C./min, kept at this temperature for crystallization for 120 min, and then allowed to cool down along with the furnace.(4) Preferably, after step (2) is finished, the zirconia base is soaked in a silane coupling agent for 1-2 min, and then soaked in a resin binder for 3-10 min. After soaking, the zirconia base is put in an oven at 90-150° C. for drying for 30 min, and then put in a denture sintering furnace where the base is heated to 1530° C. at a rate of 5° C./min, kept at this temperature for crystallization for 120 min, and then allowed to cool down along with the furnace. Method 1 will be further explained with specific examples below. Example 3: Demonstration of Effect of Roughening Treatment in Method 1 According to the above method, zirconia dentures were subjected to surface roughening treatment. A total of 18 groups were set, with their specific parameters as shown in Table 7 below. Specifically, the zirconia dentures after surface sandblasting were soaked in 20 mL of the mixed acid solution at a temperature of 80° C. Those receiving no treatment were used as the control. TABLE 7Surface roughening treatment of zirconia dentureSurface roughening treatment of zirconia dentureSurface sandblasting treatmentHot acid treatmentParticleHydrochloric acidNitric acidVolumeSoakingsizePressureProcessingconcentrationconcentrationratio of HCltimeGroup(μm)(MPa)time (s)(mol · L−1)(mol · L−1)to nitric acid(min)Group 1300.25111:210Group 2300.27111:212.5Group 3300.210111:215Group 4300.35111:310Group 5300.37111:312.5Group 6300.310111:315Group 7450.25121:210Group 8450.27121:212.5Group 9450.210121:215Group 10450.35121:310Group 11450.37121:312.5Group 12450.310121:315Group 13600.25211:210Group 14600.27211:212.5Group 15600.210211:215Group 16600.35211:310Group 17600.37211:312.5Group 18600.310211:315 The treated zirconia dentures in the individual groups were soaked in water for 2-5 min, and then air-dried for later use. Example 4: Demonstration of Effect of Coloring Liquid in Method 1 Coloring liquids were prepared, with the formula of raw materials including erbium chloride, ferric chloride, manganese nitrate, polyethylene glycol and deionized water in ratios as shown in Table 8 below. The results showed that there was no obvious change in the color of the three coloring liquids prepared in each group. The color of groups a-c gradually deepened from orange, the color of groups d-f gradually deepened from yellow, the color of groups g-i gradually deepened from gray red, and the color of groups j-l gradually deepened from yellow red. TABLE 8Formula of coloring liquidMass ratio of raw materials, %ErbiumFerricManganesechloridechloridenitrateConcentrationConcentrationConcentrationPolyethyleneDeionizedGroup(mmol · L−1)Amount(mmol · L−1)Amount(mmol · L−1)AmountglycolwaterGroup a5.435.71.25.30.5293.35.435.71.25.30.5689.35.435.71.25.30.51085.3Group b6.136.41.26.60.5293.36.136.41.26.60.5689.36.136.41.26.60.51085.3Group c7.537.21.27.70.5293.37.537.21.27.70.5689.37.537.21.27.70.51085.3Group d5.41.25.71.55.30.3295.05.41.25.71.55.30.3691.05.41.25.71.55.30.31087.0Group e6.11.26.41.56.60.3295.06.11.26.41.56.60.3691.06.11.26.41.56.60.31087.0Group f7.51.27.21.57.70.3295.07.51.27.21.57.70.3691.07.51.27.21.57.70.31087.0Group g5.41.15.70.85.30.7295.45.41.15.70.85.30.7691.45.41.15.70.85.30.71087.4Group h6.11.16.40.86.60.7295.46.11.16.40.86.60.7691.46.11.16.40.86.60.71087.4Group I7.51.17.20.87.70.7295.47.51.17.20.87.70.7691.47.51.17.20.87.70.71087.4Group j5.40.85.70.95.30.9295.45.40.85.70.95.30.9691.45.40.85.70.95.30.91087.4Group k6.10.86.40.96.60.9295.46.10.86.40.96.60.9691.46.10.86.40.96.60.91087.4Group l7.50.87.20.97.70.9295.47.50.87.20.97.70.9691.47.50.87.20.97.70.91087.4 Example 5: Demonstration of Effect of Coloring Time in Method 1 The coloring liquid with an orange color and a polyethylene glycol content of 6% in group a in Table 8 was selected to color the treated zirconia dentures in Table 1, with the coloring time and color change of zirconia dentures shown in Table 9 below. In particular, coloring time refers to the time when the color of zirconia denture no longer changes. The results showed that after the zirconia denture was treated according to the parameters in group 7, the time for the zirconia denture to reach the specified color and balance became shorter. TABLE 9Coloring time and color change of zirconia denture in individual groupsColoringGrouptime (s)Color changeGroup 130The color was lighter than the specified colorGroup 238The color was lighter than the specified colorGroup 345The color was lighter than the specified colorGroup 450The specified color was reached at 20 s, and with the extension ofcoloring time, the color gradually deepened, and the color did notchange any more after 50 sGroup 560The specified color was reached at 22 s, and with the extension ofcoloring time, the color gradually deepened, and did not changeany more after 60 sGroup 668The specified color was reached at 25 s, and with the extension ofcoloring time, the color gradually deepened, and after 68 s, reachedequilibrium and did not change any moreGroup 735The specified color was reached at 15 s, and with the extension ofcoloring time, the color gradually deepened, and after 35 s, reachedequilibrium and did not change any moreGroup 842The specified color was reached at 17 s, and with the extension ofcoloring time, the color gradually deepened, and after 42 s, reachedequilibrium and did not change any moreGroup 948The specified color was reached at 20 s, and with the extension ofcoloring time, the color gradually deepened, and after 48 s, reachedequilibrium and did not change any moreGroup 1045The specified color was reached at 23 s, and with the extension ofcoloring time, the color gradually deepened, and after 45 s, reachedequilibrium and did not change any moreGroup 1152The specified color was reached at 27 s, and with the extension ofcoloring time, the color gradually deepened, and after 52 s, reachedequilibrium and did not change any moreGroup 1261The specified color was reached at 30 s, and with the extension ofcoloring time, the color gradually deepened, and after 61 s, reachedequilibrium and did not change any moreGroup 1358The specified color was reached at 26 s, and with the extension ofcoloring time, the color gradually deepened, and after 58 s, reachedequilibrium and did not change any moreGroup 1470The specified color was reached at 30 s, and with the extension ofcoloring time, the color gradually deepened, and after 70 s, reachedequilibrium and did not change any moreGroup 1581The specified color was reached at 35 s, and with the extension ofcoloring time, the color gradually deepened, and after 81 s, reachedequilibrium and did not change any moreGroup 1664The specified color was reached at 40 s, and with the extension ofcoloring time, the color gradually deepened, and after 64 s, reachedequilibrium and did not change any moreGroup 1775The specified color was reached at 45 s, and with the extension ofcoloring time, the color gradually deepened, and after 75 s, reachedequilibrium and did not change any moreGroup 1883The specified color was reached at 52 s, and with the extension ofcoloring time, the color gradually deepened, and after 83 s, reachedequilibrium and did not change any moreControl120The specified color was reached at 60 s, and with the extension ofgroupcoloring time, the color gradually deepened, and after 120 s,reached equilibrium and did not change any more Example 6: Demonstration of Effect of Polyethylene Glycol in Method 1 After the zirconia denture was treated according to the parameters in group 7, the effect of polyethylene glycol content on coloring time was investigated, as shown in Table 10 below. The results showed that when the content of polyethylene glycol was 10%, the color of the denture remained unchanged with the extension of soaking time after 15 s. TABLE 10Effect of polyethylene glycol content on soaking timeMass ratio of raw materials, %ErbiumFerricManganesePolyethyleneDeionizedSoaking time of denture/sGroupchloridechloridenitrateglycolwater5101530120240600Group31.20.5293.3LighterLighterNormalSlightlyDarkerDarkerDarker1darkerGroup31.20.5689.3LighterLighterNormalSlightlyDarkerDarkerDarker2darkerGroup31.20.51085.3LighterLighterNormalNormalNormalNormalNormal3Group31.20.52075.3LighterLighterNormalNormalNormalNormalNormal4Group40.80.31084.9LighterLighterNormalNormalNormalNormalNormal5Group50.60.21084.2LighterLighterNormalNormalNormalNormalNormal6Group60.40.21083.4LighterLighterNormalNormalNormalNormalNormal7 Example 7: Protection Treatment in Method 1 The dentures colored in group 3 in Example 6 were soaked in the silane coupling agent for 1-2 min, and then soaked in the resin binder for 3-10 min, so that the resin binder infiltrated into micro-pores on the surface of zirconia dentures to seal the coloring liquid soaked into the pores and form a transparent film on or over the surface of zirconia dentures, which effectively avoided the fading of dentures and the penetration of bacteria, acids, enzymes and products thereof in human oral cavities into the pores on the surface of zirconia dentures. After soaking, the zirconia dentures were dried in an oven at 90-150° C. for 30 min, then put into a denture sintering furnace, heated to 1530° C. at a rate of 5° C./min, kept at this temperature to crystallize for 120 min, and then cooled down along with the furnace. Specifically, the resin binder contains 10-methacryloxydecyl phosphate (MDP) monomer, and the resin binder and silane coupling agent are common dental reagents. Method 2: 1. The second coloring liquid comprises a second coloring agent, a second dispersant, a complexing agent and a second solvent in mass percentages of 0.01-48%, 0.1-5%, 0.05-2%, and 45-99% of the coloring liquid, respectively. Specifically, the second coloring agent is one or a mixture of two or more of erbium chloride, ferric chloride, neodymium nitrate, manganese nitrate, ammonium metavanadate, cerium nitrate, praseodymium nitrate, cobalt nitrate and nickel nitrate. The second dispersant is polyethylene glycol, polyacrylic acid or polyurethane. The complexing agent is citric acid, glucose, ethylenediaminetetraacetic acid, sodium citrate or 2,3-dimercaptosuccinic acid. The second solvent is deionized water. Different coloring agents can be mixed to obtain coloring liquids with different colors which can be any one of blue, gray, tetracycline yellow, tetracycline gray, tetracycline brown, brown, pink, red, purple, green or black. The coloring liquid is prepared by adding all the components into the solvent and mixing them well. 2. The adhesive solution consists of 40-100 parts of a matrix, 2-6 parts of a diluent, 3-5 parts of an adhesive monomer, 6-15 parts of a polymerization inhibitor, 30-55 parts of carbon nanotubes, 20-60 parts of a filler, 1-8 parts of tartaric acid and 30-70 parts of water. The matrix consists of bisphenol A-glycidyl methacrylate (Bis-GMA), an epoxy resin and 10-methacryloxydecyl phosphate (MDP); or bisphenol-s-bis(3-methacryloyloxy-2-hydroxypropyl)ether, epoxy resin and 10-methacryloyloxydecyl phosphate. Preferably, the matrix is a mixture of bisphenol A-glycidyl methacrylate, the epoxy resin and 10-methacryloxydecyl phosphate in a mass ratio of 1:1:1-3. The diluent is a methacrylate, the adhesive monomer is 4-methacryloyloxyethyl trimellitic anhydride (4-META), and the polymerization inhibitor is one or a mixture of two or more of tert-butyl hydroquinone (TBHQ), hydroquinone (HQ) and p-tert-butyl catechol (TBC). Preferably, the polymerization inhibitor is a mixture of tert-butyl hydroquinone, hydroquinone and p-tert-butyl catechol in a mass ratio of 1:1:1. The filler is obtained by pretreating various metal oxides. The metal oxides are a mixture of two or more of silicon dioxide, aluminum oxide, calcium fluoride and titanium dioxide, and preferably, a mixture of silicon dioxide, aluminum oxide and calcium fluoride in a mass ratio of 1:1:1. The specific pretreatment process comprises melting the metal oxides, uniformly mixing them, and then subjecting them to quenching and grinding. In one example, the metal oxides may be melted in sequence, according to their melting points, from high to low. The particle size of the filler after grinding is smaller than the diameter of the carbon nanotube. The adhesive solution is prepared as follows:(1) Bisphenol A-glycidyl methacrylate, epoxy resin and 10-methacryloyloxydecyl phosphate in the specified ratio are added into water, mixed uniformly, then the methacrylate and 4-methacryloyloxy ethyl trimellitic anhydride are added, and the mixture is stirred uniformly for later use.(2) Silicon dioxide, aluminum oxide and calcium fluoride are melted in sequence according to their respective melting points, from high to low. Specifically, aluminum oxide is melted firstly, then silicon dioxide and finally calcium fluoride. The melted compounds are kept at the melting point of calcium fluoride for 15-30 min to achieve phase balance. Thereafter, the melted compounds are put into water for quenching, so that the melted compounds are solidified into a solid mixture, and when the temperature of the solid mixture is 200-300° C., the solid mixture is put into an oil and cooled to room temperature. The solid mixture is taken out and dried, and then crushed until the particle size is smaller than the diameter of the carbon nanotubes. In some cases, the particle size of the filler changes with the diameter of the carbon nanotubes used, and the particle size of the filler is always kept smaller than the diameter of the carbon nanotubes, preferably smaller than ¼-½ of the diameter of the carbon nanotubes, thereby obtaining a filler powder.(3) The filler powder obtained in step (2) is added into the mixed liquid obtained in step (1), and then ultrasonic dispersion is carried out, wherein the vibration frequency is 12-16 kHz, and the dispersion time is 10-20 min. Then, a mixture of tert-butyl hydroquinone, hydroquinone and p-tert-butyl catechol is added thereto, and stirred uniformly to obtain a mixed solution. Finally, carbon nanotubes with a diameter of 10-20 nm and a length of 0.5-2 μm are added into the mixed solution, and ultrasonic dispersion is continued for 15-30 min with a vibration frequency of 19-25 kHz.(4) Tartaric acid (TA) is added to the solution obtained in step (3), so as to adjust the solidification time of the whole reaction system and improve its operability, and an adhesive solution is obtained after stirring uniformly. Meanwhile, according to the situation, an appropriate amount of water can be added to the adhesive solution to adjust the consistency and/or viscosity of the adhesive solution. 3. The coloring treatment method of the zirconia base is specifically as follows.(1) The zirconia base is roughened according to the surface roughening treatment method in Method 1, and then washed. If necessary, a neutralization reaction is carried out before washing.(2) The second coloring liquid is added into the adhesive solution. The amount of the adhesive solution is conventionally selected according to the actual condition of the zirconia denture to be colored, and the color depth of the coloring liquid is adjusted by controlling the concentration of metal ions in the coloring liquid, so as to control the color finally displayed after the coloring liquid is mixed with the adhesive solution. Finally, the zirconia denture is colored to be consistent with the color of the patient's teeth. Specifically, the volume ratio of adhesive solution to the second coloring liquid is 1-3:1. According to this ratio, the color of the mixed solution is adjusted to make the color of the mixed solution consistent with the color of the patient's teeth, so that the color of the colored zirconia denture is consistent with the color of the patient's teeth. Specifically, the coloring process is carried out as follows. According to the color of the patient's teeth, a small amount of the coloring liquid with the adhesive solution is taken by dipping with a 2 mm coloring pen to paint the surface of the denture surface, with the painting amount controlled according to the color depth of the patient's teeth. After painting, the denture is put into an oven at 90-150° C. for drying for 30 min, then taken out and put into a denture sintering furnace to heat up to 1530° C. at a rate of 5° C./min, kept at this temperature for crystallization for 120 min, and then cooled down along with the furnace. Alternatively, the zirconia denture can be put into the coloring liquid with the adhesive solution, and after the color of the zirconia denture is observed to be consistent with that of the patient's teeth, the zirconia denture can be taken out, and then the subsequent sintering operation can be carried out. Further preferably, in order to make the bonding between the coloring liquid containing the adhesive solution and the zirconia denture firmer, a layer of silane coupling agent can be painted on or over the surface of zirconia denture, so as to improve the bonding strength between the coloring liquid containing the adhesive solution and the zirconia denture. Method 2 will be further explained with specific examples below. Example 8: The Second Coloring Liquid with Different Colors in Method 2 1. Blue second coloring liquids were prepared using raw materials including neodymium nitrate, polyethylene glycol, citric acid and deionized water. The specific raw material composition and displayed color of the coloring liquids are shown in Table 11 below. TABLE 11Composition and displayed color of blue coloring liquidsMass ratio of raw materials, %Neodymium nitrideConcen-trationPolyethyleneCitricDeionizedmmol · L−1AmountglycolacidwaterColor6.2110.297.8The color7.6210.296.8gradually8.7310.295.8deepened fromlight blueto blue, andfinally showednormal blue 2. Second coloring liquids with gray color were prepared using raw materials including manganese nitrate, polyethylene glycol, citric acid and deionized water. The specific raw material composition and displayed color of the coloring liquids are shown in Table 12 below. TABLE 12Composition and displayed color of blue coloring liquidsMass ratio of raw materials, %Manganese nitrateConcen-trationPolyethyleneCitricDeionized(mmol · L−1)AmountglycolacidwaterColor4.90.0510.298.75The color6.10.1010.298.70gradually9.10.1510.298.65deepened fromlight grayto gray, andfinally showednormal gray 3. Coloring liquids with tetracycline yellow color were prepared using raw materials including erbium chloride, manganese nitrate, ammonium metavanadate, cerium nitrate, polyethylene glycol, citric acid and deionized water. The specific raw material composition and displayed color of the coloring liquids are shown in Table 13 below. TABLE 13Composition and displayed color of tetracycline yellow coloring liquidsMass ratio of raw materials, %ErbiumManganeseAmmoniumCeriumchloridenitratevanadatenitrateConcen-Concen-Concen-Concen-PolyethyleneCitricDeionizedtrationAmt.trationAmt.trationAmt.trationAmt.glycolacidwaterColor5.62.8333.50.2664.30.0054.12.8610.292.836The color gradually6.84.254.70.46.50.0755.72.8610.291.215deepened from light to8.48.56.20.88.10.0157.62.8610.286.625dark, and finally showednormal tetracycline yellowNote:Concentration is in mmol/l in Table 13. 4. Coloring liquids with tetracycline gray color were prepared using raw materials including erbium chloride, ferric chloride, manganese nitrate, polyethylene glycol, citric acid and deionized water. The specific raw material composition and displayed color of the coloring liquids are shown in Table 14 below. TABLE 14Composition and displayed color of tetracycline grey coloring liquidsMass ratio of raw materials, %ErbiumFerricManganesechloridechloridenitrateConcen-Concen-Concen-PolyethyleneCitricDeionizedtrationAmt.trationAmt.trationAmt.glycolacidwaterColor6.524.50.4665.60.73310.295.601The color gradually8.236.20.77.11.110.294.0deepened from light to10.367.21.48.82.210.289.2dark, and finallyshowed normaltetracycline grayNote:Concentration is in mmol/l in Table 14. 5. Coloring liquids with tetracycline brown color were prepared using raw materials including erbium chloride, ferric chloride, polyethylene glycol, citric acid and deionized water. The specific raw material composition and displayed color of the coloring liquids are shown in Table 15 below. TABLE 15Composition and displayed color of tetracycline brown coloring liquidsMass ratio of raw materials, %ErbiumFerricchloridechlorideConcentrationConcentrationPolyethyleneCitricDeionized(mmol · L−1)Amount(mmol · L−1)AmountglycolacidwaterColor4.12.3336.90.73310.295.734The color gradually5.23.58.81.110.294.2deepened from light to6.4710.52.210.289.6dark, and finallyshowed normaltetracycline brown 6. Brown coloring liquids were prepared using raw materials including erbium chloride, ferric chloride, praseodymium nitrate, cobalt nitrate, polyethylene glycol, citric acid and deionized water. The specific raw material composition and displayed color of the coloring liquids are shown in Table 16 below. TABLE 16Composition and displayed color of brown coloring liquidsMass ratio of raw materials, %ErbiumFerricPraseodymiumCobaltchloridechloridenitratenitrateConcen-Concen-Concen-Concen-PolyethyleneCitricDeionizedtrationAmt.trationAmt.trationAmt.trationAmt.glycolacidwaterColor2.62.2662.80.7333.10.0163.20.0510.295.735The color gradually4.12.34.21.14.30.0255.30.07510.295.3deepened from light to5.36.85.12.25.10.057.10.1510.289.6dark, and finallyshowed normalbrownNote:Concentration is in mmol/l in Table 16. 7. Coloring liquids with pink color were prepared using raw materials including erbium chloride, polyethylene glycol, citric acid and deionized water. The specific raw material composition and displayed color of the coloring liquids are shown in Table 17 below. TABLE 17Composition and displayed color of pink coloring liquidsMass ratio of raw materials, %Erbium chlorideConcen-trationPolyethyleneCitricDeionized(mmol · L−1)AmountglycolacidwaterColor7.8510.293.8The color12.51010.288.8gradually16.32010.278.8deepened fromlight pinkto pink, andfinally showednormal pink 8. Coloring liquids with red color were prepared using raw materials including erbium chloride, polyethylene glycol, citric acid and deionized water. The specific raw material composition and displayed color of the coloring liquids are shown in Table 18 below. TABLE 18Composition and displayed color of red coloring liquidsMass ratio of raw materials, %Erbium chlorideConcen-trationPolyethyleneCitricDeionized(mmol · L−1)AmountglycolacidwaterColor25.61010.288.8The color31.22010.278.8gradually36.44010.258.8deepened fromlight redto red, andfinally showednormal red 9. Coloring liquids with purple color were prepared using raw materials including neodymium nitrate, polyethylene glycol, citric acid and deionized water. The specific raw material composition and displayed color of the coloring liquids are shown in Table 19 below. TABLE 19Composition and displayed color of purple coloring liquidsMass ratio of raw materials, %Neodymium nitrideConcen-trationPolyethyleneCitricDeionized(mmol · L−1)AmountglycolacidwaterColor38.8110.295.8The color45.2410.294.8gradually54.6610.292.8deepened fromlight purpleto purple, andfinally showednormal purple 10. Coloring liquids with green color were prepared using raw materials including nickel nitrate, polyethylene glycol, citric acid and deionized water. The specific raw material composition and displayed color of the coloring liquids are shown in Table 20 below. TABLE 20Composition and displayed color of green coloring liquidsMass ratio of raw materials, %Nickel nitrateConcen-trationPolyethyleneCitricDeionized(mmol · L−1)AmountglycolacidwaterColor8.90.0110.298.79The color10.50.0310.298.77gradually13.60.0510.298.75deepened fromlight greento green, andfinally showednormal green 11. Coloring liquids with black color were prepared using raw materials including erbium chloride, ferric chloride neodymium nitrate, polyethylene glycol, citric acid and deionized water. The specific raw material composition and displayed color of the coloring liquids are shown in Table 21 below. TABLE 21Composition and displayed color of black coloring liquidsMass ratio of raw materials, %ErbiumFerricNeodymiumchloridechloridenitrideConcentrationConcentrationConcentrationPolyethyleneCitricDeionized(mmol · L−1)Amt.(mmol · L−1)Amt.(mmol · L−1)Amt.glycolacidwaterColor5.8107.20.54.12.510.285.8The color gradually7.1208.115.4510.272.8deepened from12.0409.626.51010.246.8light black to black,and finally showednormal black It can be seen from the coloring liquids prepared in the above tables that with the increase of metal ion concentration, the color of the coloring liquid deepened correspondingly. Example 9: Adhesive Solution in Method 2 The adhesive solution was prepared according to the above method, with the specific composition shown in Table 22 below. TABLE 22Composition of adhesive solutionsMeth-CarbonSiliconAluminumCalciumGroupBis-GMAEpoxyMDPacrylate4-METATBHQHQTBCnanotubesdioxideoxidefluorideTAWaterGroup1515152322230888335aGroup1515302.53.32.52.52.535101010440bGroup15154533.633340121212545cGroup2020204444445141414650dGroup20204054.34.54.54.550181818755eGroup20206064.655555202020860fNote:In Table 22, the components of the adhesive solution are in parts by weight. Example 10: Roughening Treatment of Zirconia Base in Method 2 According to the above method, the zirconia ceramic was subjected to surface roughening treatment, totally 18 groups were set, with the specific parameters of each group as shown in Table 23 below, wherein the zirconia denture after surface sandblasting was soaked in 20 mL of the mixed acid solution, and the heating temperature of the mixed acid was 80° C. TABLE 23Surface roughening treatment of zirconia dentureSurface roughening treatment of zirconia dentureSurface sandblasting treatmentHot acid treatmentParticleHydrochloric acidNitric acidVolume ratio ofSoakingsizePressureTreatmentconcentrationconcentrationhydrochloric acidtimeGroup(μm)(MPa)time (s)(mol · L−1)(mol · L−1)to nitric acid(min)Group 1300.25111:210Group 2300.27111:212.5Group 3300.210111:215Group 4300.35111:310Group 5300.37111:312.5Group 6300.310111:315Group 7450.25121:210Group 8450.27121:212.5Group 9450.210121:215Group 10450.35121:310Group 11450.37121:312.5Group 12450.310121:315Group 13600.25211:210Group 14600.27211:212.5Group 15600.210211:215Group 16600.35211:310Group 17600.37211:312.5Group 18600.310211:315 The treated zirconia dentures in the above groups were soaked in water for 2-5 min, and then air dried for later use. Example 11: Demonstration of Coloring Effect of One Embodiment of Method 2 A coloring liquid with any one of the colors from Table 11 to Table 21 was selected, mixed with the six groups of adhesive solutions in Table 22, and the color of the mixed solution was adjusted to be consistent with the color of the patient's teeth. Specifically, the color of the coloring liquid can be adjusted by increasing or decreasing the concentration of metal ions, so as to adjust the color of the mixed solution until it is consistent with the color of the patient's teeth. The volume ratio of the adhesive solution to the second coloring liquid was 1:1. The treated zirconia dentures in Table 23 were colored with the six groups of mixed coloring liquids containing the adhesive solution, that is, the treated zirconia dentures in each group in Table 23 were colored with the six groups of coloring liquids respectively. The coloring results are shown in detail in Table 24 below, wherein the bonding strength refers to the bonding strength between the coloring liquid containing the adhesive solution and the treated zirconia denture. The results showed that the treated zirconia denture in group 7 had the best bonding effect with the zirconia denture after being mixed with the adhesive solution and coloring liquid prepared in group d. TABLE 24Coloring results and bonding strengthZirconiaBonding strengthdenture surfacebetween coloringrougheningAdhesiveliquid and zirconiatreatment groupsolution groupEffectdenture (MPa)Group 1Group aAfter 40 s, the solution painted on or over the surface of zirconia25.62 ± 0.65denture began to solidifyGroup bAfter 46 s, the solution painted on or over the surface of zirconia27.23 ± 0.15denture began to solidifyGroup cAfter 52 s, the solution painted on or over the surface of zirconia28.12 ± 0.31denture began to solidifyGroup dAfter 64 s, the solution painted on or over the surface of zirconia29.69 ± 0.21denture began to solidifyGroup eAfter 72 s, the solution painted on or over the surface of zirconia29.21 ± 0.17denture began to solidifyGroup fAfter 82 s, the solution painted on or over the surface of zirconia28.98 ± 0.11denture began to solidifyGroup 2Group aAfter 45 s, the solution painted on or over the surface of zirconia25.77 ± 0.31denture began to solidifyGroup bAfter 52 s, the solution painted on or over the surface of zirconia28.63 ± 0.45denture began to solidifyGroup cAfter 59 s, the solution painted on or over the surface of zirconia29.31 ± 0.21denture began to solidifyGroup dAfter 68 s, the solution painted on or over the surface of zirconia30.21 ± 0.55denture began to solidifyGroup eAfter 78 s, the solution painted on or over the surface of zirconia29.99 ± 0.12denture began to solidifyGroup fAfter 90 s, the solution painted on or over the surface of zirconia39.45 ± 0.07denture began to solidifyGroup 3Group aAfter 48 s, the solution painted on or over the surface of zirconia27.56 ± 0.65denture began to solidifyGroup bAfter 55 second s, the solution painted on or over the surface of29.12 ± 0.61zirconia denture began to solidifyGroup cAfter 62 s, the solution painted on or over the surface of zirconia29.66 ± 0.31denture began to solidifyGroup dAfter 70 s, the solution painted on or over the surface of zirconia30.55 ± 0.54denture began to solidifyGroup eAfter 81 s, the solution painted on or over the surface of zirconia30.82 ± 0.40denture began to solidifyGroup fAfter 93 s, the solution painted on or over the surface of zirconia30.45 ± 0.21denture began to solidifyGroup 4Group aAfter 55 second s, the solution painted on or over the surface of29.33 ± 1.02zirconia denture began to solidifyGroup bAfter 58 s, the solution painted on or the surface of zirconia denture32.18 ± 0.77began to solidifyGroup cAfter 64 s, the solution painted on or over the surface of zirconia32.68 ± 0.36denture began to solidifyGroup dAfter 71 s, the solution painted on or over the surface of zirconia33.11 ± 0.46denture began to solidifyGroup eAfter 84 s, the solution painted on or over the surface of zirconia32.99 ± 0.24denture began to solidifyGroup fAfter 95 s, the solution painted on or over the surface of zirconia31.40 ± 0.17denture began to solidifyGroup 5Group aAfter 60 s, the solution painted on or over the surface of zirconia30.61 ± 0.79denture began to solidifyGroup bAfter 63 s, the solution painted on or over the surface of zirconia32.81 ± 0.65denture began to solidifyGroup cAfter 65 s, the solution painted on or over the surface of zirconia33.31 ± 0.11denture began to solidifyGroup dAfter 73 s, the solution painted on or over the surface of zirconia34.78 ± 0.23denture began to solidifyGroup eAfter 86 s, the solution painted on or over the surface of zirconia35.24 ± 0.45denture began to solidifyGroup fAfter 98 s, the solution painted on or over the surface of zirconia34.03 ± 0.02denture began to solidifyGroup 6Group aAfter 65 s, the solution painted on or over the surface of zirconia31.08 ± 0.73denture began to solidifyGroup bAfter 68 s, the solution painted on or over the surface of zirconia33.54 ± 0.46denture began to solidifyGroup cAfter 73 s, the solution painted on or over the surface of zirconia34.06 ± 0.31denture began to solidifyGroup dAfter 75 s, the solution painted on or over the surface of zirconia35.98 ± 0.25denture began to solidifyGroup eAfter 89 s, the solution painted on or over the surface of zirconia36.05 ± 0.32denture began to solidifyGroup fAfter 102 s, the solution painted on or over the surface of zirconia35.44 ± 0.12denture began to solidifyGroup 7Group aAfter 72 s, the solution painted on or over the surface of zirconia40.15 ± 0.49denture began to solidifyGroup bAfter 75 s, the solution painted on or over the surface of zirconia45.12 ± 0.47denture began to solidifyGroup cAfter 78 s, the solution painted on or over the surface of zirconia47.68 ± 0.10denture began to solidifyGroup dAfter 81 s, the solution painted on or over the surface of zirconia56.27 ± 0.98denture began to solidifyGroup eAfter 90 s, the solution painted on or over the surface of zirconia51.82 ± 0.12denture began to solidifyGroup fAfter 105 s, the solution painted on or over the surface of zirconia48.11 ± 0.47denture began to solidifyGroup 8Group aAfter 81 s, the solution painted on or over the surface of zirconia32.56 ± 0.19denture began to solidifyGroup bAfter 83 s, the solution painted on or over the surface of zirconia34.01 ± 0.37denture began to solidifyGroup cAfter 85 s, the solution painted on or over the surface of zirconia34.89 ± 0.21denture began to solidifyGroup dAfter 87 s, the solution painted on or over the surface of zirconia36.56 ± 0.14denture began to solidifyGroup eAfter 93 s, the solution painted on or over the surface of zirconia36.99 ± 0.11denture began to solidifyGroup fAfter 107 s, the solution painted on or over the surface of zirconia36.05 ± 0.21denture began to solidifyGroup 9Group aAfter 85 s, the solution painted on or over the surface of zirconia32.89 ± 0.22denture began to solidifyGroup bAfter 88 s, the solution painted on or over the surface of zirconia34.56 ± 0.14denture began to solidifyGroup cAfter 90 s, the solution painted on or over the surface of zirconia35.06 ± 0.17denture began to solidifyGroup dAfter 91 s, the solution painted on or over the surface of zirconia36.77 ± 0.21denture began to solidifyGroup eAfter 96 s, the solution painted on or over the surface of zirconia37.05 ± 0.11denture began to solidifyGroup fAfter 110 s, the solution painted on or over the surface of zirconia36.66 ± 0.05denture began to solidifyGroup 10Group aAfter 90 s, the solution painted on or over the surface of zirconia33.03 ± 0.13denture began to solidifyGroup bAfter 92 s, the solution painted on or over the surface of zirconia35.05 ± 0.14denture began to solidifyGroup cAfter 94 s, the solution painted on or over the surface of zirconia35.90 ± 0.33denture began to solidifyGroup dAfter 96 s, the solution painted on or over the surface of zirconia37.09 ± 0.14denture began to solidifyGroup eAfter 99 s, the solution painted on or over the surface of zirconia37.93 ± 0.12denture began to solidifyGroup fAfter 112 s, the solution painted on or over the surface of zirconia38.01 ± 0.01denture began to solidifyGroup 11Group aAfter 96 s, the solution painted on or over the surface of zirconia33.76 ± 0.34denture began to solidifyGroup bAfter 97 s, the solution painted on or over the surface of zirconia35.69 ± 0.37denture began to solidifyGroup cAfter 99 s, the solution painted on or over the surface of zirconia36.08 ± 0.54denture began to solidifyGroup dAfter 101 s, the solution painted on or over the surface of zirconia38.07 ± 0.44denture began to solidifyGroup eAfter 103 s, the solution painted on or over the surface of zirconia38.97 ± 0.34denture began to solidifyGroup fAfter 113 s, the solution painted on or over the surface of zirconia38.41 ± 0.15denture began to solidifyGroup 12Group aAfter 102 s, the solution painted on or over the surface of zirconia34.85 ± 0.69denture began to solidifyGroup bAfter 103 s, the solution painted on or over the surface of zirconia36.06 ± 0.61denture began to solidifyGroup cAfter 105 s, the solution painted on or over the surface of zirconia36.97 ± 0.60denture began to solidifyGroup dAfter 107 s, the solution painted on or over the surface of zirconia39.00 ± 0.37denture began to solidifyGroup eAfter 110 s, the solution painted on or over the surface of zirconia37.99 ± 0.32denture began to solidifyGroup fAfter 116 s, the solution painted on or over the surface of zirconia37.06 ± 0.13denture began to solidifyGroup 13Group aAfter 88 s, the solution painted on or over the surface of zirconia26.88 ± 0.84denture began to solidifyGroup bAfter 89 s, the solution painted on or over the surface of zirconia27.48 ± 0.71denture began to solidifyGroup cAfter 91 s, the solution painted on or over the surface of zirconia28.31 ± 0.70denture began to solidifyGroup dAfter 93 s, the solution painted on or over the surface of zirconia29.24 ± 0.51denture began to solidifyGroup eAfter 96 s, the solution painted on or over the surface of zirconia29.98 ± 0.44denture began to solidifyGroup fAfter 110 s, the solution painted on or over the surface of zirconia28.78 ± 0.11denture began to solidifyGroup 14Group aAfter 84 s, the solution painted on or over the surface of zirconia27.09 ± 0.23denture began to solidifyGroup bAfter 87 s, the solution painted on or over the surface of zirconia28.07 ± 0.54denture began to solidifyGroup cAfter 89 s, the solution painted on or over the surface of zirconia29.79 ± 0.56denture began to solidifyGroup dAfter 90 s, the solution painted on or over the surface of zirconia30.88 ± 0.37denture began to solidifyGroup eAfter 93 s, the solution painted on or over the surface of zirconia30.14 ± 0.08denture began to solidifyGroup fAfter 105 s, the solution painted on or over the surface of zirconia29.98 ± 0.04denture began to solidifyGroup 15Group aAfter 80 s, the solution painted on or over the surface of zirconia28.08 ± 0.66denture began to solidifyGroup bAfter 84 s, the solution painted on or over the surface of zirconia29.00 ± 0.46denture began to solidifyGroup cAfter 86 s, the solution painted on or over the surface of zirconia30.15 ± 0.34denture began to solidifyGroup dAfter 88 s, the solution painted on or over the surface of zirconia31.55 ± 0.30denture began to solidifyGroup eAfter 91 s, the solution painted on or over the surface of zirconia30.01 ± 0.29denture began to solidifyGroup fAfter 101 s, the solution painted on or over the surface of zirconia29.66 ± 0.15denture began to solidifyGroup 16Group aAfter 76 s, the solution painted on or over the surface of zirconia28.99 ± 0.45denture began to solidifyGroup bAfter 80 s, the solution painted on or over the surface of zirconia29.74 ± 0.23denture began to solidifyGroup cAfter 83 s, the solution painted on or over the surface of zirconia31.01 ± 0.21denture began to solidifyGroup dAfter 86 s, the solution painted on or over the surface of zirconia32.74 ± 0.24denture began to solidifyGroup eAfter 88 s, the solution painted on or over the surface of zirconia32.09 ± 0.16denture began to solidifyGroup fAfter 97 s, the solution painted on or over the surface of zirconia31.01 ± 0.16denture began to solidifyGroup 17Group aAfter 71 s, the solution painted on or over the surface of zirconia29.47 ± 0.41denture began to solidifyGroup bAfter 77 s, the solution painted on or over the surface of zirconia30.83 ± 0.45denture began to solidifyGroup cAfter 80 s, the solution painted on or over the surface of zirconia32.01 ± 0.14denture began to solidifyGroup dAfter 84 s, the solution painted on or over the surface of zirconia32.97 ± 0.24denture began to solidifyGroup eAfter 86 s, the solution painted on or over the surface of zirconia32.06 ± 0.10denture began to solidifyGroup fAfter 93 s, the solution painted on or over the surface of zirconia31.62 ± 0.01denture began to solidifyGroup 18Group aAfter 64 s, the solution painted on or over the surface of zirconia30.15 ± 0.59denture began to solidifyGroup bAfter 74 s, the solution painted on or over the surface of zirconia31.26 ± 0.49denture began to solidifyGroup cAfter 79 s, the solution painted on or over the surface of zirconia32.88 ± 0.47denture began to solidifyGroup dAfter 81 s, the solution painted on or over the surface of zirconia33.65 ± 0.40denture began to solidifyGroup eAfter 83 s, the solution painted on or over the surface of zirconia32.98 ± 0.18denture began to solidifyGroup fAfter 89 s, the solution painted on or over the surface of zirconia32.01 ± 0.11denture began to solidifycontrol groupGroup aAfter 34 s, the solution painted on or over the surface of zirconia20.18 ± 0.89denture began to solidifyGroup bAfter 37 s, the solution painted on or over the surface of zirconia22.34 ± 0.75denture began to solidifyGroup cAfter 42 s, the solution painted on or over the surface of zirconia23.56 ± 0.44denture began to solidifyGroup dAfter 46 s, the solution painted on or over the surface of zirconia24.12 ± 0.24denture began to solidifyGroup eAfter 50 s, the solution painted on or over the surface of zirconia23.31 ± 0.13denture began to solidifyGroup fAfter 53 s, the solution painted on or over the surface of zirconia22.03 ± 0.10denture began to solidify Example 12: Demonstration of Coloring Method of Another Embodiment of Method 2 In another embodiment of Method 2, the second coloring liquid is not mixed with the adhesive solution. First, the zirconia base after surface roughening treatment is colored with the second coloring liquid. When the color of the zirconia base is observed to be consistent with that of the patient's teeth, coloring is stopped, the zirconia base is oven-dried and then soaked in the adhesive solution for 1-20 min, so that the adhesive solution seals the coloring liquid in the pores of the zirconia and fills the pores on the surface of the zirconia to form a protective film on or over the surface of the zirconia ceramic, which prevents bacteria, enzymes and other substances in the oral cavity from entering the pores and causing infection and other hazards. Finally, the zirconia base is taken out, put into a denture sintering furnace, heated up to 1530° C. at a rate of 5° C./min, kept at this temperature for crystallization for 120 min, and then cooled down along with the furnace. | 57,830 |
11858868 | DETAILED DESCRIPTION OF THE EMBODIMENTS In order to make the object and advantages of the present disclosure clearer and more comprehensible, the present disclosure will be further described in detail below with reference to the examples. It should be appreciated that the specific example described herein is only intended to explain the present disclosure and is not intended to limit the present disclosure. The present disclosure provides an anti-corrosion and anti-coking ceramic coating with easy state identification for a coal-fired boiler, which is formed by compounding a bottom coating layer and a surface coating layer, whereinthe bottom coating layer is prepared from raw materials comprising, in parts by weight, 20-30 parts of sodium silicate, 1-4 parts of lanthanum oxide, 1-4 parts of niobium pentoxide, 10-20 parts of aluminum oxide, 7-12 parts of bismuth oxide, 1-3 parts of boron oxide, 1-3 parts of zinc oxide, 1-3 parts of silicon oxide, 5-10 parts of titanium dioxide, 2-6 parts of nano whisker, 1-5 parts of titanium nitride, and 10-15 parts of graphite fluoride; andthe surface coating layer is prepared from raw materials comprising, in parts by weight, 20-30 parts of sodium silicate, 1-4 parts of lanthanum oxide, 1-4 parts of niobium pentoxide, 5-10 parts of chromium oxide, 5-10 parts of aluminum oxide, 7-12 parts of bismuth oxide, 1-3 parts of boron oxide, 1-3 parts of zinc oxide, 1-3 parts of silicon oxide, 10-15 parts of graphite fluoride, 1-5 parts of titanium nitride, 5-10 parts of silicon carbide, 2-6 parts of nano whisker, and 2-6 parts of cobalt green. In some embodiments, the bottom coating layer is prepared from the following raw materials: in parts by weight, 25 parts of the sodium silicate, 2 parts of the lanthanum oxide, 2 parts of the niobium pentoxide, 15 parts of the aluminum oxide, 9 parts of the bismuth oxide, 2 parts of the boron oxide, 2 parts of the zinc oxide, 2 parts of the silicon oxide, 7 parts of the titanium dioxide, 4 parts of the nano whisker, 3 parts of the titanium nitride, and 12 parts of the graphite fluoride; the surface coating layer is prepared from the following raw materials: in parts by weight, 25 parts of the sodium silicate, 2 parts of the lanthanum oxide, 2 parts of the niobium pentoxide, 7 parts of the chromium oxide, 7 parts of the aluminum oxide, 9 parts of the bismuth oxide, 2 parts of the boron oxide, 2 parts of the zinc oxide, 2 parts of the silicon oxide, 12 parts of the graphite fluoride, 3 parts of the titanium nitride, 7 parts of the silicon carbide, 4 parts of the nano whisker, and 4 parts of the cobalt green. In some embodiments, in the anti-corrosion and anti-coking ceramic coating, the nano whisker is any one selected from the group consisting of nano silicon carbide whisker and nano zirconia whisker. In some embodiments, in the raw materials for the bottom coating layer, the lanthanum oxide, the niobium pentoxide, the aluminum oxide, the bismuth oxide, the boron oxide, the zinc oxide, the silicon oxide, the titanium dioxide, and the titanium nitride are in the form of powder with a particle size of 1-10 μm, respectively; the graphite fluoride has a thickness of 1-10 μm and a particle size of 1-30 μm; the nano whisker has a length of 10-60 μm. In the bottom coating layer, the sodium silicate is used as an adhesive. Due to the addition of aluminum oxide, bismuth oxide, boron oxide, zinc oxide, and silicon oxide, a low-temperature sintering could be achieved and the relative density of the ceramic coating could be improved, thereby ensuring the isolation of the substrate from the external corrosive medium. In addition, due to the addition of aluminum oxide, the high-temperature corrosion resistance of the ceramic coating is further improved. Due to the addition of lanthanum oxide and niobium pentoxide, the sintering temperature range is broadened and the sintering quality is improved. Due the addition of nano whisker, the toughness of the ceramic coating is enhanced, thereby improving the bonding with the substrate metal and the mechanical properties of the ceramic coating. Due to the addition of the titanium nitride and graphite fluoride, the wettability between the ceramic coating and the molten slag is reduced, thereby imparting the anti-coking and anti-slagging performance to the ceramic coating. Also, the self-lubricity of graphite fluoride and the micro-nano-scale rough structure with low surface energy of the ceramic coating further help to improve the anti-coking and anti-slagging performance of the ceramic coating. The presence of titanium dioxide makes the ceramic coating with a white appearance. In some embodiments, in the raw materials for the surface coating layer, the lanthanum oxide, the niobium pentoxide, the chromium oxide, the aluminum oxide, the bismuth oxide, the boron oxide, the zinc oxide, the silicon oxide, the titanium nitride, the silicon carbide, and the cobalt green are in the form of powders with a particle size of 1-10 μm, respectively; the graphite fluoride has a thickness of 1-10 μm and a particle size of 1-30 μm; the nano whisker has a length of 10-60 μm. In the surface coating layer, the sodium silicate is used as an adhesive. Due to the addition of aluminum oxide, bismuth oxide, boron oxide, zinc oxide, and silicon oxide, a low-temperature sintering could be achieved and the relative density of the ceramic coating could be improved, thereby ensuring the isolation of the substrate from the external corrosive medium. In addition, due to the addition of aluminum oxide, the high-temperature corrosion resistance of the ceramic coating is improved. Due to the addition of chromium oxide, the high-temperature corrosion resistance of the ceramic coating is further improved. Due to the addition of lanthanum oxide and niobium pentoxide, a sintering temperature range is broadened, and the sintering quality is improved. Due to the addition of nano whisker, the toughness of the ceramic coating is enhanced. Due to the addition of the titanium nitride and graphite fluoride, the wettability between the ceramic coating and the molten slag is reduced, thereby imparting anti-coking and anti-slagging performance to the ceramic coating. Also, the self-lubricity of graphite fluoride and the micro-nano-scale rough structure with low surface energy of the ceramic coating further help to improve the anti-coking and anti-slagging performance of the ceramic coating. Due to the addition of the silicon carbide, the wear resistance of the ceramic coating is improved. The addition of the cobalt green makes the ceramic coating with a green appearance. Due to the addition of the chromium oxide, the color stability of the ceramic coating during operation is further ensured. EXAMPLE 1 Step 1, deionized water that was 1.75 times the loose packing volume of all raw materials for a bottom coating layer was provided.Step 2, the deionized water was added to 25 g of sodium silicate, and they were stirred to be uniform, obtaining a mixture I.Step 3, 2 g of lanthanum oxide, 2 g of niobium pentoxide, 15 g of aluminum oxide, 9 g of bismuth oxide, 2 g of boron oxide, 2 g of zinc oxide, 2 g of silicon oxide, 7 g of titanium dioxide, and 3 g of titanium nitride, each of which had a particle size of 1-10 μm respectively, were mixed and ball milled in a high-energy ball mill for 4-6 h, obtaining a further refined powder mixture II.Step 4, 12 g of graphite fluoride with a thickness of 1-10 μm and a particle size of 1-30 μm, and 4 g of nano silicon carbide whisker with a length of 10-60 μm were added to the powder mixture II obtained in step 3, and they were stirred in a mixer for 0.5-1 h at a stirring rate of 50-150 rpm, obtaining a mixture III.Step 5, the mixture I obtained in step 2 was added to the mixture III obtained in step 4, and they were stirred in a mixer for 0.5-1 h at a stirring rate of 50-150 rpm, obtaining a bottom coating.Step 6, deionized water that was 1.75 times the loose packing volume of all raw materials for a surface coating layer was provided.Step 7, the deionized water was added to 25 g of the sodium silicate, and they were stirred to be uniform, obtaining a mixture IV.Step 8, 2 g of lanthanum oxide, 2 g of niobium pentoxide, 7 g of chromium oxide, 7 g of aluminum oxide, 9 g of bismuth oxide, 2 g of boron oxide, 2 g of zinc oxide, 2 g of silicon oxide, 3 g of titanium nitride, 7 g of silicon carbide, 4 g of nano silicon carbide whisker, and 4 g of cobalt green, each of which had a particle size of 1-10 μm respectively, were mixed and ball milled in a high-energy ball mill for 4-6 h, obtaining a further refined powder mixture V.Step 9, 12 g of graphite fluoride with a thickness of 1-10 μm and a particle size of 1-30 μm, and 4 g of nano silicon carbide whisker with a length of 10-60 μm were added to the powder mixture V obtained in step 8, and they were stirred in a mixer for 0.5-1 h at a stirring rate of 50-150 rpm, obtaining a mixture VI.Step 10, the mixture IV obtained in step 7 was added to the mixture VI obtained in step 9, and they were stirred in a mixer for 0.5-1 h at a stirring rate of 50-150 rpm, obtaining a surface coating.Step 11, the environment was inspected, and a temperature of 25° C. and a relative humidity of 60% were maintained in the construction environment, and the temperature of a substrate was ensured to be at least 3° C. higher than the dew point temperature.Step 12, a surface of the substrate was pretreated by using a sandblasting technology until a cleanliness of Sa3.0 level and a roughness of 25-75 μm were reached.Step 13, the coating was stirred again at 50-150 rpm for 0.5-1 h before spraying. The bottom coating was sprayed onto the surface of the substrate by using an air atomization spray gun, and dried. The thickness of the bottom coating layer was measured, and controlled to be 50-100 μm. When the thickness of the bottom coating layer was qualified, the surface coating was sprayed onto the bottom coating layer, and dried. The overall thickness of the ceramic coating was measured, and controlled to be 200-300 μm. When the overall thickness was qualified, the substrate sample with the two-layer-compounded coating was heated to 400° C. and maintained at the temperature for 30 min, obtaining the anti-corrosion and anti-coking ceramic coating with easy state identification. The cross-sectional structure of the ceramic coating obtained in Example 1 is shown inFIG.1. As can be seen fromFIG.1, the bottom coating layer is well combined with the substrate; the bottom coating layer is well combined with the surface coating layer with no obvious gap; the internal structure of the ceramic coating is dense with no visible pores. In the present disclosure, the powder of raw materials is refined by using a high-energy ball mill, such that a micro-nano-scale rough structure with low surface energy is formed on the surface of the prepared ceramic coating, as shown inFIG.2. Table 1 shows test results of key use parameters such as bonding strength and thermal shock performance of the ceramic coating. The results show that the ceramic coating exhibits a bonding strength of about 38 MPa, and could withstand at least 80-time thermal shock test, indicating that the ceramic coating exhibits excellent reliability in use.FIGS.3A-3Bshows an operating state of a water wall in a combustion region of a boiler of a power station in Hami, China before renovation by using the ceramic coating according to the present disclosure. As shown inFIGS.3A-3B, the surface of the water wall is seriously coked and there is high-temperature corrosion (FIG.3Ashows the coking situation, andFIG.3Bshows the surface corrosion after coke cleaning).FIG.4shows a state of the water wall in this area after operation of 14,000 h, the water wall being renovated by using the ceramic coating according to the present disclosure. As shown inFIG.4, there is no coking and slagging on the surface of the water wall, and the high-temperature corrosion is completely alleviated. FIG.5shows an inspection situation of a water wall of a boiler of a power station in Changji, China after operation of 8,000 h, the water wall being renovated by using the ceramic coating according to the present disclosure. As shown inFIG.5, the current operating state of the ceramic coating can be directly judged by visual inspection (a green area represents that the current surface coating layer is in good condition; a white area represents a loss of the surface coating layer, and a further surface coating needs to be re-sprayed onto the white bottom coating layer). TABLE 1Performance test results of ceramic coatings prepared in examplesIndexValueRemarksBonding38 MPaTesting according to GB/Tstrength5210-2006Thermal80 times withoutHeating to 1,200° C. andshock performancecracking or falling offquenching with cold water The foregoing description is only preferred implementations of the present disclosure. It should be noted that a person of ordinary skill in the art can also make several improvements and modifications without departing from the principle of the present disclosure. These improvements and modifications should also fall within the scope of the present disclosure. | 13,250 |
11858869 | DETAILED DESCRIPTION Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the disclosure belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, typical methods and materials are described. The articles “a” and “an” are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. By way of example, “an element” means one element or more than one element. In the context of this specification, the term “about,” is understood to refer to a range of numbers that a person of skill in the art would consider equivalent to the recited value in the context of achieving the same function or result. Throughout this specification and the claims which follow, unless the context requires otherwise, the word “comprise”, and variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. The term “plant productivity” as used herein refers to any aspect of growth or development of a plant, that is a reason for which the plant is grown. Thus, for purposes of the present disclosure, improved or increased plant productivity refers broadly to improvements in biomass or yield of leaves, stems, grain, fruit, vegetables, flowers, or other plant parts harvested or used for various purposes, and improvements in growth of plant parts, including stems, leaves and roots. For example, when referring to food crops, such as grains, fruits or vegetables, plant productivity may refer to the yield of grain, fruit, vegetables or seeds harvested from a particular crop. For crops such as pasture, plant productivity may refer to growth rate, plant density or the extent of groundcover. “Plant growth” refers to the growth of any plant part, including stems, leaves and roots. Growth may refer to the rate of growth of any one of these plant parts. The term “yield” refers to the amount of produced biological material and may be used interchangeably with “biomass”. For crop plants, “yield” may also mean the amount of harvested material per unit of production or per area (e.g. hectare). Yield may be defined in terms of quantity or quality. The harvested material may vary from crop to crop, for example, it may be seeds, above-ground biomass, below-ground biomass (e.g. potatoes), roots, fruits, or any other part of the plant which is of economic value. “Yield” also encompasses yield stability of the plants. “Yield” also encompasses yield potential, which is the maximum obtainable yield under optimal growth conditions. Yield may be dependent on a number of yield components, which may be monitored by certain parameters. These parameters are well known to persons skilled in the art and vary from crop to crop. For example, breeders are well aware of the specific yield components and the corresponding parameters for the crop they are aiming to improve. For example, key yield parameters for potato include tuber weight, number of tubers, and number of stems per plant. By “improving soil quality” is meant increasing the amount and/or availability of nutrients required by, or beneficial to plants, for growth. By way of example only, such nutrients include nitrogen, phosphorous, potassium, copper, zinc, boron and molybdenum. Also encompassed by the term “improving soil quality” is reducing or minimising the amount of an element that may be detrimental to plant growth or development such as, for example iron and manganese. Thus, improving soil quality by use of microbial inoculants and fertilizer compositions of the present disclosure thereby assists and promotes the growth of plants in the soil. The term “remediating” as used herein in relation to degraded pasture or soil refers to the improvement in plant nutrient content in the soil to facilitate improved plant growth and/or yield. Degraded pasture includes overgrazed pasture. As used herein, the term “effective amount” refers to an amount of microbial inoculant or fertilizer composition applied to a given area of soil or vegetation that is sufficient to effect one or more beneficial or desired outcomes, for example, in terms of plant growth rates, crop yields, or nutrient availability in the soil. An “effective amount” can be provided in one or more administrations. The exact amount required will vary depending on factors such as the identity and number of individual strains employed, the plant species being treated, the nature and condition of the soil to be treated, the exact nature of the microbial inoculant or fertilizer composition to be applied, the form in which the inoculant or fertilizer is applied and the means by which it is applied, and the stage of the plant growing season during which application takes place. Thus, it is not possible to specify an exact “effective amount”. However, for any given case, an appropriate “effective amount” may be determined by one of ordinary skill in the art using only routine experimentation. The term “crop” as used herein refers to any plant grown to be harvested or used for any economic purpose, including for example human foods, livestock fodder, fuel or pharmaceutical production (e.g. poppies). The term “optionally” is used herein to mean that the subsequently described feature may or may not be present or that the subsequently described event or circumstance may or may not occur. Hence the specification will be understood to include and encompass embodiments in which the feature is present and embodiments in which the feature is not present, and embodiments in which the event or circumstance occurs as well as embodiments in which it does not. In accordance with the present disclosure, novel microbial inoculants and microbial fertilizer compositions are presented which find application in increasing plant productivity and improving soil quality. In particular embodiments the microbial species present in the microbial inoculant or fertilizer composition provide a symbiotic combination of organisms. In the broadest embodiments, a microbial inoculant of the present disclosure comprises strains of one or more bacterialLactobacillusspecies. TheLactobacillusspecies may be selected fromLactobacillus parafarraginis, Lactobacillus buchneri, Lactobacillus rapiandLactobacillus zeae. The inoculant may further comprise at least oneAcetobacterspecies and at least oneCandidaspecies. TheLactobacillus parafarraginisstrain may beLactobacillus parafarraginisLp18. In a particular embodiment theLactobacillus parafarraginisstrain isLactobacillus parafarraginisLp18 deposited with National Measurement Institute, Australia on 27 Oct. 2011 under Accession Number V11/022945. TheLactobacillus buchneristrain may beLactobacillus buchneriLb23. In a particular embodiment theLactobacillus buchneristrain isLactobacillus buchneriLb23 deposited with National Measurement Institute, Australia on 27 Oct. 2011 under Accession Number V11/022946. TheLactobacillus rapistrain may beLactobacillus rapiLr24. In a particular embodiment theLactobacillus rapistrain isLactobacillus rapiLr24 deposited with National Measurement Institute, Australia on 27 Oct. 2011 under Accession Number V11/022947. TheLactobacillus zeaestrain may beLactobacillus zeaeLz26. In a particular embodiment theLactobacillus zeaestrain isLactobacillus zeaeLz26 deposited with National Measurement Institute, Australia on 27 Oct. 2011 under Accession Number V11/022948. The inoculant may further comprise a strain ofAcetobacter fabarum. TheAcetobacter fabarumstrain may beAcetobacter fabarumAf15. In a particular embodiment theAcetobacter fabarumstrain isAcetobacter fabarumAf15 deposited with the National Measurement Institute, Australia on 27 Oct. 2011 under Accession Number V11/022943. The inoculant may further comprise a yeast. The yeast may be a strain ofCandida ethanolica. TheCandida ethanolicastrain may beCandida ethanolicaCe31. In a particular embodiment theCandida ethanolicastrain isCandida ethanolicaCe31 deposited with the National Measurement Institute, Australia on 27 Oct. 2011 under Accession Number V11/022944. The concentrations of each microbial strain to be added to microbial inoculants and fertilizer compositions as disclosed herein will depend on a variety of factors including the identity and number of individual strains employed, the plant species being treated, the nature and condition of the soil to be treated, the exact nature of the microbial inoculant or fertilizer composition to be applied, the form in which the inoculant or fertilizer is applied and the means by which it is applied, and the stage of the plant growing season during which application takes place. For any given case, appropriate concentrations may be determined by one of ordinary skill in the art using only routine experimentation. By way of example only, the concentration of each strain present in the inoculant or fertilizer composition may be from about 1×102cfu/ml to about 1×1010cfu/ml, and may be about 1×103cfu/ml, about 2.5×103cfu/ml, about 5×103cfu/ml, 1×104cfu/ml, about 2.5×104cfu/ml, about 5×104cfu/ml, 1×105cfu/ml, about 2.5×105cfu/ml, about 5×105cfu/ml, 1×106cfu/ml, about 2.5×106cfu/ml, about 5×106cfu/ml, 1×107cfu/ml, about 2.5×107cfu/ml, about 5×107cfu/ml, 1×108cfu/ml, about 2.5×108cfu/ml, about 5×108cfu/ml, 1×109cfu/ml, about 2.5×109cfu/ml, or about 5×109cfu/ml. In particular exemplary embodiments the final concentration of theLactobacillusstrains is about 2.5×105cfu/ml, the final concentration ofAcetobacter fabarummay be about 1×106cfu/ml and the final concentration ofCandida ethanolicamay be about 1×105cfu/ml. Also contemplated by the present disclosure are variants of the microbial strains described herein. As used herein, the term “variant” refers to both naturally occurring and specifically developed variants or mutants of the microbial strains disclosed and exemplified herein. Variants may or may not have the same identifying biological characteristics of the specific strains exemplified herein, provided they share similar advantageous properties in terms of promoting plant growth and providing nutrients for plant growth in the soil. Illustrative examples of suitable methods for preparing variants of the microbial strains exemplified herein include, but are not limited to, gene integration techniques such as those mediated by insertional elements or transposons or by homologous recombination, other recombinant DNA techniques for modifying, inserting, deleting, activating or silencing genes, intraspecific protoplast fusion, mutagenesis by irradiation with ultraviolet light or X-rays, or by treatment with a chemical mutagen such as nitrosoguanidine, methylmethane sulfonate, nitrogen mustard and the like, and bacteriophage-mediated transduction. Suitable and applicable methods are well known in the art and are described, for example, in J. H. Miller,Experiments in Molecular Genetics, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y. (1972); J. H. Miller,A Short Course in Bacterial Genetics, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y. (1992); and J. Sambrook, D. Russell, Molecular Cloning: A Laboratory Manual, 3rd ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y. (2001), inter alia. Also encompassed by the term “variant” as used herein are microbial strains phylogenetically closely related to strains disclosed herein and strains possessing substantial sequence identity with the strains disclosed herein at one or more phylogenetically informative markers such as rRNA genes, elongation and initiation factor genes, RNA polymerase subunit genes, DNA gyrase genes, heat shock protein genes and recA genes. For example, the 16S rRNA genes of a “variant” strain as contemplated herein may share about 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% sequence identity with a strain disclosed herein. Microbial inoculants and fertilizer compositions of the present disclosure may optionally further comprise one or more additional microbial organisms, for example, additional agronomically beneficial microorganisms. Such agronomically beneficial microorganisms may act in synergy or concert with, or otherwise cooperate with the organisms of the present disclosure in the inoculant or fertilizer. Examples of agronomically beneficial microorganisms includeBacillussp.,Pseudomonassp.,Rhizobiumsp.,Azospirillumsp.,Azotobactersp., phototrophic and cellulose degrading bacteria,Clostridiumsp.,Trichodermasp. and the like. Those skilled in the art will appreciate that this list is merely exemplary only, and is not limited by reference to the specific examples here provided. In the soil environment, inoculated bacteria can find survival difficult among naturally occurring competitor and predator organisms. To aid in survival of microorganisms present in microbial inoculants and fertilizer compositions of the present disclosure upon application in the environment, one or more of the strains may be encapsulated in, for example, a suitable polymeric matrix. In one example, encapsulation may comprise alginate beads such as has been described by Young et al, 2006, Encapsulation of plant growth-promoting bacteria in alginate beads enriched with humic acid,Biotechnology and Bioengineering95:76-83, the disclosure of which is incorporated herein by reference in its entirety. Those skilled in the art will appreciate that any suitable encapsulation material or matrix may be used. Encapsulation may be achieved using methods and techniques known to those skilled in the art. Encapsulated microorganisms can include nutrients or other components of the inoculant or fertilizer composition in addition to the microorganisms. Those skilled in the art will appreciate that any plant may benefit from the application of microbial inoculants and fertilizer compositions of the present disclosure to soil, seeds and/or vegetation. Particular embodiments are employed to aid the growth, development, yield or productivity of crops and pastures or other plants of economic value, including ornamentals and plants grown for oils or biofuel. The crop plant may be, for example, a food crop (for humans or other animals) such as any fruit, vegetable, nut, seed or grain producing plant. Exemplary crop plants include, but are not limited to, tubers and other below-ground vegetables (such as potatoes, beetroots, radishes, carrots, onions, etc.), ground-growing or vine vegetables (such as pumpkin and other members of the squash family, beans, peas, asparagus, etc.), leaf vegetables (such as lettuces, chard, spinach, alfalfa, etc.), other vegetables (such as tomatoes,brassicaincluding broccoli, avocadoes, etc.), fruits (such as berries, olives, stone fruits including nectarines and peaches, tropical fruits including mangoes and bananas, apples, pears, mandarins, oranges, mandarins, kiwi fruit, coconut, etc.), cereals (such as rice, maize, wheat, barley, millet, oats, rye etc.), nuts (such as macadamia nuts, peanuts, brazil nuts, hazel nuts, walnuts, almonds, etc.), and other economically valuable crops and plants (such as sugar cane, soybeans, sunflower, canola, sorghum, pastures, turf grass, etc). Microbial inoculants and fertilizer compositions of the present disclosure may be applied directly to plants, plant parts (such as foliage) or seeds, or alternatively may be applied to soil in which the plants are growing or to be grown or in which seeds have been or are to be sown. Application may be by any suitable means and may be on any suitable scale. For example, application may comprise pouring, spreading or spraying, including broad scale or bulk spreading or spraying, soaking of seeds before planting, and/or drenching of seeds after planting or seedlings. Those skilled in the art will appreciate that multiple means of application may be used in combination (for example soaking of seeds prior to planting followed by drenching of planted seeds and/or application to seedlings or mature plants). Seeds, seedlings or mature plants may be treated as many times as appropriate. The number of applications required can readily be determined by those skilled in the art depending on, for example, the plant in question, the stage of development of the plant at which treatment is initiated, the state of health of the plant, the growth, environmental and/or climatic conditions in which the plant is grown and the purpose for which the plant is grown. For example, in the case of flowering crops such as tomatoes, it may be desirable to apply the microbial inoculant or fertilizer composition once or more than once during the flowering period. Thus, in accordance with the present disclosure, microbial inoculants and fertilizer products as disclosed herein may be prepared in any suitable form depending on the means by which the inoculant or fertilizer composition is to be applied to the soil or to plant seeds or vegetation. Suitable forms can include, for example, slurries, liquids, and solid forms. Solid forms include powders, granules, larger particulate forms and pellets. Solid form fertilizer particles can be encapsulated in water soluble coatings (for example dyed or undyed gelatin spheres or capsules), extended release coatings, or by micro-encapsulation to a free flowing powder using one or more of, for example, gelatin, polyvinyl alcohol, ethylcellulose, cellulose acetate phthalate, or styrene maleic anhydride. Liquids may include aqueous solutions and aqueous suspensions, and emulsifiable concentrates. In order to achieve effective dispersion, adhesion and/or conservation or stability within the environment of inoculants and fertilizer compositions disclosed herein, it may be advantageous to formulate the inoculants and compositions with suitable carrier components that aid dispersion, adhesion and conservation/stability. Suitable carriers will be known to those skilled in the art and include, for example, chitosan, vermiculite, compost, talc, milk powder, gels and the like. Additional components may be incorporated into inoculants and fertilizer compositions of the present disclosure, such as humic substances, trace elements, organic material, penetrants, macronutrients, micronutrients and other soil and/or plant additives. Humus or humic substances that may be incorporated may include, but are not limited to, humic acid derived from, for example oxidised lignite or leonardite, fulvic acid and humates such as potassium humate. Organic material added may include, but is not limited to, biosolids, animal manure, compost or composted organic byproducts, activated sludge or processed animal or vegetable byproducts (including blood meal, feather meal, cottonseed meal, ocean kelp meal, seaweed extract, fish emulsions and fish meal). Penetrants include, but are not limited to, non-ionic wetting agents, detergent based surfactants, silicones, and/or organo-silicones. Suitable penetrants will be known to those skilled in the art, non-limiting examples including polymeric polyoxyalkylenes, allinol, nonoxynol, octoxynol, oxycastrol, TRITON, TWEEN, Sylgard 309, Silwet L-77, and Herbex (silicone/surfactant blend). Exemplary trace elements for inclusion in microbial inoculants and fertilizer compositions are provided in Example 1. However those skilled in the art will recognise that suitable trace elements are not limited thereto, and that any trace elements (natural or synthetic) may be employed. Optional further soil and/or plant additives that can be added to inoculants and fertilizer compositions of the present disclosure include, for example, water trapping agents such as zeolites, enzymes, plant growth hormones such as gibberellins, and pest control agents such as acaracides, insecticides, fungicides and nematocides. The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an acknowledgment or admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates. The present disclosure will now be described with reference to the following specific examples, which should not be construed as in any way limiting the scope of the invention. EXAMPLES The following examples are illustrative of the invention and should not be construed as limiting in any way the general nature of the disclosure of the description throughout this specification. Example 1—Microbial Strains The following microbial strains were used in the production of a biofertilizer. Lactobacillus parafarraginisLp18 was isolated from an environmental source. Partial 16S rRNA sequencing indicated 100% similarity toLactobacillus parafarraginisAB 262735 which has a risk group of 1 (TRBA). When cultured on MRS media for 3 days at 34° C., anaerobically, Lp18 produces cream, round, slight sheen, convex, colony diameter 1-2 mm (facultative anaerobe). Its microscopic appearance is Gram positive, non-motile, short rods rectangular, mainly diploid.Lactobacillus parafarraginisLp18 was deposited with the National Measurement Institute, Australia on 27 Oct. 2011 under Accession Number V11/022945. Lactobacillus buchneriLb23 was isolated from an environmental source. Partial 16S rRNA sequencing indicated 99% similarity toLactobacillus buchneriAB 429368 which has a risk group of 1 (TRBA). When cultured on MRS media for 4 days at 34° C., anaerobically, Lb23 produces cream, shiny, convex, colony diameter 1-2 mm (facultative anaerobe). Its microscopic appearance is Gram positive, non-motile, rods in chains.Lactobacillus buchneriLb23 was deposited with the National Measurement Institute, Australia on 27 Oct. 2011 under Accession Number V11/022946. Lactobacillus rapiLr24 was isolated from an environmental source. Partial 16S rRNA sequencing indicated 99% similarity toLactobacillus rapiAB 366389 which has a risk group of 1 (DSMZ). When cultured on MRS media for 4 days at 34° C., anaerobically, Lr24 produces cream, round, shiny colonies with a diameter of 0.5 mm (facultative anaerobe). Its microscopic appearance is Gram positive, non-motile, short rods single or diploid.Lactobacillus rapiLr24 was deposited with the National Measurement Institute, Australia on 27 Oct. 2011 under Accession Number V11/022947. Lactobacillus zeaeLz26 was isolated from an environmental source. Partial 16S rRNA sequencing indicated 99% similarity toLactobacillus zeaeAB 008213.1 which has a risk group of 1 (TRBA). When cultured on MRS media for 48 hours at 34° C., anaerobically, Lz26 produces white, round, shiny, convex, colonies with a diameter of 1 mm (facultative anaerobe). Its microscopic appearance is Gram positive, non-motile, short rods almost coccoid, diploid and some chains.Lactobacillus zeaeLz26 was deposited with the National Measurement Institute, Australia on 27 Oct. 2011 under Accession Number V11/022948. Acetobacter fabarumAf15 was isolated from an environmental source. Partial 16S rRNA sequencing indicated 100% similarity toAcetobacter fabarumAM 905849 which has a risk group of 1 (DSMZ). When cultured on Malt extract media for 3 days at 34° C., AF15 produces opaque, round, shiny, convex, colony diameter 1 mm (aerobic). Its microscopic appearance is Gram negative, rods single or diploid.Acetobacter fabarumAf15 was deposited with the National Measurement Institute, Australia on 27 Oct. 2011 under Accession Number V11/022943. Candida ethanolicaCe31 was isolated from an environmental source. Partial 16S rRNA sequencing indicated 89% similarity toCandida ethanolicaAB534618. When cultured on Malt extract media for 2 days at 34° C., Ce31 produces cream, flat, dull, roundish, colony diameter 2-3 mm (aerobic). Its microscopic appearance is budding, ovoid yeast.Candida ethanolicaCe31 was deposited with the National Measurement Institute, Australia on 27 Oct. 2011 under Accession Number V11/022944. Maintenance of Cultures 30% glycerol stocks were made of each isolate and maintained at −80° C. for long-term culture storage. Short-term storage of the cultures are maintained at 4° C. on agar slopes (3 month storage) and on agar plates which are subcultured monthly. To maintain the isolates original traits, a fresh plate is made from the −80° C. stock following three plate subcultures. Inoculum and Growth Media TheLactobacillusstrains were grown with or without air (L. rapiprefers anaerobic) either in MRS broth (Difco) or on MRS agar plates depending on application. The cultures were routinely grown for 2 days at a mesophilic temperature of 30-34° C. TheAcetobacterandEthanolicastrains are grown aerobically either in Malt extract broth (Oxoid) or on Malt extract agar plates depending on application. The cultures are routinely grown for 2 days at a mesophilic temperature of 30-34° C. Fermenter ‘Seed’ Preparation For individual strains, using a sterile nichrome wire a single colony is removed from a fresh culture plate and transferred to a universal bottle containing 15 mL of sterile media. The bottle is securely placed in a shaking incubator set at 30° C., 140 rpm for 48 hrs (L. rapiis not shaken). After incubation a cloudy bacterial growth should be visible. ‘Seed’ inoculation bottles are stored at 4° C. until required (maximum 1 week). Typically a 5% bacterial inoculation is required for a fermenter run. The stored 15 ml culture seed is added to a Schott bottle containing a volume of sterile media which is 5% of the total fermenter working volume. The culture is incubated and shaken in the same way as the 15 ml seed. Large scale automatic fermenters are used to grow pure cultures of each isolate. There is an automatic feed of alkali, antifoam and glucose. Typically the temperature is maintained at 30-34° C., pH 5.5 but the oxygen and agitation varies depending on the microorganism. Sample Analysis After each large scale culturing of an isolate a sample is aseptically withdrawn and a viability count undertaken using 10 fold serial dilutions, performed in a laminar flow hood. A wet slide is also prepared and purity observed using a phase contrast microscope to double check for contaminants that may be present but unable to grow on the culture media. After 48 hours the viability plates are checked for a pure culture (same colony morphology) and the colonies counted to produce a colony forming unit per ml (cfu/ml) value. A Grams stain is also performed. Example 2—Pasture Trials Field trials on pasture were conducted using a biofertlizer as disclosed herein, in comparison to untreated pasture and pasture treated with conventional inorganic fertilizers. The biofertilizer (hereinafter “IMP Bio”) comprised the six microbial strains listed in Example 1, at final concentrations of 2.5×105cfu/ml for each of theLactobacillusstrains, 1.0×105cfu/ml forCandida ethanolicaand 1.0×106cfu/ml forAcetobacter fabarum. The strains were grown as described in Example 1 and mixed with 2% trace elements, 0.3% humate (Soluble Humate, LawrieCo), 3% molasses and 0.1-0.2% phosphoric acid. Phosphoric acid was added to the point where pH was in the range 3.8 to 4.0. The trace elements component typically comprised the following (per 1,000 L): TABLE 1Trace elements component of biofertilizerMaterialVolume (kg)Water200kgPotassium Sulphate15.25kgCopper Complex125.6kgMagnesium Citrate2175.0kgChromium Citrate310.0kgCalcium Sokolate452.0kgCitric Acid11.15kgFerrous Sulphate4.0kgCobalt Sulphate750gNickel Sulphate250gManganese Sulphate4.0kgUrea31.0kgZinc Sulphate4.0kgBorax4.5kgM A P13.25kgSodium Molybdate2.5kgAcetic Acid10.8kgSugar50.0kg Conventional inorganic fertilizers used as comparators were Spray Gro Liquid Urea, DAP (diammonium phosphate), and 14:16:11 commercial NPK mix. Sites for the pasture trials were selected based on rainfall levels, soil type, pasture composition and past fertilizing practices. The following locations in Tasmania were used: Nabageena (high rainfall; rye grass, cocksfoot, Yorkshire fog and other grasses), Cuprona (high rainfall; rye grass), West Moorville/Upper Burnie (high rainfall; rye grass), Connorville (dryland pasture; degraded) and Connorville (irrigated pasture; rye grass). At each location, multiple 4×10 m strips of pasture were prepared by mowing to a height of 45 mm (and removal of clipped plant material prior to fertilizing). At West Moorville/Upper Burnie and Nabageena, IMP Bio was applied to replicate plots at 20 L/ha, 30 L/ha or 50 L/ha, and 14:16:11 NPK mix was applied to replicate plots at 250 kg/ha. At West Moorville, DAP was also applied to replicate plots at 125 kg/ha. At Cuprona, IMP Bio was applied to replicate plots at 20 L/ha, 30 L/ha or 50 L/ha, and Spray Gro Liquid Urea was applied at 50 L/ha. At Connorville, IMP Bio was applied to replicate plots at 20 L/ha, 30 L/ha or 50 L/ha, and DAP was applied to replicate plots at 125 kg/ha. IMP Bio and SprayGro Urea were applied as large droplets through 2 m backpack boom sprays in a single pass. 14:16:11 NPK mix and DAP were applied by hand distribution. At each location, replicate control (unfertilized) plots were set aside. Plant yield and leaf nutrient content were analysed 6-8 weeks after treatment. Results for plant yield are shown in Table 2 below. These results indicate that the IMP Bio fertilizer produced yields at least similar to, and in some cases superior to, conventional inorganic fertilizers. TABLE 2Yield (kg/ha/day)ConventionalIMP BioIMP BioAreaControlfertilizer(30 L/ha)(half strength)Cuprona6579 (Spray Gro)75—Nabageena6078 (14:16:11)73—Connorville3534 (DAP)3231(dryland)Connorville4456 (DAP)5144(irrigated)West6790 (DAP)87—Moorville Plant material nutrient analysis was conducted, as shown in Table 3 below. Key elements required by, or beneficial to, the pasture for growth (such as nitrogen, phosphorous, potassium, calcium, copper, zinc, boron, molybdenum) were present in plant material from the IMP Bio treated plots at levels equivalent to or higher than those plots treated with the comparator conventional inorganic fertilizer, despite these nutrients not being added in the IMP Bio fertilizer. TABLE 3ConventionalIMP BioNutrientControlfertilizer(30 L/ha)Connorville (irrigated)Nitrogen (%)1.952.231.94Phosphorus (%)0.280.380.26Potassium (%)2.612.692.53Sulphur (%)0.260.270.24Carbon (%)43.543.743.8Calcium (%)0.330.300.41Magnesium (%)0.280.250.28Sodium (%)0.240.450.30Copper (ppm)4.24.55.3Zinc (ppm)192124Manganese (ppm)372339309Iron (ppm)11390109Boron (ppm)4.94.76.0Molybdenum (ppm)0.70.70.7Cobalt (ppm)0.20.10.2Silicon (ppm)201169193Nitrogen:Sulphur ratio7.48.48.1Nitrogen:Phopshorus ratio7.05.97.4Nitrogen:Potassium ratio0.70.80.8Carbon:Nitrogen ratio22.319.622.6Crude protein (% N × 6.25)12.213.912.1West MoorvilleNitrogen (%)1.561.571.64Phosphorus (%)0.340.330.31Potassium (%)2.262.432.11Sulphur (%)0.250.240.24Carbon (%)44.044.143.9Calcium (%)0.780.590.57Magnesium (%)0.240.200.18Sodium (%)0.180.140.15Copper (ppm)4.84.34.7Zinc (ppm)181819Manganese (ppm)373335Iron (ppm)172114120Boron (ppm)107.78.3Molybdenum (ppm)1.31.01.1Cobalt (ppm)0.1<0.1<0.1Silicon (ppm)316268244Nitrogen:Sulphur ratio6.26.57.0Nitrogen:Phopshorus ratio4.54.75.3Nitrogen:Potassium ratio0.70.60.8Carbon:Nitrogen ratio28.228.126.8Crude protein (% N × 6.25)9.89.810.2CupronaNitrogen (%)3.683.603.68Phosphorus (%)0.390.380.39Potassium (%)3.433.432.90Sulphur (%)0.380.410.41Carbon (%)43.644.243.6Calcium (%)0.510.490.58Magnesium (%)0.240.270.26Sodium (%)0.260.360.44Copper (ppm)8.79.18.4Zinc (ppm)242522Manganese (ppm)10611874Iron (ppm)104110103Boron (ppm)6.24.24.4Molybdenum (ppm)0.30.30.9Cobalt (ppm)<0.1<0.1<0.1Silicon (ppm)267284214Nitrogen:Sulphur ratio9.88.89.1Nitrogen:Phopshorus ratio9.59.59.3Nitrogen:Potassium ratio1.11.11.3Carbon:Nitrogen ratio11.812.311.9Crude protein (% N × 6.25)23.022.523.0 Example 3—Soil Quality To determine the effect of a biofertilizer as disclosed herein on soil quality, 2×150 g of soil from a farm in Tasmania were each weighed into 2× clean 150 ml Schott bottle. 10 mls of a 1:10 dilution of IMP Bio fertilizer (see Examples 1 and 2) was dripped over the top of the soil in one bottle and the lid replaced and incubated at 34° C. for one week. The second bottle had no biofertilizer added was incubated 34° C. The soil from both bottles was analysed by Environmental Analytical Laboratories (EAL, Southern Cross University Lismore, NSW) using standard soil testing methods. The results for the one week treatment of soil with IMP Bio are summarised in Table 4. Soil tests on the untreated incubated sample are not shown as these were substantially the same as the initial untreated soil test. It is clear from the soil tests on the two treated samples that there is a marked difference in the soil after incubation with IMP Bio. The second sample analysed, shows a general trend of increasing the levels of available cations (calcium, magnesium, potassium, sodium and all trace elements—zinc, manganese, iron and copper) and ammonium nitrogen, while the total levels under the acid extractions were slightly lower across all nutrients. Organic matter increased by 1% (14.6% to 15.5%) between the samples dates. The overall decrease in total nutrients does not appear to be significant. There was a greater than three-fold increase in ammonium nitrogen, although no increase in nitrates. This indicates an increase in mineralisation of nitrogen from the organic nitrogen pool, and may be linked to the transformation of organic material, the level of which in this soil is particularly high. This could also indicate nitrogen fixation. TABLE 4Prior to IMP BioAfter IMP BioNutrient/soil characteristictreatmenttreatmentCalcium (mg/kg)10061431Magnesium (mg/kg)181279Potassium (mg/kg)218317Phosphorus (mg/kg)2.23.3Nitrate nitrogen (mg/kg)13.314.2Ammonium nitrogen (mg/kg)21.272.6Sulfur (mg/kg)28.533.8Zinc (mg/kg)3.03.6Manganese (mg/kg)1948Iron (mg/kg)335369Copper (mg/kg)3.43.5Boron (mg/kg)0.820.98Silicon (mg/kg)2428Total carbon (%)8.338.85Total nitrogen (%)0.520.53Carbon:Nitrogen ratio16.116.6Organic matter (%)14.615.5pH6.416.36Conductivity (dS/m)0.1320.202 Example 4—Potato Trials A field trial was conducted in which Bondi variety potatoes were treated with the IMP Bio biofertilizer (see Example 2) at planting. The trial was conducted at Waterhouse, Tasmania. IMP Bio was applied in furrows to rows 30 m long at a rate of 50 L/ha, either alone, or together with the conventional chemical fertilizer 5-10-16 at either 650 kg/ha (delivering 32 kg/ha nitrogen, 63 kg/ha phosphorus and 100 kg/ha potassium) or 1250 kg/ha (delivering 63 kg/ha nitrogen, 125 kg/ha phosphorus and 200 kg/ha potassium). In a fourth replicate, 5-10-16 was applied at 1250 kg/ha together with the fungicide Amistar. Four plots of 4 m length were dug from each treatment and tubers assessed for size and yield. The results are shown in Table 5. TABLE 5Potato yieldTotal yieldYieldYield>45 gSeed>350 g<45 gStems/Treatment(t/ha)(t/ha)(t/ha)(t/ha)plantIMP Bio42.438.14.32.93.7IMP Bio + 5-10-39.235.43.81.73.316 (650 kg/ha)IMP Bio + 5-10-35.630.05.61.63.316 (1250 kg/ha)5-10-16 + Amistar39.333.45.91.83.2 There was an increase in stem numbers per plant in the IMP Bio treatment, which is desirable (higher stem numbers typically correlating with higher tuber numbers). The reduction in large (>350 g) tubers observed with IMP Bio treatment is also significant as larger tubers have lower commercial value than seed sized tubers (45-350 g). Additionally, the 14% increase (5 tonnes/ha) in seed weight in the IMP Bio compared to the 5-10-16+Amistar treatment is also of significant economic value. The IMP Bio treated potato plants were also observed to be approximately three weeks more developed (in terms of maturity) than those treated with 5-10-16. Example 5—Tick Bean Trials A greenhouse experiment was conducted to establish the effect of IMP Bio biofertilizer (see Example 2) on tick bean plant growth, compared to the commercial fertilizer Baileys TriStar (8.3% N, 0% P, 16% K, 14% S, 1% Fe, 2% Mg). The treatment groups and regimes employed for seedlings post-germination were as follows: Control: 300 μl water “T40”: 300 μl TriStar at 40 L/ha “SGL40”: 300 μl IMP Bio at 40 L/ha “T25% GL40”: 300 μl TriStar 25% plus IMP Bio at 40 L/ha “GL40”: 300 μl IMP Bio at 40 L/ha Seeds in the T40, SGL40 and T25% GL40 groups were soaked for 1 hour in 100 ml of a 1:10 dilution of IMP Bio solution prior to planting. Control and GL40 seeds remained dry prior to planting. Three replicates of each treatment group (and two replicates of the control group) were used. Seeds were planted 5 mm deep in the middle of each pot and the pots placed in a temperature-controlled greenhouse at 16-18° C. under hydroponic lights. After germination, all seedlings were treated every two weeks (for a total of four weeks) using the treatments described above. Seedlings were watered once a day. At the conclusion of the experiment it was observed that the tallest plants, and the plants with the strongest main stem were those of the T25% GL40 treatment group. Overall, the best growth was observed in the T25% GL40 and SGL40 groups (data not shown). However the most noticeable differences observed were in root development (seeFIG.1). Roots of the control plants were the least dense and the shortest (FIG.1A). Roots of the T40 plants had good root density and length (FIG.1B), however development was not as extensive as in the plants treated with IMP Bio. In the SGL40 plants the root system shown good density and length (FIG.1C). Root nodules were present as were black nodule-like growths. In the T25% GL40 plants the root system was more dense and longer than in other treatment groups (FIG.1D). Root nodules were present but black nodule-like growth was not seen. In the GL40 plants the root system was similarly dense, long and well developed (FIG.1E). Root nodules were present as were black nodule-like growths. Example 6—Tomato Trials A greenhouse experiment was conducted to investigate the effect of IMP Bio biofertilizer (see Example 2) on the growth rate of tomato plants over a 20 day period. Tomato seedlings were provided by Cedenco. Water only was used as a control, and the commercial fertilizer FlowPhos (Yara Nipro) used as a comparator. Seedlings were potted into 50 mm pots in one of three different soils obtained from different locations (Cedenco) and drenched once with either: (i) 10 ml water; (ii) 10 ml of IMP Bio (100 ml in 900 ml water); (iii) 10 ml of FlowPhos (7.5 ml in 900 ml water); or (iv) 10 ml of FlowPhos plus IMP Bio (7.5 ml FlowPhos and 100 ml IMP Bio made to a total volume of 1000 ml with water). Three replicates of the control (water) group and eight replicates of each of the treatment groups. Plants were watered twice a day with 30 ml water. Plant height was measured every third day over the 20 day period of the experiment. The average rate of change of growth (height) of tomato seedlings over the 20 day period for all treatment groups, in each of the three soils, is shown inFIG.2. As can be seen, the IMP Bio treated plants were the only plants that consistently showed increases in growth over the course of the experiment, resulting in taller plants.FIG.3shows an exemplary comparison of difference in plant height, foliage and root system development in control plants, FlowPhos treated plants and IMP Bio (GreatLand) treated plants, in which the advantages of IMP Bio treatment are clearly evident. A field trial was then conducted at Timmering, Victoria in which tomato plants were treated with IMP Bio by foliar application during flowering, either at a rate of 80 L/ha or 40 L/ha during early flowering followed by 40 L/ha during mid flowering. Yield of tomato fruit was determined and compared to the yield from the same number of untreated plants. For the plants that received 80 L/ha IMP Bio, total fruit yield was 149.87 tonnes/ha, compared to 128.87 tonnes/ha for the untreated plants. For the plants that received two applications of 40 L/ha IMP Bio, total fruit yield was 130.15 tonnes/ha, compared to 103.05 tonnes/ha for the untreated plants. Example 7—Macadamia Trials A field trial was conducted in which macadamia trees in a 100 ha farm in Lismore, NSW were treated with the IMP Bio biofertilizer (see Example 2) by spraying at the rate of 40 L/ha, every 2-3 months for a period of 12 months. IMP Bio was applied in conjunction with chemical fertilizer (Easy N Fertilizer), the same fertilizer used for at least the previous four years. The yield of macadamia nuts following the 12 month treatment was approximately 70 tonnes, compared to an average yield of 35 tonnes per year over the previous four years. The benefits offered by the IMP Bio biofertilizer allowed for a significant reduction in the application of chemical fertilizer. Leaf and soil analysis was also conducted at four sites across the farm after 45 days of IMP Bio use. Significant increases were observed in levels of zinc, manganese, iron and boron in macadamia leaves, and in ammonium nitrogen, nitrate nitrogen, phosphorus, potassium, calcium, copper and boron in the soil. Example 8—Strawberry Trials A field trial was conducted in Beerwah, Qld to establish the effect of IMP Bio biofertilizer (see Example 2) on strawberry plant growth and fruit yield over an 8 ha plot. The IMP Bio was applied at a rate of 40 L/ha to the soil pre-planting, again at the same rate at planting, and weekly during the vegetative growth and flowering stage (weeks 2-4), during the fruiting stage (weeks 5-8) and during the picking stage (weeks 9-16). In comparison to conventional fertilizer (NitroPhoska (blue) applied preplanting at 1000 kg/ha), plant growth rate was significantly increased and plants showed increased vegetative growth and leaf area (FIG.4). Fruit yield was also significantly increased (38,000 kg as compared to 20,000 kg). Example 9—Other Trials Preliminary trials have also been conducted on sugar cane, lettuce, raspberries, roses, wheat, basil and turf grass (golf course green). In each case IMP Bio biofertilizer (see Example 2) was observed to result in increased rate of growth of plants compared to untreated plants (data not shown). | 42,648 |
11858870 | DETAILED DESCRIPTION The present invention may be embodied in different forms, and two examples of anaerobic digester systems constructed in accordance with, and embodying, the principles of the present invention will be described below. First Example Anaerobic Digester System Referring initially toFIG.1of the drawing, depicted therein is a first example anaerobic digester system20.FIG.1further illustrates that that biogas is removed from the digester system through a biogas conduit22. The first example anaerobic digester system20may be used with a separator (not shown) for separating separator feed material into dry solids and liquids, and the liquids may be directed to a long term storage lagoon or the like (not shown). As shown inFIG.1, the first example anaerobic digester system20comprises a primary digester tank30and a secondary or buffer digester tank32. A primary feed material portion34abeing processed by the example digester system20is within the primary digester tank30as shown inFIG.1. The primary feed material portion34awithin the primary digester tank30defines a primary feed material level36a.FIG.1also illustrates that a secondary feed material portion34bis within the secondary digester tank32, and the secondary feed material portion34bwithin the secondary digester tank32defines a secondary feed material level36b. A first conduit40connects the primary digester tank30to the secondary digester tank32. In particular, the first conduit40is configured to define a digester tank lower opening50and a secondary tank lower opening52. The first conduit40is arranged such that the primary tank lower opening50and secondary tank lower opening52are within the primary and secondary digester tanks30and32below the primary feed material level36aand secondary feed material level36b, respectively. The biogas conduit22defines a biogas opening58through which biogas passes from the primary digester tank30into the biogas conduit22, and the biogas opening58is also above the primary feed material level36a. Further, for reasons that will be explained in further detail below, the primary tank lower opening50is arranged at or near a bottom of the interior of the primary tank30. FIG.1further illustrates that a flow control valve60is arranged to control flow of fluid through the first conduit40. The flow control valve60operates in a closed configuration and at least one open configuration. Typically, the flow control valve60may operate in a continuum of open configurations between the closed configuration and a fully open configuration. In the closed configuration, the flow control valve60prevents flow of fluid through the first conduit40. In any open configuration, the flow control valve60allows fluid flow between the primary digester tank30and the secondary digester tank32through the first conduit40. The first example anaerobic digester system20operates generally as follows. The primary feed material34ais introduced into the primary digester tank30. The primary digester tank30is operated in a conventional manner to generate biogas and digestate. The biogas is removed from the primary digester tank30through the biogas opening58and the biogas conduit22. The primary digester tank30is sized and dimensioned relative to the secondary digester tank32such that the head pressure within the primary digester tank30is much greater than the head pressure within the secondary digester tank32. Periodically, a portion of the primary feed material34acomprising the digestate, liquid material, and solid contaminate (such as sand) is allowed to flow at a first, relatively high, flow rate from the primary digester tank30into the secondary digester tank32. In particular, a portion of the primary feed material34aflows through the first conduit40and the flow control valve60and into the secondary digester tank32to form the secondary feed material34b. The first conduit40and flow control valve60are sized, dimensioned, and/or controlled such that the head pressure within the primary digester tank30forces a portion of the secondary feed material34afrom the primary digester tank30to the secondary digester tank32at the first flow rate (e.g., 6000 gpm) for a short flush time period. The flush time duration depends on factors such as the relative sizes of the primary digester tank30and secondary digester tank32, the size of the first conduit40, and the nature of the feed material. The flush time duration should be sufficient to flush feed material having a relatively high concentration of solid contaminate from the primary digester tank30. However, the flush time duration should be kept short enough such that primarily feed material with a relatively high concentration of solid contaminate is removed from the primary digester tank30. The valve60is configured to be fully open for a flush time duration within a first range of approximately 10-15 seconds or a second range of approximately 5-20 seconds. Because they type of valve use as the example valve60(e.g., butterfly valve) may take from 3-5 seconds to open, the total time from initiation of the flush process to cessation of the flush process may be in a first range of 16-25 seconds or a second range of 11-30 seconds. The location of the primary tank lower opening50is arranged and the first flow rate selected such that the solid contaminate that has accumulated at the bottom of the primary digester tank30is flushed out of the primary digester tank30along with some digestate and liquid material. Accordingly, the secondary feed material34bwithin the secondary digester tank32typically contains a much higher percentage of solid contaminate than the primary feed material34awithin the primary digester tank30. The anaerobic digestion process continues to act on the secondary feed material34bin the secondary digester tank32. At the same time, the secondary feed material34bmay be periodically or continuously removed from the secondary digester tank32at a second, relatively low, flow rate (e.g., 50 gpm). The removed secondary feed material34bmay be further separated into dry solids and liquids. Any digestate in the removed secondary feed material34bforms at least a part of the dry solids and may be removed from contaminate and used or otherwise safely disposed of. Solid contaminate, especially non-digestible, relatively dense solids such as sand, will thus be carried by the intense, short duration flow of feed material from the primary digester tank30to the secondary digester tank32. In particular, non-digestible solids that are more dense than the liquids (primarily water) forming the primary feed material34awill sink to the bottom of the primary digester tank30such that such solid contaminates, and especially non-digestible, relatively dense solid contaminates such as sand, are relatively highly concentrated within the bottom of the primary digester tank30. The primary feed material34aflushed from the primary digester tank30and into the secondary digester tank32through the first conduit40and the flow control valve60will thus contain a higher concentration of solid contaminates than the primary feed material34athat remains within the primary digester tank30. Accordingly, by periodically removing a relatively small amount of primary feed material34awith a high concentration of solid contaminate, especially non-digestible, relatively dense solids such as sand, from the primary digester tank30, the primary digester tank30is continually cleaned and thus allowed to operate at a relatively high level of efficiency in comparison to a digester system not having a secondary digester tank32. The following discussion defines certain characteristics of the first example anaerobic digester system20. In particular, Table A defines characteristics defining the first flow rate and the relationship of the first flow rate to the second flow rate. The text following Table A generally describes the relationship between the respective volumes of the first and second digester tanks30and32, the typical size and dimensions of the second digester tank32, the cross-sectional area of the first conduit40, and the frequency and length of the flush time duration. TABLE AFirst PreferredSecond PreferredCharacteristicExampleRangeRangeFirst Flow Rate6000 gpm5000-7000 gpm2000-20000 gpmSecond Flow Rate50 gpm25-100 gpm10-1000 gpmRatio of First to120:150-280:12-2000:1Second Flow RateSecondary Conduit4″3-5″2-10″Diameter The volume of the primary digester tank30can vary significantly depending upon the requirements of a particular installation, with the volume of the primary digester tank30potentially being as large as a million (1,000,000) gallons. The volume of the secondary digester tank32need not scale linearly with the volume of the primary digester tank30. As the volume of the primary digester tank30is scaled up, the frequency and possibly flush time duration, rather than the size of the secondary digester tank, may be increased to handle larger volume primary digester tanks. Typically, the diameter of the secondary digester tank32will be in the range of from four to eight feet (4-8′). The height of the secondary digester tank32is, at a minimum, sufficient to provide sufficient volume within the secondary tank32to handle the short burst of feed material flushed from the primary digester tank30. In addition, the height of the secondary digester tank32is typically selected to be approximately at least as tall as the height of the primary digester tank30such that failure of the valve60will simply fill up, but not overflow, the secondary digester tank32. II. Second Example Anaerobic Digester System Referring now toFIG.2of the drawing, depicted therein is a second example anaerobic digester system120. Biogas is removed from the second example digester system120through a biogas conduit122. The second example anaerobic digester system120configured to be used with a separator124for separating separator feed material into dry solids and liquids. Liquids may be directed to a long term storage lagoon126or the like.FIG.2further illustrates that the second example anaerobic digester system120is also operatively connected to a feed pump128that feeds raw feed material into the digester system120. The separator124, long term storage lagoon126, and feed pump128are or may be conventional and are described herein only to the extent necessary for a complete understanding of the present invention. As shown inFIG.2, the second example anaerobic digester system120comprises a primary digester tank130and a secondary or buffer digester tank132. A primary feed material portion134abeing processed by the example digester system120is within the primary digester tank130as shown inFIG.2. The primary feed material portion134awithin the primary digester tank130defines a primary feed material level136a.FIG.2also illustrates that a secondary feed material portion134bis within the secondary digester tank132, and the secondary feed material portion134bwithin the secondary digester tank132defines a secondary feed material level136b. First and second conduits140and142connect the primary digester tank130to the secondary digester tank132. In particular, the first conduit140is configured to define a primary tank lower opening150and a secondary tank lower opening152. The second conduit142is configured to define a digester tank upper opening154and a secondary tank upper opening156. The first conduit140is arranged such that the primary tank lower opening150and secondary tank lower opening152are within the primary and secondary digester tanks130and132below the primary feed material level136aand secondary feed material level136b, respectively. The second conduit142is arranged such that the digester tank upper opening154and secondary tank upper opening156are within the primary and secondary digester tanks130and132above the primary feed material level136aand secondary feed material level136b, respectively. The biogas conduit122defines a biogas opening158through which biogas passes from the primary digester tank130into the biogas conduit122, and the biogas opening158is also above the primary feed material level136a. Further, for reasons that will be explained in further detail below, the primary tank lower opening150is arranged at or near a bottom of the interior of the primary digester tank130. FIG.2further illustrates that a flow control valve160is arranged to control flow of fluid through the first conduit140. The flow control valve160operates in a closed configuration and at least one open configuration. Typically, the flow control valve160may operate in a continuum of open configurations between the closed configuration and a fully open configuration. In the closed configuration, the flow control valve160prevents flow of fluid through the first conduit140. In any open configuration, the flow control valve160allows fluid flow between the primary digester tank130and the secondary digester tank132through the first conduit140. A pump170is configured to force fluid from the secondary digester tank132to the separator124. The second example anaerobic digester system120operates generally as follows. The feed pump128pumps the primary feed material134ainto the primary digester tank130. The primary digester tank130is operated in a conventional manner to generate biogas and digestate. The biogas is removed from the primary digester tank130through the biogas opening158and the biogas conduit122. The primary digester tank130is sized and dimensioned relative to the secondary digester tank132such that the head pressure within the primary digester tank130is much greater than the head pressure within the secondary digester tank132. Periodically, a portion of the primary feed material134acomprising the digestate, liquid material, and solid contaminate (such as sand) is allowed to flow at a first, relatively high, flow rate from the primary digester tank130into the secondary digester tank132. In particular, a portion of the primary feed material134aflows through the first conduit140and the flow control valve160and into the secondary digester tank132to form the secondary feed material134b. The first conduit140and flow control valve160are sized, dimensioned, and/or controlled such that the head pressure within the primary digester tank130forces a portion of the secondary feed material134afrom the primary digester tank130to the secondary digester tank132at the first flow rate (e.g., 6000 gpm) for a short period of flush time. The flush time duration depends on factors such as the relative sizes of the primary digester tank130and secondary digester tank132, the size of the first conduit140, and the nature of the feed material. The flush time duration should be sufficient to flush feed material having a relatively high concentration of solid contaminate from the primary digester tank130. However, the flush time duration should be kept short enough such that primarily feed material with a relatively high concentration of solid contaminate is removed from the primary digester tank130. The valve160is configured to be fully open for a flush time duration within a first range of approximately 10-15 seconds or a second range of approximately 5-20 seconds. Because they type of valve use as the example valve160(e.g., butterfly valve) may take from 3-5 seconds to open, the total time from initiation of the flush process to cessation of the flush process may be in a first range of 16-25 seconds or a second range of 11-30 seconds. The primary tank lower opening150is arranged and the first flow rate selected such that the solid contaminate that has accumulated at the bottom of the primary digester tank130is flushed out of the primary digester tank130along with some of the digestate and liquid material. Accordingly, the secondary feed material134bwithin the secondary digester tank132typically contains a much higher percentage of solid contaminate than the primary feed material134awithin the primary digester tank130. The anaerobic digestion process continues to act on the secondary feed material134bin the secondary digester tank132, and any biogas generated in the secondary digester tank132flows from the secondary digester tank132into the primary digester tank130through the second conduit142. At the same time, the secondary feed material134bmay be periodically or continuously pumped by the pump170out of the secondary digester tank132and into the separator124at a second, relatively low, flow rate (e.g., 50 gpm). The separator124separates the secondary feed material134binto dry solids and liquids. The digestate forms at least a part of the dry solids and may be removed from contaminate and used or otherwise safely disposed of. Solid contaminate, especially non-digestible, relatively dense solids such as sand, will thus be carried by the intense, short duration flow of feed material from the primary digester tank130to the secondary digester tank132. In particular, non-digestible solids that are more dense than the liquids (primarily water) forming the primary feed material134awill sink to the bottom of the primary digester tank130such that such solid contaminates, and especially non-digestible, relatively dense solid contaminates such as sand, are relatively highly concentrated within the bottom of the primary digester tank130. The primary feed material134aflushed from the primary digester tank130and into the secondary digester tank132through the first conduit140and the flow control valve160will thus contain a higher concentration of solid contaminates than the primary feed material134athat remains within the primary digester tank130. Accordingly, by periodically removing a relatively small amount of primary feed material134awith a high concentration of solid contaminate, especially non-digestible, relatively dense solids such as sand, from the primary digester tank130, the primary digester tank130is continually cleaned and thus allowed to operate at a relatively high level of efficiency in comparison to a digester system not having a secondary digester tank132. Characteristics of the second example anaerobic digester system120may be the same as those defined above with reference to the first example digester system20. III. Third Example Anaerobic Digester System Referring now toFIGS.3and4of the drawing, depicted therein is a third example anaerobic digester system220. Biogas is removed from the second example digester system220through a biogas conduit222. The third example anaerobic digester system220configured to be used with a separator224for separating separator feed material into dry solids and liquids. Liquids may be directed to a long term storage lagoon (not shown) or the like. The third example anaerobic digester system220may also be operatively connected to a feed pump (not shown) that feeds raw feed material into the digester system220. The separator224, long term storage lagoon, and feed pump are or may be conventional and are described herein only to the extent necessary for a complete understanding of the present invention. As shown inFIG.3, the third example anaerobic digester system220comprises a primary digester tank230and a secondary or buffer digester tank232. A primary feed material portion234abeing processed by the example digester system220is within the primary digester tank230as shown inFIG.3. The primary feed material portion234awithin the primary digester tank230defines a primary feed material level236a.FIG.3also illustrates that a secondary feed material portion234bis within the secondary digester tank232, and the secondary feed material portion234bwithin the secondary digester tank232defines a secondary feed material level236b. A primary feed material level sensor238is arranged within the primary digester tank230to determine a level of the primary feed material234awithin the primary digester tank230. First and second conduits240and242connect the primary digester tank230to the secondary digester tank232. The first conduit240is configured to define a primary tank lower opening250and a secondary tank lower opening252. The second conduit242is configured to define a digester tank upper opening254and a secondary tank upper opening256. The first conduit240is arranged such that the primary tank lower opening250and secondary tank lower opening252are within the primary and secondary digester tanks230and232below the primary feed material level236aand secondary feed material level236b, respectively. The second conduit240is arranged such that the digester tank upper opening254and secondary tank upper opening256are within the primary and secondary digester tanks230and232above the primary feed material level236aand secondary feed material level236b, respectively. The biogas conduit222defines a biogas opening258through which biogas passes from the primary digester tank230into the biogas conduit222, and the biogas opening258is also above the primary feed material level236a. Further, for reasons that will be explained in further detail below, the primary tank lower opening250is arranged at or near a bottom of the interior of the primary tank230. FIG.3further illustrates that a flow control valve260is arranged to control flow of fluid through the first conduit240. The flow control valve260operates in a closed configuration and at least one open configuration. Typically, the flow control valve260may operate in a continuum of open configurations between the closed configuration and a fully open configuration. In the closed configuration, the flow control valve260prevents flow of fluid through the first conduit240. In any open configuration, the flow control valve260allows fluid flow between the primary digester tank230and the secondary digester tank232through the first conduit240. A pump270is configured to force fluid from the secondary digester tank232to the separator224. FIGS.3and4illustrate that a bottom wall280of the example primary digester tank230defines a trough region282. In particular, the bottom wall280comprises inner and outer side walls284aand284band an intermediate wall286connecting the inner and outer side walls284aand284b. Optionally, a sump288may be arranged along at least a portion of the intermediate wall286to facilitate draining of the primary digester tank230. FIGS.3and4further illustrate that the example intermediate wall286defines a flat, annular shape and is substantially horizontal during normal operation of the third example anaerobic digester system220. The inner side wall284atakes the form of an inverted frustoconical shape, while the outer side wall284btakes the form a frustoconical shape of greater diameter than the shape defined by the inner side wall284a. Solid contaminate, and in particular relatively dense solid contaminate such as sand, that settles to the bottom of the primary digester tank230will be directed inwardly by the side walls284aand284band onto the intermediate wall286, thus further concentrating the solid contaminate at the bottom of the primary digester tank. FIG.3further illustrates that the example first conduit240defines a downwardly extending portion290that is configured such that the primary tank lower opening250is arranged immediately above and directed towards a portion of the intermediate wall286and is also arranged between portions of the inner and outer side walls284aand284b. The downwardly extending portion290of the example first conduit240is sized, dimensioned, and arranged to optimize the flow of primary feed material234awith a higher concentration of solid contaminates out of the primary digester tank230when the flow control valve260is in its open configuration. The third example anaerobic digester system220operates generally as follows. The feed pump continuously or periodically pumps the primary feed material234ainto the primary digester tank230. The primary digester tank230is operated in a conventional manner to generate biogas and digestate. The biogas is removed from the primary digester tank230through the biogas opening and the biogas conduit. When the primary feed material level sensor238determines that the primary feed material level236areaches a predetermined value, the flow control valve260is placed in an open configuration. The head pressure within the primary digester tank230is much greater than the head pressure within the secondary digester tank232. Accordingly, when the flow control valve260is open, a portion of the primary feed material234acomprising the digestate, liquid material, and solid contaminate (such as sand) flows at a first, relatively high, flow rate from the primary digester tank230into the secondary digester tank232. In particular, a portion of the primary feed material234aflows through the first conduit240and the flow control valve260and into the secondary digester tank232to form the secondary feed material234b. The first conduit240and flow control valve260are sized, dimensioned, and/or controlled such that the head pressure within the primary digester tank230forces a portion of the primary feed material234afrom the primary digester tank230to the secondary digester tank232at the first flow rate (e.g., 6000 gpm) for a short period of time. The location of the primary tank lower opening250is arranged and the first flow rate selected such that the solid contaminate that has accumulated at the bottom of the primary digester tank230is flushed out of the primary digester tank230along with the digestate and liquid material. Accordingly, the secondary feed material234bwithin the secondary digester tank232typically contains a much higher percentage of solid contaminate than the primary feed material234awithin the primary digester tank230. The anaerobic digestion process continues to act on the secondary feed material234bin the secondary digester tank232, and any biogas generated in the secondary digester tank232flows from the secondary digester tank232into the primary digester tank230through the second conduit242. At the same time, the secondary feed material234bmay be periodically or continuously pumped by the pump270out of the secondary digester tank232and into the separator222at a second, relatively low, flow rate (e.g., 50 gpm). The separator222separates the secondary feed material234binto dry solids and liquids. The digestate forms at least a part of the dry solids and may be removed from contaminate and used or otherwise safely disposed of. Solid contaminate, especially non-digestible, relatively dense solids such as sand, will thus be carried by the intense, short duration flow of feed material from the primary digester tank230to the secondary digester tank232. In particular, non-digestible solids that are more dense than the liquids (primarily water) forming the primary feed material234awill sink to the bottom of the primary digester tank230such that such solid contaminates, and especially non-digestible, relatively dense solid contaminates such as sand, are relatively highly concentrated within the bottom of the primary digester tank230. The primary feed material234aflushed from the primary digester tank230and into the secondary digester tank232through the first conduit240and the flow control valve260will thus contain a higher concentration of solid contaminates than the primary feed material234athat remains within the primary digester tank230. Accordingly, by periodically removing a small amount of primary feed material234awith a high concentration of solid contaminate, especially non-digestible, relatively dense solids such as sand, from the primary digester tank230, the primary digester tank230is continually cleaned and thus allowed to operate at a relatively high level of efficiency in comparison to a digester system not having a secondary digester tank232. Characteristics of the third example anaerobic digester system220may be the same as those defined above with reference to the first example digester system20. IV. Fourth Example Anaerobic Digester System Referring now toFIG.5of the drawing, depicted therein is a fourth example anaerobic digester system320. Biogas is removed from the fourth example digester system320through a biogas conduit322. The fourth example anaerobic digester system320configured to be used with a separator324for separating separator feed material into dry solids and liquids. Liquids may be directed to a long term storage lagoon326or the like.FIG.5further illustrates that the fourth example anaerobic digester system320is also operatively connected to a feed pump328that feeds raw feed material into the digester system320. The separator324, long term storage lagoon326, and feed pump328are or may be conventional and are described herein only to the extent necessary for a complete understanding of the present invention. As shown inFIG.5, the fourth example anaerobic digester system320comprises a primary digester tank330and a secondary or buffer digester tank332. A primary feed material portion334abeing processed by the example digester system320is within the primary digester tank330as shown inFIG.5. The primary feed material portion334awithin the primary digester tank330defines a primary feed material level336a.FIG.5also illustrates that a secondary feed material portion334bis within the secondary digester tank332, and the secondary feed material portion334bwithin the secondary digester tank332defines a secondary feed material level336b. First and second conduits340and342connect the primary digester tank330to the secondary digester tank332. In particular, the first conduit340is configured to define a primary tank lower opening350and a secondary tank lower opening352. The second conduit342is configured to define a digester tank upper opening354and a secondary tank upper opening356. The first conduit340is arranged such that the primary tank lower opening350and secondary tank lower opening352are within the primary and secondary digester tanks330and332below the primary feed material level336aand secondary feed material level336b, respectively. The second conduit342is arranged such that the digester tank upper opening354and secondary tank upper opening356are within the primary and secondary digester tanks330and332above the primary feed material level336aand secondary feed material level336b, respectively. The biogas conduit322defines a biogas opening358through which biogas passes from the primary digester tank330into the biogas conduit322, and the biogas opening358is also above the primary feed material level336a. Further, for reasons that will be explained in further detail below, the primary tank lower opening350is arranged at or near a bottom of the interior of the primary digester tank332. FIG.5further illustrates that a flow control valve360is arranged to control flow of fluid through the first conduit340. The flow control valve360operates in a closed configuration and at least one open configuration. Typically, the flow control valve360may operate in a continuum of open configurations between the closed configuration and a fully open configuration. In the closed configuration, the flow control valve360prevents flow of fluid through the first conduit340. In any open configuration, the flow control valve360allows fluid flow between the primary digester tank330and the secondary digester tank332through the first conduit340. A pump370is configured to force fluid from the secondary digester tank332to the separator324. A membrane380is arranged within the example primary digester tank330. The example membrane380separates the region of the primary digester tank330above the primary feed material level336ainto first and second regions382and384. Biogas created by the digestion process collects in the first region382, and the biogas opening358is in fluid communication with the first region382. The example membrane380is flexible and fluid tight. In the fourth example anaerobic digester system320, the digester tank upper opening354is also in fluid communication with the first region382. The fourth example anaerobic digester system320operates generally as follows. The feed pump328pumps the primary feed material334ainto the primary digester tank330. The primary digester tank330is operated in a conventional manner to generate biogas and digestate. Biogas will collect or accumulate within first region382and deform the example membrane380. The biogas is removed from the first region382of the primary digester tank330through the biogas opening358and the biogas conduit322. The primary digester tank330is sized and dimensioned relative to the secondary digester tank332such that the head pressure within the primary digester tank330is much greater than the head pressure within the secondary digester tank332. Periodically, a portion of the primary feed material334acomprising the digestate, liquid material, and solid contaminate (such as sand) is allowed to flow at a first, relatively high, flow rate from the primary digester tank330into the secondary digester tank332. In particular, a portion of the primary feed material334aflows through the first conduit340and the flow control valve360and into the secondary digester tank332to form the secondary feed material334b. The first conduit340and flow control valve360are sized, dimensioned, and/or controlled such that the head pressure within the primary digester tank330forces a portion of the secondary feed material334afrom the primary digester tank330to the secondary digester tank332at the first flow rate (e.g., 6000 gpm) for a short period of flush time. The flush time duration depends on factors such as the relative sizes of the primary digester tank330and secondary digester tank332, the size of the first conduit340, and the nature of the feed material. The flush time duration should be sufficient to flush feed material having a relatively high concentration of solid contaminate from the primary digester tank330. However, the flush time duration should be kept short enough such that primarily feed material with a relatively high concentration of solid contaminate is removed from the primary digester tank330. The valve360is configured to be fully open for a flush time duration within a first range of approximately 30-15 seconds or a second range of approximately 5-20 seconds. Because they type of valve use as the example valve360(e.g., butterfly valve) may take from 3-5 seconds to open, the total time from initiation of the flush process to cessation of the flush process may be in a first range of 36-25 seconds or a second range of 31-30 seconds. The primary tank lower opening350is arranged and the first flow rate selected such that the solid contaminate that has accumulated at the bottom of the primary digester tank330is flushed out of the primary digester tank330along with some of the digestate and liquid material. Accordingly, the secondary feed material334bwithin the secondary digester tank332typically contains a much higher percentage of solid contaminate than the primary feed material334awithin the primary digester tank330. The anaerobic digestion process continues to act on the secondary feed material334bin the secondary digester tank332, and any biogas generated in the secondary digester tank332flows from the secondary digester tank332into the primary digester tank330through the second conduit342. At the same time, the secondary feed material334bmay be periodically or continuously pumped by the pump370out of the secondary digester tank332and into the separator324at a second, relatively low, flow rate (e.g., 50 gpm). The separator324separates the secondary feed material334binto dry solids and liquids. The digestate forms at least a part of the dry solids and may be removed from contaminate and used or otherwise safely disposed of. Solid contaminate, especially non-digestible, relatively dense solids such as sand, will thus be carried by the intense, short duration flow of feed material from the primary digester tank330to the secondary digester tank332. In particular, non-digestible solids that are more dense than the liquids (primarily water) forming the primary feed material334awill sink to the bottom of the primary digester tank330such that such solid contaminates, and especially non-digestible, relatively dense solid contaminates such as sand, are relatively highly concentrated within the bottom of the primary digester tank330. The primary feed material334aflushed from the primary digester tank330and into the secondary digester tank332through the first conduit340and the flow control valve360will thus contain a higher concentration of solid contaminates than the primary feed material334athat remains within the primary digester tank330. Accordingly, by periodically removing a relatively small amount of primary feed material334awith a high concentration of solid contaminate, especially non-digestible, relatively dense solids such as sand, from the primary digester tank330, the primary digester tank330is continually cleaned and thus allowed to operate at a relatively high level of efficiency in comparison to a digester system not having a secondary digester tank332. Characteristics of the fourth example anaerobic digester system320may be the same as those defined above with reference to the first example digester system20. V. Fifth Example Anaerobic Digester System Referring now toFIGS.6and7of the drawing, depicted therein is a fifth example anaerobic digester system420. Biogas is removed from the second example digester system420through a biogas conduit422. The fifth example anaerobic digester system420configured to be used with a separator424for separating separator feed material into dry solids and liquids. Liquids may be directed to a long term storage lagoon (not shown) or the like. The fifth example anaerobic digester system420may also be operatively connected to a feed pump (not shown) that feeds raw feed material into the digester system420. The separator424, long term storage lagoon, and feed pump are or may be conventional and are described herein only to the extent necessary for a complete understanding of the present invention. As shown inFIG.6, the fifth example anaerobic digester system420comprises a primary digester tank430and a secondary or buffer digester tank432. A primary feed material portion434abeing processed by the example digester system420is within the primary digester tank430as shown inFIG.6. The primary feed material portion434awithin the primary digester tank430defines a primary feed material level436a.FIG.6also illustrates that a secondary feed material portion434bis within the secondary digester tank432, and the secondary feed material portion434bwithin the secondary digester tank432defines a secondary feed material level436b. A primary feed material level sensor438is arranged within the primary digester tank430to determine a level of the primary feed material434awithin the primary digester tank430. First and second conduits440and442connect the primary digester tank430to the secondary digester tank432. The first conduit440is configured to define a primary tank lower opening450and a secondary tank lower opening452. The second conduit442is configured to define a digester tank upper opening454and a secondary tank upper opening456. The first conduit440is arranged such that the primary tank lower opening450and secondary tank lower opening452are within the primary and secondary digester tanks430and432below the primary feed material level436aand secondary feed material level436b, respectively. The second conduit442is arranged such that the digester tank upper opening454and secondary tank upper opening456are within the primary and secondary digester tanks430and432above the primary feed material level436aand secondary feed material level436b, respectively. The biogas conduit422defines a biogas opening458through which biogas passes from the primary digester tank430into the biogas conduit422, and the biogas opening458is also above the primary feed material level436a. Further, for reasons that will be explained in further detail below, the primary tank lower opening450is arranged at or near a bottom of the interior of the primary tank430. FIG.6further illustrates that a flow control valve460is arranged to control flow of fluid through the first conduit440. The flow control valve460operates in a closed configuration and at least one open configuration. Typically, the flow control valve460may operate in a continuum of open configurations between the closed configuration and a fully open configuration. In the closed configuration, the flow control valve460prevents flow of fluid through the first conduit440. In any open configuration, the flow control valve460allows fluid flow between the primary digester tank430and the secondary digester tank432through the first conduit440. A pump470is configured to force fluid from the secondary digester tank432to the separator424. FIGS.6and7illustrate that a bottom wall480of the example primary digester tank430defines a trough region482. In particular, the bottom wall480comprises inner and outer side walls484aand484band an intermediate wall486connecting the inner and outer side walls484aand484b. Optionally, a sump488may be arranged along at least a portion of the intermediate wall486to facilitate draining of the primary digester tank430. FIGS.6and7further illustrate that the example intermediate wall486defines a flat, annular shape and is substantially horizontal during normal operation of the fifth example anaerobic digester system420. The inner side wall484atakes the form of an inverted frustoconical shape, while the outer side wall484btakes the form a frustoconical shape of greater diameter than the shape defined by the inner side wall484a. Solid contaminate, and in particular relatively dense solid contaminate such as sand, that settles to the bottom of the primary digester tank430will be directed inwardly by the side walls484aand484band onto the intermediate wall486, thus further concentrating the solid contaminate at the bottom of the primary digester tank. FIG.6further illustrates that the example first conduit440defines a downwardly extending portion490that is configured such that the primary tank lower opening450is arranged immediately above and directed towards a portion of the intermediate wall486and is also arranged between portions of the inner and outer side walls484aand484b. The downwardly extending portion490of the example first conduit440is sized, dimensioned, and arranged to optimize the flow of primary feed material434awith a higher concentration of solid contaminates out of the primary digester tank430when the flow control valve460is in its open configuration. A membrane492is arranged within the example primary digester tank430. The example membrane492separates the region of the primary digester tank430above the primary feed material level436ainto first and second regions494and496. Biogas created by the digestion process collects in the first region482, and the biogas opening458is in fluid communication with the first region482. The example membrane480is flexible and fluid tight. In the fourth example anaerobic digester system420, the digester tank upper opening454is also in fluid communication with the first region482. The fifth example anaerobic digester system420operates generally as follows. The feed pump continuously or periodically pumps the primary feed material434ainto the primary digester tank430. The primary digester tank430is operated in a conventional manner to generate biogas and digestate. Biogas will collect or accumulate within first region482and deform the example membrane492. The biogas is removed from the primary digester tank430through the biogas opening and the biogas conduit. When the primary feed material level sensor438determines that the primary feed material level436areaches a predetermined value, the flow control valve460is placed in an open configuration. The head pressure within the primary digester tank430is much greater than the head pressure within the secondary digester tank432. Accordingly, when the flow control valve460is open, a portion of the primary feed material434acomprising the digestate, liquid material, and solid contaminate (such as sand) flows at a first, relatively high, flow rate from the primary digester tank430into the secondary digester tank432. In particular, a portion of the primary feed material434aflows through the first conduit440and the flow control valve460and into the secondary digester tank432to form the secondary feed material434b. The first conduit440and flow control valve460are sized, dimensioned, and/or controlled such that the head pressure within the primary digester tank430forces a portion of the primary feed material434afrom the primary digester tank430to the secondary digester tank432at the first flow rate (e.g., 6000 gpm) for a short period of time. The location of the primary tank lower opening450is arranged and the first flow rate selected such that the solid contaminate that has accumulated at the bottom of the primary digester tank430is flushed out of the primary digester tank430along with the digestate and liquid material. Accordingly, the secondary feed material434bwithin the secondary digester tank432typically contains a much higher percentage of solid contaminate than the primary feed material434awithin the primary digester tank430. The anaerobic digestion process continues to act on the secondary feed material434bin the secondary digester tank432, and any biogas generated in the secondary digester tank432flows from the secondary digester tank432into the primary digester tank430through the second conduit442. At the same time, the secondary feed material434bmay be periodically or continuously pumped by the pump470out of the secondary digester tank432and into the separator424at a second, relatively low, flow rate (e.g., 50 gpm). The separator424separates the secondary feed material434binto dry solids and liquids. The digestate forms at least a part of the dry solids and may be removed from contaminate and used or otherwise safely disposed of. Solid contaminate, especially non-digestible, relatively dense solids such as sand, will thus be carried by the intense, short duration flow of feed material from the primary digester tank430to the secondary digester tank432. In particular, non-digestible solids that are more dense than the liquids (primarily water) forming the primary feed material434awill sink to the bottom of the primary digester tank430such that such solid contaminates, and especially non-digestible, relatively dense solid contaminates such as sand, are relatively highly concentrated within the bottom of the primary digester tank430. The primary feed material434aflushed from the primary digester tank430and into the secondary digester tank432through the first conduit440and the flow control valve460will thus contain a higher concentration of solid contaminates than the primary feed material434athat remains within the primary digester tank430. Accordingly, by periodically removing a small amount of primary feed material434awith a high concentration of solid contaminate, especially non-digestible, relatively dense solids such as sand, from the primary digester tank430, the primary digester tank430is continually cleaned and thus allowed to operate at a relatively high level of efficiency in comparison to a digester system not having a secondary digester tank432. Characteristics of the fifth example anaerobic digester system420may be the same as those defined above with reference to the first example digester system20. VI. Sixth Example Anaerobic Digester System Referring now toFIG.8of the drawing, depicted therein is a sixth example anaerobic digester system520. Biogas is removed from the sixth example digester system520through a biogas conduit522. The sixth example anaerobic digester system520configured to be used with a separator524for separating separator feed material into dry solids and liquids. Liquids may be directed to a long term storage lagoon526or the like.FIG.8further illustrates that the sixth example anaerobic digester system520is also operatively connected to a feed pump528that feeds raw feed material into the digester system520. The separator524, long term storage lagoon526, and feed pump528are or may be conventional and are described herein only to the extent necessary for a complete understanding of the present invention. As shown inFIG.8, the sixth example anaerobic digester system520comprises a primary digester tank530and a secondary or buffer digester tank532. A primary feed material portion534abeing processed by the example digester system520is within the primary digester tank530as shown inFIG.8. The primary feed material portion534awithin the primary digester tank530defines a primary feed material level536a.FIG.8also illustrates that a secondary feed material portion534bis within the secondary digester tank532, and the secondary feed material portion534bwithin the secondary digester tank532defines a secondary feed material level536b. A first conduit540connects the primary digester tank530to the secondary digester tank532. In particular, the first conduit540is configured to define a primary tank lower opening550and a secondary tank lower opening552. The first conduit540is arranged such that the primary tank lower opening550and secondary tank lower opening552are within the primary and secondary digester tanks530and532below the primary feed material level536aand secondary feed material level536b, respectively. The biogas conduit522defines a biogas opening558through which biogas passes from the primary digester tank530into the biogas conduit522, and the biogas opening558is also above the primary feed material level536a. Further, for reasons that will be explained in further detail below, the primary tank lower opening550is arranged at or near a bottom of the interior of the primary digester tank532. FIG.8further illustrates that a flow control valve560is arranged to control flow of fluid through the first conduit540. The flow control valve560operates in a closed configuration and at least one open configuration. Typically, the flow control valve560may operate in a continuum of open configurations between the closed configuration and a fully open configuration. In the closed configuration, the flow control valve560prevents flow of fluid through the first conduit540. In any open configuration, the flow control valve560allows fluid flow between the primary digester tank530and the secondary digester tank532through the first conduit540. A pump570is configured to force fluid from the secondary digester tank532to the separator524. A membrane580is arranged within the example primary digester tank530. The example membrane580separates the region of the primary digester tank530above the primary feed material level536ainto first and second regions582and584. Biogas created by the digestion process collects in the first region582, and the biogas opening558is in fluid communication with the first region582. The example membrane580is flexible and fluid tight. The sixth example anaerobic digester system520operates generally as follows. The feed pump528pumps the primary feed material534ainto the primary digester tank530. The primary digester tank530is operated in a conventional manner to generate biogas and digestate. Biogas will collect or accumulate within first region582and deform the example membrane580. The biogas is removed from the first region582of the primary digester tank530through the biogas opening558and the biogas conduit522. The primary digester tank530is sized and dimensioned relative to the secondary digester tank532such that the head pressure within the primary digester tank530is much greater than the head pressure within the secondary digester tank532. Periodically, a portion of the primary feed material534acomprising the digestate, liquid material, and solid contaminate (such as sand) is allowed to flow at a first, relatively high, flow rate from the primary digester tank530into the secondary digester tank532. In particular, a portion of the primary feed material534aflows through the first conduit540and the flow control valve560and into the secondary digester tank532to form the secondary feed material534b. The first conduit540and flow control valve560are sized, dimensioned, and/or controlled such that the head pressure within the primary digester tank530forces a portion of the secondary feed material534afrom the primary digester tank530to the secondary digester tank532at the first flow rate (e.g., 6000 gpm) for a short period of flush time. The flush time duration depends on factors such as the relative sizes of the primary digester tank530and secondary digester tank532, the size of the first conduit540, and the nature of the feed material. The flush time duration should be sufficient to flush feed material having a relatively high concentration of solid contaminate from the primary digester tank530. However, the flush time duration should be kept short enough such that primarily feed material with a relatively high concentration of solid contaminate is removed from the primary digester tank530. The valve560is configured to be fully open for a flush time duration within a first range of approximately 50-15 seconds or a second range of approximately 5-20 seconds. Because they type of valve use as the example valve560(e.g., butterfly valve) may take from 5-5 seconds to open, the total time from initiation of the flush process to cessation of the flush process may be in a first range of 56-25 seconds or a second range of 51-30 seconds. The primary tank lower opening550is arranged and the first flow rate selected such that the solid contaminate that has accumulated at the bottom of the primary digester tank530is flushed out of the primary digester tank530along with some of the digestate and liquid material. Accordingly, the secondary feed material534bwithin the secondary digester tank532typically contains a much higher percentage of solid contaminate than the primary feed material534awithin the primary digester tank530. The anaerobic digestion process continues to act on the secondary feed material534bin the secondary digester tank532. At the same time, the secondary feed material534bmay be periodically or continuously pumped by the pump570out of the secondary digester tank532and into the separator524at a second, relatively low, flow rate (e.g., 50 gpm). The separator524separates the secondary feed material534binto dry solids and liquids. The digestate forms at least a part of the dry solids and may be removed from contaminate and used or otherwise safely disposed of. Solid contaminate, especially non-digestible, relatively dense solids such as sand, will thus be carried by the intense, short duration flow of feed material from the primary digester tank530to the secondary digester tank532. In particular, non-digestible solids that are more dense than the liquids (primarily water) forming the primary feed material534awill sink to the bottom of the primary digester tank530such that such solid contaminates, and especially non-digestible, relatively dense solid contaminates such as sand, are relatively highly concentrated within the bottom of the primary digester tank530. The primary feed material534aflushed from the primary digester tank530and into the secondary digester tank532through the first conduit540and the flow control valve560will thus contain a higher concentration of solid contaminates than the primary feed material534athat remains within the primary digester tank530. Accordingly, by periodically removing a relatively small amount of primary feed material534awith a high concentration of solid contaminate, especially non-digestible, relatively dense solids such as sand, from the primary digester tank530, the primary digester tank530is continually cleaned and thus allowed to operate at a relatively high level of efficiency in comparison to a digester system not having a secondary digester tank532. Characteristics of the sixth example anaerobic digester system520may be the same as those defined above with reference to the first example digester system20. VII. Seventh Example Anaerobic Digester System Referring now toFIGS.9and10of the drawing, depicted therein is a seventh example anaerobic digester system620. Biogas is removed from the seventh example digester system620through a biogas conduit622. The seventh example anaerobic digester system620configured to be used with a separator624for separating separator feed material into dry solids and liquids. Liquids may be directed to a long term storage lagoon (not shown) or the like. The seventh example anaerobic digester system620may also be operatively connected to a feed pump (not shown) that feeds raw feed material into the digester system620. The separator624, long term storage lagoon, and feed pump are or may be conventional and are described herein only to the extent necessary for a complete understanding of the present invention. As shown inFIG.9, the seventh example anaerobic digester system620comprises a primary digester tank630and a secondary or buffer digester tank632. A primary feed material portion634abeing processed by the example digester system620is within the primary digester tank630as shown inFIG.9. The primary feed material portion634awithin the primary digester tank630defines a primary feed material level636a.FIG.9also illustrates that a secondary feed material portion634bis within the secondary digester tank632, and the secondary feed material portion634bwithin the secondary digester tank632defines a secondary feed material level636b. A primary feed material level sensor638is arranged within the primary digester tank630to determine a level of the primary feed material634awithin the primary digester tank630. A first conduit640connects the primary digester tank630to the secondary digester tank632. The first conduit640is configured to define a primary tank lower opening650and a secondary tank lower opening652. The first conduit640is arranged such that the primary tank lower opening650and secondary tank lower opening652are within the primary and secondary digester tanks630and632below the primary feed material level636aand secondary feed material level636b, respectively. The biogas conduit622defines a biogas opening658through which biogas passes from the primary digester tank630into the biogas conduit622, and the biogas opening658is also above the primary feed material level636a. Further, for reasons that will be explained in further detail below, the primary tank lower opening650is arranged at or near a bottom of the interior of the primary tank630. FIG.9further illustrates that a flow control valve660is arranged to control flow of fluid through the first conduit640. The flow control valve660operates in a closed configuration and at least one open configuration. Typically, the flow control valve660may operate in a continuum of open configurations between the closed configuration and a fully open configuration. In the closed configuration, the flow control valve660prevents flow of fluid through the first conduit640. In any open configuration, the flow control valve660allows fluid flow between the primary digester tank630and the secondary digester tank632through the first conduit640. A pump670is configured to force fluid from the secondary digester tank632to the separator624. FIGS.9and10illustrate that a bottom wall680of the example primary digester tank630defines a trough region682. In particular, the bottom wall680comprises inner and outer side walls684aand684band an intermediate wall686connecting the inner and outer side walls684aand684b. Optionally, a sump688may be arranged along at least a portion of the intermediate wall686to facilitate draining of the primary digester tank630. FIGS.9and10further illustrate that the example intermediate wall686defines a flat, annular shape and is substantially horizontal during normal operation of the seventh example anaerobic digester system620. The inner side wall684atakes the form of an inverted frustoconical shape, while the outer side wall684btakes the form a frustoconical shape of greater diameter than the shape defined by the inner side wall684a. Solid contaminate, and in particular relatively dense solid contaminate such as sand, that settles to the bottom of the primary digester tank630will be directed inwardly by the side walls684aand684band onto the intermediate wall686, thus further concentrating the solid contaminate at the bottom of the primary digester tank. FIG.9further illustrates that the example first conduit640defines a downwardly extending portion690that is configured such that the primary tank lower opening654is arranged immediately above and directed towards a portion of the intermediate wall686and is also arranged between portions of the inner and outer side walls684aand684b. The downwardly extending portion690of the example first conduit640is sized, dimensioned, and arranged to optimize the flow of primary feed material634awith a higher concentration of solid contaminates out of the primary digester tank630when the flow control valve660is in its open configuration. A membrane692is arranged within the example primary digester tank630. The example membrane692separates the region of the primary digester tank630above the primary feed material level636ainto first and second regions694and696. Biogas created by the digestion process collects in the first region694, and the biogas opening658is in fluid communication with the first region694. The example membrane680is flexible and fluid tight. The seventh example anaerobic digester system620operates generally as follows. The feed pump continuously or periodically pumps the primary feed material634ainto the primary digester tank630. The primary digester tank630is operated in a conventional manner to generate biogas and digestate. Biogas will collect or accumulate within first region694and deform the example membrane692. The biogas is removed from the primary digester tank630through the biogas opening and the biogas conduit. When the primary feed material level sensor638determines that the primary feed material level636areaches a predetermined value, the flow control valve660is placed in an open configuration. The head pressure within the primary digester tank630is much greater than the head pressure within the secondary digester tank632. Accordingly, when the flow control valve660is open, a portion of the primary feed material634acomprising the digestate, liquid material, and solid contaminate (such as sand) flows at a first, relatively high, flow rate from the primary digester tank630into the secondary digester tank632. In particular, a portion of the primary feed material634aflows through the first conduit640and the flow control valve660and into the secondary digester tank632to form the secondary feed material634b. The first conduit640and flow control valve660are sized, dimensioned, and/or controlled such that the head pressure within the primary digester tank630forces a portion of the primary feed material634afrom the primary digester tank630to the secondary digester tank632at the first flow rate (e.g., 6000 gpm) for a short period of time. The location of the primary tank lower opening650is arranged and the first flow rate selected such that the solid contaminate that has accumulated at the bottom of the primary digester tank630is flushed out of the primary digester tank630along with the digestate and liquid material. Accordingly, the secondary feed material634bwithin the secondary digester tank632typically contains a much higher percentage of solid contaminate than the primary feed material634awithin the primary digester tank630. The anaerobic digestion process continues to act on the secondary feed material634bin the secondary digester tank632. At the same time, the secondary feed material634bmay be periodically or continuously pumped by the pump670out of the secondary digester tank632and into the separator624at a second, relatively low, flow rate (e.g., 50 gpm). The separator624separates the secondary feed material634binto dry solids and liquids. The digestate forms at least a part of the dry solids and may be removed from contaminate and used or otherwise safely disposed of. Solid contaminate, especially non-digestible, relatively dense solids such as sand, will thus be carried by the intense, short duration flow of feed material from the primary digester tank630to the secondary digester tank632. In particular, non-digestible solids that are more dense than the liquids (primarily water) forming the primary feed material634awill sink to the bottom of the primary digester tank630such that such solid contaminates, and especially non-digestible, relatively dense solid contaminates such as sand, are relatively highly concentrated within the bottom of the primary digester tank630. The primary feed material634aflushed from the primary digester tank630and into the secondary digester tank632through the first conduit640and the flow control valve660will thus contain a higher concentration of solid contaminates than the primary feed material634athat remains within the primary digester tank630. Accordingly, by periodically removing a small amount of primary feed material634awith a high concentration of solid contaminate, especially non-digestible, relatively dense solids such as sand, from the primary digester tank630, the primary digester tank630is continually cleaned and thus allowed to operate at a relatively high level of efficiency in comparison to a digester system not having a secondary digester tank632. Characteristics of the seventh example anaerobic digester system620may be the same as those defined above with reference to the first example digester system20. | 66,000 |
11858871 | DETAILED DESCRIPTION As seen inFIGS.1and2there is according to one aspect of the invention a renewable methane production module10generally comprising:1. a water capture generator12designed for directly capturing water from atmosphere to provide water in a liquid form at14;2. an electrolyser16operatively coupled to the water capture generator12for electrolysis of the liquid water to produce hydrogen at18;3. a reactor20operatively coupled to the electrolyser16for reacting the hydrogen with carbon dioxide at22to produce renewable methane at24. In this embodiment the water capture generator12includes a pair of water capture panels26aand26beach including an absorbent material (not shown) designed to be exposed to atmosphere for directly absorbing water from the atmosphere on to the absorbent material. Each of the water capture panels26a/bof this embodiment also includes heating means (not shown) designed to absorb heat from a renewable energy source such as solar energy and transfer it to the absorbent material to release the absorbed water to provide water in a liquid form for the electrolyser16. In this example the absorbent material and solar heating means are together integrated within the water capture panels26a/b. In this embodiment the renewable methane production module10also comprises an electricity generating assembly (not designated) powered by a renewable energy source such as solar energy. The electricity generating assembly of this example includes a plurality of solar panels such as28a/28band30a/30boperatively coupled to an inverter32for production of electricity for powering the electrolyser16. In the absence of an inverter, the solar panels are directly coupled to the electrolyser16. The solar panels such as28a/band30a/bare in the form of solar photovoltaic (PV) panels arranged in an elongate bank of panels. In this case the solar PV panels are arranged in a first elongate bank of panels34in two rows such as30aand30brespectively on opposing faces of a first solar framework structure36. The solar PV panels are also located in a second elongate bank of panels38in two rows of panels such as28aand28brespectively on opposing faces of a second solar framework structure40. The first and second solar framework structures36and40are aligned with one another and oriented in a generally magnetic North to South direction. Each of the first and second solar framework structures36/40is in cross-section shaped in the form of an isosceles triangle having each of the two rows of PV panels such as30a/band28a/bmounted to respective of leg-sides such as42a/band44a/bof the first and second solar framework structures36and40respectively. It will be understood that this North to South orientation combined with the triangular solar framework structures36and40provides increased exposure of the solar PV panels30a/band28a/bto sunlight. In this embodiment the renewal methane production module10also comprises a carbon dioxide extractor50for extracting carbon dioxide from atmosphere. The carbon dioxide extractor50directly captures carbon dioxide from atmosphere using a metal-organic framework (MOF) or other absorbent structure (not shown). In this example the carbon dioxide extractor50is operatively coupled to a heat exchanger52to heat the absorbent structure of the carbon dioxide extractor50to release the absorbed carbon dioxide from the absorbent structure. The released carbon dioxide at22is fed to the reactor20to react with the hydrogen in producing the renewable methane at24. In this example the reactor20is an exothermic reactor which produces renewable methane in a Sabatier reaction. The exothermic Sabatier reactor20is operatively coupled to the heat exchanger52where steam at54from the Sabatier reactor20exchanges heat with the carbon dioxide extractor50to release the absorbed dioxide from the absorbent structure associated with the carbon dioxide extractor50. The steam on exchanging its heat at the heat exchanger52condenses to provide return liquid water at56to be circulated to the electrolyser16for the production of hydrogen. In this embodiment the renewable methane production module10comprises a water storage vessel58designed to store both the released water14from the water capture generator12, and the return liquid water56from the heat exchanger52. The water storage vessel58supplies the liquid water at60to the electrolyser16for the production of hydrogen. It is expected that the water capture generator12will supply liquid water to the storage vessel58predominantly during daylight hours when the absorbed water from the absorbent material of the water capture panels26a/bis released on solar heating. The supply of the return liquid water56to the storage vessel58will occur during production of renewable methane at the Sabatier reactor20whilst steam is being condensed at the heat exchanger52. In this embodiment the renewable methane production module10further comprises one or more hydrogen storage vessels62arranged to receive the hydrogen18produced from the electrolyser16. The hydrogen storage vessel62is intended to provide an extended supply of hydrogen to the Sabatier reactor20for continued operation without being limited to daylight hours during which water is predominantly released from the water capture generator12. That is, the hydrogen storage vessel62provides an effective buffer in storing hydrogen for supply to the Sabatier reactor20. This hydrogen storage capability is consistent with operation of the electrolyser16during predominantly daylight hours when powered by the solar PV panels such as28a/band30a/band the associated inverter32. In this configuration the renewable methane production module10includes an equipment platform70at which the electrolyser16, the Sabatier reactor20, the inverter32, the carbon dioxide extractor50, the heat exchanger52, the water storage vessel58and the hydrogen storage vessel62are located. The equipment platform70is in this embodiment located between the first and second solar framework structures36and40. The pair of water capture panels26a/bare mounted to a water capture framework structure72located adjacent the equipment platform70. In this example the water capture framework structure72is of substantially the same configuration as and aligned with the second solar framework structure40. It will be understood that this configuration provides the pair of water capture modules26a/bwith increased solar exposure in a similar manner to the solar PV panels such as28a/b. The carbon dioxide extractor50of this embodiment may be operatively coupled to one or more batteries (not shown) for extended operation without being limited to sunlight hours. In this configuration the inverter32is arranged to provide electricity for charging of the batteries. The electricity produced from the batteries may be used predominantly outside daylight hours for not only heating the MOF or other absorbent structure of the carbon dioxide extractor50for releasing carbon dioxide but also to power pumps and/or fans (not shown) associated with the carbon dioxide extractor50. The carbon dioxide extractor50is otherwise powered during daylight hours by the solar PV panels such as28a/band30a/bvia the associated inverter such as32. This means the carbon dioxide extractor can potentially operate 24/7 in producing carbon dioxide for supply to the Sabatier reactor20which likewise can operate around the clock. As seen inFIG.3there is according to another aspect of the invention a renewable methane production system100generally comprising:1. a water capture module120for directly capturing water from air to provide water in a liquid form;2. an electrolysis module140for electrolysis of the liquid water to produce hydrogen;3. an exothermic reactor160for reacting the hydrogen from the electrolysis module140with carbon dioxide to produce renewable methane. In this embodiment the water capture module120is in the form of a direct air capture module including a metal-organic framework (MOF) or other absorbent designed to capture or absorb water from the air. The MOF is the absorbent material within an absorbent unit of the water capture module120. The water capture module120also includes i) a heating unit (not shown) designed to heat the MOF to release the absorbed water, and ii) a condensing unit (not shown) designed to condense the water released from the MOF by cooling of the released water to provide the liquid water for the electrolysis module140. In this example the heating unit includes a) a solar heating unit130, and/or b) a heat recovery unit150associated with the exothermic reactor160for recovering waste heat from the associated exothermic reaction, in both cases the heating unit being arranged for heating of the MOF. In this embodiment the electrolysis module140includes an electricity generating module170powered by a renewable energy source, such as solar energy arranged to power an electricity generator (not shown) configured to provide electricity for powering the electrolysis module140for the production of hydrogen from the liquid water. It will be understood that the electrolysis module140may be powered by other renewable energy sources including but not limited to wind, wave, or tidal sources. The production system100of this embodiment also comprises a water recirculation module180arranged to recirculate liquid water produced from the exothermic reactor160to the electrolysis module140for the production of hydrogen. In this embodiment the production system100also comprises a carbon dioxide module200for extracting carbon dioxide from air. The carbon dioxide module is based on MOF technology with the absorbent material designed to absorb carbon200dioxide from the air. The carbon dioxide capture module200, in a similar manner to the water capture module120, heats the absorbent material such as the MOF via a solar heating unit190. Alternatively the carbon dioxide may be obtained from a biogas reactor. In either case the carbon dioxide combines with hydrogen in the exothermic reactor160for the production of renewable methane. In this example this reaction is a Sabatier reaction where, under the influence of a suitable catalyst, carbon dioxide reacts with hydrogen to produce renewable synthetic methane. In a further aspect of the invention, in the context of the renewable methane production system100, there is a method of producing renewable methane comprising the general steps of:1. directly capturing water from air at the water capture module120to provide water in a liquid form;2. producing hydrogen by electrolysis of liquid water at the electrolysis module140;4. reacting the hydrogen with carbon dioxide to produce renewable methane at the exothermic reactor160. As seen inFIG.4there is a hydrogen production system500of yet another aspect of the invention for producing hydrogen. In this embodiment the hydrogen produced is in the form of hydrogen fuel for fuel cell vehicles. It will be understood that the hydrogen produced from this aspect of the technology may have other uses including but not limited to fertiliser and ammonia production, production of chemicals including hydrochloric acid, pharmaceuticals, semiconductor manufacturing, petroleum refining, hydrogenation, reduction of metallic ores, welding, cryogenics, methanol production, and glass purification. The hydrogen fuel production system500of this embodiment generally comprises:1. a water capture module520for directly capture water from air to provide water in a liquid form;2. an electrolysis module540for electrolysis of the liquid water to produce hydrogen;3. a purifying module560for purifying the hydrogen from the electrolysis module540to provide hydrogen fuel. In this embodiment the water capture module520and the electrolysis module540are of substantially the same construction as the corresponding modules of the renewable methane production system100. The hydrogen fuel production system50departs insofar as it includes the purifying module560which in this embodiment includes a purifying filter (not shown) for filtering the hydrogen produced by the electrolysis module540. The purifying module560thus filters the hydrogen produced by the electrolysis module540to obtain hydrogen fuel at purity levels required for fuel cell vehicles. In another departure from the renewable methane production system100, the electrolysis module540relies primarily on the water capture module520for its supply of the liquid water. Now that a preferred embodiment of a renewable methane production module and other aspects of the invention have been described it will be apparent to those skilled in the art that it has the following advantages:1. the production module in production of renewable methane is powered solely by renewable energy sources and in particular solar energy;2. the renewable methane production module and the other production systems are efficient in harnessing waste heat from the Sabatier reactor to assist with direct capture of carbon dioxide from atmosphere;3. the production module exploits the production of steam or liquid water in the Sabatier reactor for return to the electrolyser in the production of hydrogen;4. the production module in its preferred orientation of solar panels more effectively harnesses solar energy increasing utilisation of the electrolyser for extended production of hydrogen;5. both production systems in the production of renewable methane and hydrogen are powered or derived from renewable energy sources and in particular solar energy. Those skilled in the art will appreciate that the invention as described herein is susceptible to variations and modifications other than those specifically described. For example, the specific number and configuration of the solar panels of the production module may vary from that described. The direct capture of water and/or carbon dioxide from atmosphere may be different to the MOF or other technologies of the preferred embodiment. For example, the direct capture of water from air may be effected by refrigeration using a reverse cycle air-conditioning system which is effective in releasing water from air in a liquid form. In this variation, the waste heat from the Sabatier reaction may be harnessed in refrigeration of the air to release the liquid water. In another example, evacuated tubes may be used as an alternative heat source for releasing carbon dioxide from the absorbent material of the carbon dioxide extractor. In the context of the production of renewable methane, the liquid water from the Sabatier reactor need not be recirculated to the electrolysis module. It is to be understood that references to solar panels extends to printed solar such as thin film PV. It is to be understood that any acknowledgement of prior art in this specification is not to be taken as an admission that this prior art forms part of the common general knowledge as at the priority date of the claims. All such variations and modifications are to be considered within the scope of the present invention the nature of which is to be determined from the foregoing description. | 15,160 |
11858872 | DETAILED DESCRIPTION OF THE INVENTION The following is a detailed description of the disclosure provided to aid those skilled in the art in practicing the present disclosure. Those of ordinary skill in the art may make modifications and variations in the embodiments described herein without departing from the spirit or scope of the present disclosure. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The terminology used in the description of the disclosure herein is for describing particular embodiments only and is not intended to be limiting of the disclosure. This application relates to methods and systems for producing jet range hydrocarbons from triglycerides sourced from natural sources. Jet range hydrocarbons may include paraffins, naphthenes, and aromatics with carbon numbers from 9 to 16 (C9-C16), and isomers thereof. The process described herein is versatile and may be suitable for producing jet range hydrocarbons from many different grades and sources of triglycerides. Further, the process described herein may be selective to jet range hydrocarbons which may result in increased yield as compared to hydrocracking or other processes for producing jet range hydrocarbons from triglycerides. The processes described herein may include several unit operations including hydrolysis of the triglycerides to produce fatty acids and olefin cross metathesis of the fatty acids to produce the jet range hydrocarbons. While the processes described herein may be suitable for use for a variety of triglycerides, the process may be particularly suited for triglycerides which produce fatty acids where the carbon chain is 18 carbons long with the double bond on the 9thcarbon, sometimes referred to as C 18:1. There are several potential advantages to the methods and systems disclosed herein, only some of which are alluded to in the present disclosure. As discussed above, current techniques for producing jet range hydrocarbons from triglycerides can be problematic due to the relatively high cost of materials and production of products which fall outside the acceptable carbon number range of jet fuel. The olefin cross metathesis described herein provides a scalable process with improved kinetics and selectivity to jet range hydrocarbons without the typical problems associated with low jet range hydrocarbon yield. Embodiments of the methods and systems described herein may include triglyceride as a starting material. Suitable triglycerides may include any triglyceride which includes at least one unsaturated fatty acid molecule with a carbon chain length of at least C18 to C32 and at least one unsaturated bond on at least the 9thcarbon or greater. Any symmetrical or unsymmetrical triglyceride which meets these constraints may be used in the present process. While in principle, any triglyceride with any degree of unsaturation may be utilized, each degree of unsaturation of the fatty acid will result in a separate hydrocarbon molecule in the olefin cross metathesis reaction thereby potentially reducing the yield to jet range hydrocarbons as hydrocarbons outside of the C9-C16 range may be produced. As such, at least a portion of the triglyceride should contain at least one fatty acid with a carbon number from C18-C32 and a single degree of saturation on the 9thcarbon. One example of a suitable triglyceride may include triolein which is a symmetrical triglyceride derived from glycerol and three units of oleic acid. The triglyceride may be from any source including natural sources such as a seed and/or plant oils. Some example sources may include, without limitation, soy oil, canola oil, camelina oil, olive oil, macadamia oil, sunflower oil, and combinations thereof. Examples of vegetable oils that can be used in accordance with this invention include, but are not limited to rapeseed (canola) oil, soybean oil, sunflower oil, palm oil, palm kernel oil, peanut oil, linseed oil, tall oil, corn oil, castor oil, jatropha oil, jojoba oil, olive oil, flaxseed oil, camelina oil, safflower oil, babassu oil, and rice bran oil. Algal sources for algae oils can include, but are not limited to, unicellular and multicellular algae. Examples of such algae can include a rhodophyte, chlorophyte, heterokontophyte, tribophyte, glaucophyte, chlorarachniophyte, euglenoid, haptophyte, cryptomonad, dinoflagellum, phytoplankton, and the like, and combinations thereof. In one embodiment, algae can be of the classes Chlorophyceae and/or Haptophyta. Specific species can include, but are not limited to,Neochloris oleoabundans, Scenedesmus dimorphus, Euglena gracilis, Phaeodactylum tricornutum, Pleurochrysis camerae, Prymnesium parvum, Tetraselmis chui, andChlamydomonas reinhardtii. Additional or alternate algal sources can include one or more microalgae of theAchnanthes, Amphiprora, Amphora, Ankistrodesmus, Asteromonas, Boekelovia, Borodinella, Botryococcus, Bracteococcus, Chaetoceros,Carteria, Chlamydomonas, Chlorococcum, Chlorogonium,Chlorella, Chroomonas, Chrysosphaera, Cricosphaera, Crypthecodinium, Cryptomonas,Cyclotella, Dunaliella, Ellipsoidon, Emiliania, Eremosphaera, Ernodesmius,Euglena, Franceia,Fragilaria, Gloeothamnion,Haematococcus, Halocafeteria, Hymenomonas,Isochrysis, Lepocinclis, Micractinium, Monoraphidium, Nannochloris,Nannochloropsis, Navicula, Neochloris, Nephrochloris, Nephroselmis,Nitzschia, Ochromonas,Oedogonium, Oocystis, Ostreococcus,Pavlova, Parachlorella, Pascheria,Phaeodactylum, Phagus, Platymonas,Pleurochrysis, Pleurococcus, Prototheca, Pseudochlorella, Pyramimonas, Pyrobotrys,Scenedesmus, Skeletonema, Spyrogyra, Stichococcus,Tetraselmis, Thalassiosira, Viridiella, andVolvoxspecies, and/or one or more cyanobacteria of theAgmenellum, Anabaena, Anabaenopsis, Anacystis, Aphanizomenon, Arthrospira, Asterocapsa,Borzia, Calothrix, Chamaesiphon, Chlorogloeopsis, Chroococcidiopsis,Chroococcus, Crinalium, Cyanobacterium, Cyanobium, Cyanocystis,Cyanospira, Cyanothece,Cylindrospermopsis, Cylindrospermum, Dactylococcopsis, Dermocarpella,Fischerella, Fremyella, Geitleria, Geitlerinema, Gloeobacter,Gloeocapsa, Gloeothece, Halospirulina, Iyengariella,Leptolyngbya, Limnothrix,Lyngbya, Microcoleus, Microcystis, Myxosarcina, Nodularia, Nostoc, Nostochopsis, Oscillatoria, Phormidium, Planktothrix, Pleurocapsa, Prochlorococcus, Prochloron, Prochlorothrix,Pseudanabaena, Rivularia, Schizothrix, Scytonema, Spirulina, Stanieria, Starria,Stigonema, Symploca, Synechococcus, Synechocystis, Tolypothrix, Trichodesmium, Tychonema, andXenococcusspecies. Alternatively, or in addition to seed and/or plant oils, the triglyceride may be sourced from an algae that is capable of producing triglycerides which include at least one unsaturated fatty acid molecule with a carbon chain length of at least C18 to C32 and at least one unsaturated bond on at least the 9thcarbon or greater. The algae strain may be selected for its tendency to produce the triglyceride described above or may be genetically engineered to produce triglycerides with the properties suitable for production of jet range hydrocarbons. A first step in the process can include converting the triglyceride to the corresponding fatty acids and glycerol by hydrolyzing the triglyceride, sometimes referred to as fat splitting. One suitable method may be the continuous Colgate-Emery process, where nearly complete (>95%) hydrolysis can be achieved by operating around 200-260° C. and pressures up to 50 barg. The reaction may be carried out counter-currently with fat addition at the bottom of the tower and water added at the top of the tower. Residence times of both phases may be on the order of 2-3 hours. The hydrolysis may be performed by contacting the triglyceride with steam at conditions which convert at least a portion of the triglyceride into the corresponding fatty acids and glycerol. The hydrolysis reaction may be carried out in a hydrolysis reactor such as a batch reactor whereby steam may be sparged into the batch reactor until the desired fraction of triglyceride has been converted. Alternatively, hydrolysis may be carried out continuously by counter-currently contacting the triglyceride with steam in a column-type reactor, for example, where the triglyceride is introduced into a top of the column-type reactor and steam is sparged into the bottom of the column-type reactor. The steam may ascend through the column reactor and contact the triglyceride thereby breaking the triglyceride into the corresponding fatty acids and glycerol. Glycerol may be stripped from the fatty acids by the steam and carried out of the column-type reactor as an overhead stream while the fatty acids formed may be drawn off as a bottoms stream. The steam used in the hydrolysis reaction may be at any temperature and pressure suitable to hydrolyze the triglyceride without substantially polymerizing the resultant fatty acids. For example, the steam may be at a temperature of about 200° C. to about 260° C. and at a pressure of up to about 50 barg. In some examples, the conversion of the triglyceride to fatty acid may be in the range of 10% to 99%, depending on the residence time of the hydrolysis reactor. Hydrolysis may be rate limited by kinetics such that a longer residence time may generally correspond to greater conversion of the triglyceride. In some embodiments, an additional catalyst may be utilized to increase reaction rate. After the hydrolysis step, the fatty acids and glycerol may be separated, for example by stripping the glycerol from the fatty acids using steam or adding water to the glycerol/fatty acid product thereby dissolving at least a portion of the glycerol in an aqueous phase which may then be removed by separating the aqueous phase from a fatty acid phase. Alternatively, the fatty acids and glycerol may be separated by distillation to produce a fatty acid steam with reduced glycerol content. Lower carbon number unsaturated fatty acids generated during the hydrolysis step may not be suitable for olefin cross metathesis as the resultant hydrocarbons may be outside the suitable carbon numbers for jet fuel. As discussed above, the lowest carbon number typically suitable for jet fuel is C9 and as such, any fatty acids with carbon numbers less than C18 may generate hydrocarbons outside jet fuel range when cross metathesized. Another step may be to fractionate the fatty acids generated in the hydrolysis before cross metathesis such that hydrocarbons generated are within the jet hydrocarbon range. The fatty acids may be fractionated by distillation, for example, to generate a bottoms stream with C18 and heavier fatty acids and an overheads stream with C17 and lighter fatty acids. The C18 and heavier stream may include C18s, such as stearic acid (C18:0), oleic acid (C18:1), and linoleic acid (C18:2), for example. In some embodiments, the C18 and heavier stream may further include heavier saturated fatty acids such as arachidic acid and behenic acid, and heavier unsaturated fatty acids such as arachidonic acid, for example. The C18s may be fractionated further to produce a C18:1 oleic acid stream and a stream containing C18:0 and C18:2, if present. In some examples, additional fractionation aids such as urea and/or methanol may be utilized during fractionation to further separate the fatty acids. Alternatively, or in addition for fractionation, the fatty acids may be further purified by crystallization techniques such as extractive crystallization to separate saturated fatty acids from unsaturated fatty acids. A second step in the process can involve reacting the C18:1 fatty acid produced from hydrolysis with ethylene in an olefin cross metathesis reactor to produce 1-decene and 9-decenoic acid. The olefin cross metathesis reactor may include a Grubbs catalyst such as a first-generation Grubbs catalyst, second generation Grubbs catalyst, third generation Grubbs catalyst, or combinations thereof. The C18:1 fatty acid and ethylene may be introduced into the reactor and contacted with the Grubbs catalyst, thereby reacting at least a portion of the C18:1 fatty acid to produce the 1-decene and 9-decanoic acid. In some embodiments, the metathesis reactor may be operated at a temperature in a range of 40° C. to about 120° C. Alternatively, the cross metathesis reactor may be operated at a temperature in a range of about 30° C. to about 45° C., about 45° C. to about 50° C., about 50° C. to about 75° C., about 75° C. to about 90° C., or any ranges therebetween. In some embodiments, the cross metathesis reactor may be operated at a pressure of about 10-50 barg partial pressure of ethylene. In some examples, ethylene may be provided in a stoichiometric ratio with C18:1 or may be provided in excess of stoichiometric by about 5% to about 50%. Alternatively, the ethylene may be provided in an amount of about 5% to about 20% excess, about 20% to about 35% excess, or about 35% to about 50% excess. Without being limited by theory, the extent of reaction of the cross-metathesis reaction of ethylene with C18:1 fatty acid may be limited by kinetics. As such, the longer the reaction is allowed to proceed, the greater the extent of reaction may tend to be. Conversion of 90% or greater by weight of the C18:1 fatty acid may be realized by relatively longer reactor residence time. For example, residence times may be between about 1 hour to about 6 hours when utilizing a Grubbs catalyst. In some embodiments, the ethylene used in the metathesis reaction may be provided by the dehydration of ethanol. For example, ethanol may be dehydrated by concentrated sulfuric acid, concentrated phosphoric acid, or any other suitable acid dehydration agent such as alumina solid catalyst in a fixed bed reactor. One advantage of utilizing ethanol for production of ethylene may be that ethanol may be produced from naturally occurring sources such as crops grown on-purpose for ethanol production. Thus, ethylene derived from natural sources in conjunction with olefin cross metathesis of fatty acids derived from triglycerides ensures that all carbon in the jet grade hydrocarbons is derived from natural sources. Alternatively, the ethylene may be provided from on-purpose ethylene production from steam cracking, oxidative coupling of methane, catalytic dehydrogenation such as by passing ethane over a dehydration catalyst, such as ZSM-5, or any other method to produce ethylene. While the 1-decene and 9-decanoic acid produced in the cross metathesis reactor may be suitable for inclusion in jet fuel blends, the 1-decene and 9-decanoic acid may be readily upgraded by hydrogenation to improve the properties for blending in jet fuel. Hydrotreating units may utilize hydrotreating catalysts such as sulfides of Co and Mo or Ni and Mo on a support to catalyze the addition of hydrogen to a feed material. Additionally, platinum or palladium without sulfur may be utilized for deoxygenation and olefin saturation. Hydrotreating catalysts may be affected by the presence of oxygen in the 9-decanoic acid thereby reducing the activity of the hydrotreating catalyst. It may be advantageous to utilize a standalone hydrotreating unit, separate from other hydrotreating units in a chemical plant and/or refinery, for upgrading the stream from the cross-metathesis reactor such that the acid does not deactivate the catalyst for the entire plant. In a standalone hydrotreating unit, the 1-decene and 9-decanoic acid can be simultaneously upgraded to straight chain decane paraffin. In addition to 1-decene and 9-decanoic acid, other saturated and unsaturated fatty acids produced in the hydrolysis reactor may be introduced into the hydrotreating unit to be converted to their corresponding paraffins. While the straight chain decane is within the jet range hydrocarbons, decane may not have the physical properties such as cold pour point, freezing point, density, and octane value required for jet fuel. As such, the decane may be further isomerized in an isomerization unit to produce iso-decane with properties that align with the desired properties of jet fuel. In an embodiment, the 1-decene and 9-decanoic acid produced in the cross metathesis reactor may be separated, for example by distillation, to produce an overhead stream comprising the 1-decene and a bottoms stream comprising the 9-decanoic acid. In such an embodiment, the 1-decene may be routed to an existing kerosene/jet fuel hydrotreater for saturation to decane without the 9-decanoic acid affecting the hydrotreating catalyst. Thereafter the decane may be sent straight to a jet blending pool. In another embodiment, jet range hydrocarbons may be produced from hydrotreating the fatty acids produced in the hydrolysis reactor to produce the corresponding saturated fatty acids. As discussed above, a product from the hydrolysis reactor may include C18s, such as stearic acid (C18:0), oleic acid (C18:1), and linoleic acid (C18:2), for example. The hydrotreatment of the C18s may convert at least a portion of the C18:1 and C18:2 fatty acids to produce saturated products including stearic acid. The stearic acid, and any unreacted C18:1 and C18:2, if present, may be introduced into a hydrocracking unit under conditions sufficient to hydrocrack at least a portion of the molecules to produce jet range hydrocarbons. FIG.1is a block flow diagram illustrating a process producing jet range hydrocarbons from triglycerides in accordance with some embodiments disclosed herein. InFIG.1, a triglyceride stream2may be introduced into hydrolysis unit10. Triglyceride stream2may include any of the triglycerides discussed above. In hydrolysis unit10, triglycerides from triglyceride stream2may be reacted with steam to produce the corresponding fatty acids from the triglycerides as well as glycerol. Hydrolysis unit10may include various different equipment for hydrolyzing the triglyceride with steam, including but not limited to, hydrolysis reactors such as hydrolysis reactors104onFIG.2. For example, the hydrolysis unit may include a batch reactor or a continuous reactor such as a column reactor. In some examples the hydrolysis unit may be configured to perform the Colgate-Emery process and include the associated reactors, flash tanks, and settling tanks required. At least a portion of the triglycerides produced may be C18:1 oleic acid. Intermediate stream3containing at least a portion of the fatty acids from hydrolysis unit10may be introduced into olefin cross-metathesis unit112. In olefin cross-metathesis unit112, the C18:1 may be reacted with ethylene in the presence of a Grubbs catalyst to produce 1-decene and 9-decanoic acid. Intermediate stream4containing at least a portion of the 1-decene and 9-decanoic acid produced in olefin cross-metathesis unit112may be introduced into hydrotreating unit30. Hydrotreating unit30may include reactors comprising hydrotreating catalysts, heaters, separators, and columns configured to perform hydrotreating operations. Hydrotreating may include a range of catalytic processes which react an input stream with hydrogen over a catalyst bed to add hydrogen to the input stream. In hydrotreating unit30, at least a portion of the 1-decene and 9-decanoic acid from intermediate stream4may be hydrotreated to produce decane. Decane stream5may be introduced into isomerization unit40where at least a portion of the decane may be isomerized to iso-decane. Isomerization unit40may include isomerization reactors comprising an isomerization catalyst, as well as associated dryers, separation columns, pumps, and other equipment necessary to isomerize an input stream. Product stream6, containing the iso-decane may be withdrawn from isomerization unit40. FIG.2is a schematic illustration of a process100for producing jet range hydrocarbons from triglycerides in accordance with some embodiments disclosed herein. Process100may begin with triglyceride storage102. Triglyceride storage102may be any storage system, such as a tank farm, barrels, pipeline, or any other suitable storage for the triglycerides described above. Triglycerides from triglyceride storage102may be conveyed to hydrolysis reactor104through conveyance128. Conveyance128may include pipes, tubulars, pumps, and other equipment required to convey the triglycerides from triglyceride storage102to hydrolysis reactor104. Hydrolysis reactor104may be any of the previously mentioned reactor types such as batch reactor or column-type reactor. Steam stream134may be introduced into hydrolysis reactor104and be contacted with triglycerides provided from conveyance128. The triglycerides may be hydrolyzed to form the corresponding fatty acids and glycerol as described above. Hydrolysis reactor104may be operated at any of the conditions described above. Glycerol as well as water and/or steam may be withdrawn from hydrolysis reactor104as stream133and the free fatty acid may be withdrawn from hydrolysis reactor104as stream130. In some embodiments, additional glycerol removal may be utilized such as aqueous phase absorption of the glycerol, followed by phase separation from the fatty acids. Fatty acids in stream130may include a range of fatty acids, the carbon number of which depends on the carbon numbers of the triglycerides which were hydrolyzed. In some embodiments, stream130may include fatty acids with carbon number ranging from C6 to C22, for example. Stream130containing the produced fatty acids may be introduced into distillation column106where the produced fatty acids may be fractionated by molecular weight into overhead stream142containing the fatty acids with carbon numbers of C17 and below and bottom stream132containing the fatty acids with carbon numbers of C18 and above, e.g., C18s. In separator108, the C18s may be further separated into C18:1 stream136and fatty acid stream138. C18:1 stream136may include a majority of the C18:1 fatty acid from bottom stream132while fatty acid stream138may contain a majority of the C18:0 and C18:2 from bottom stream132. If additional fatty acids heavier than C18 are present in bottom stream132, separator108may additionally separate the heavier fatty acids into fatty acid stream138. Ethanol stream124may be introduced to ethanol dehydrator110which may dehydrate the ethanol to produce ethylene stream126. Ethanol dehydrator110may utilize any of the ethanol dehydration techniques disclosed herein to produce ethylene from ethanol. In some embodiments, ethanol dehydrator110may include a steam cracking furnace or other on-purpose units for producing ethylene. From ethanol dehydrator110, ethylene stream126may be introduced into olefin cross metathesis unit112. From separator108, C18:1 stream136may be introduced into olefin cross metathesis unit112. Olefin cross metathesis unit112may include any of the previously described Grubbs catalysts including first, second, and/or third generation Grubbs catalyst. Olefin cross metathesis unit112may be operated at conditions suitable to react at least a portion of the ethylene from ethylene stream126and C18:1 fatty acid from stream136to produce 1-decene and 9-decanoic acid. Product stream140containing the produced 1-decene and 9-decanoic acid may be withdrawn from olefin cross metathesis unit112. Overhead stream142, fatty acid stream138, and product stream140may be combined and introduced into hydrotreating unit114. Hydrotreating unit114may include any hydrotreating units and catalysts previously described. Hydrotreating unit114may further include a hydrogen stream input such that the hydrotreating unit114may be operated at conditions suitable react at least a portion of the feed with the hydrogen to produce paraffins corresponding to olefins, saturated fatty acids, and unsaturated fatty acids in the feed to hydrotreating unit114. Hydrotreated stream150may include decane as a reaction product corresponding to the 1-decene and 9-decanoic acid from product stream140. Product stream140may further include paraffins corresponding to the fatty acids with carbon numbers of C17 from overhead stream142as well as paraffins corresponding to the fatty acids C18:0 and C18:2 from fatty acid stream138. Hydrotreated stream150may be introduced into isomerization unit116. Isomerization unit116may include any of the previously described isomerization units and may be operated at conditions sufficient to isomerize at least a portion of the paraffins in hydrotreated stream150to the corresponding iso-paraffins including iso-decane corresponding to the 1-decene and 9-decanoic acid from product stream140. For example, the isomerization unit may be operated at about 245 to about 270° C. and about 21 to about 35 kg/cm2. Isomerized stream144may be withdrawn from isomerization unit116and introduced into product fractionator118. Product fractionator118may include a distillation column, for example, configured to separate components of isomerized stream144into stream based on molecular mass. For example, product fractionator118may separate isomerized stream144into jet range hydrocarbon stream146comprising hydrocarbons from isomerized stream144with carbon numbers from 9 to 16 and diesel range hydrocarbon stream148comprising any other hydrocarbons from isomerized stream144. Jet range hydrocarbon stream146may be send to jet mixing pool120while diesel range hydrocarbon stream148may be send to diesel mixing pool122. FIG.3illustrates a process300for producing jet range hydrocarbons according to some embodiments disclosed herein. Process200may begin with triglyceride storage202. Triglyceride storage202may be any storage system, such as a tank farm, barrels, pipeline, or any other suitable storage for the triglycerides described above. Triglycerides from triglyceride storage202may be conveyed to hydrolysis reactor204through conveyance228. Conveyance228may include pipes, tubulars, pumps, and other equipment required to convey the triglycerides from triglyceride storage202to hydrolysis reactor204. Hydrolysis reactor204may be any of the previously mentioned reactor types such as batch reactor or column-type reactor. Steam stream234may be introduced into hydrolysis reactor204and be contacted with triglycerides provided from conveyance228. The triglycerides may be hydrolyzed to form the corresponding fatty acids and glycerol as described above. Hydrolysis reactor204may be operated at any of the conditions described above. Glycerol as well as water and/or steam may be withdrawn from hydrolysis reactor204as stream233and the free fatty acid may be withdrawn from hydrolysis reactor204as stream230. In some embodiments, additional glycerol removal may be utilized such as aqueous phase absorption of the glycerol, followed by phase separation from the fatty acids. Fatty acids in stream230may include a range of fatty acids, the carbon number of which depends on the carbon numbers of the triglycerides which were hydrolyzed. In some embodiments, stream230may include fatty acids with carbon number ranging from C6 to C22, for example. Stream230may be introduced into hydrotreating unit206. Hydrotreating unit206may include any hydrotreating units and catalysts previously described. Hydrotreating unit206may further include a hydrogen stream input such that the hydroprocessing unit may be operated at conditions suitable react at least a portion of the feed to hydrotreating unit206with the hydrogen to produce paraffins corresponding to saturated fatty acids and unsaturated fatty acids produced in hydrolysis reactor204and conveyed to hydrotreating unit206by stream230. As discussed above, a product from the hydrolysis reactor may include C18s, such as stearic acid (C18:0), oleic acid (C18:1), and linoleic acid (C18:2), for example. The hydrotreatment of the C18s may convert at least a portion of the C18:1 and C18:2 fatty acids to produce saturated products including stearic acid. Hydrotreated stream235may be withdrawn from hydrotreating unit206and may be introduced into hydrocracker unit208. In hydrocracker unit208, a hydrogen stream and the paraffins produced in hydrotreating unit206may be reacted at conditions sufficient to crack paraffins present in hydrotreated stream235to shorter chain hydrocarbons such as saturated paraffins including jet range hydrocarbons. Hydrocracked stream237comprising the hydrocracked hydrocarbons from hydrocracker unit208Hydrocracked stream237from hydrocracker unit208may be introduced into product fractionator210. Product fractionator210may include a distillation column, for example, configured to separate components of hydrocracked stream237into streams based on molecular mass. For example, product fractionator210may separate hydrocracked stream237into jet range hydrocarbon stream239comprising hydrocarbons from hydrocracked stream237with carbon numbers from 9 to 16 and diesel range hydrocarbon stream241comprising any other hydrocarbons from hydrocracked stream237. Jet range hydrocarbon stream239may be send to jet mixing pool212while diesel range hydrocarbon stream241may be send to diesel mixing pool214. Accordingly, the preceding description describes methods and systems for producing jet range hydrocarbons from triglycerides sourced from natural sources including triglycerides. The processes and systems disclosed herein may include any of the various features disclosed herein, including one or more of the following embodiments. Embodiment 1. A method for producing jet range hydrocarbons comprising: hydrolyzing a triglyceride stream in a hydrolysis unit to produce at least a C18:1 free fatty acid, wherein the triglyceride stream comprises at least one triglyceride comprising at least one C18:1 fatty acid, wherein hydrolyzing the triglyceride stream comprises contacting the at least one triglyceride from the triglyceride stream with at least one of water or steam at conditions sufficient to hydrolyze at least a portion of the at least one triglyceride to produce the C18:1 free fatty acid; introducing the C18:1 free fatty acid into an olefin cross-metathesis reactor and reacting at least a portion of the C18:1 free fatty acid with ethylene in the presence of a Grubbs catalyst to produce 1-decene and 9-decanoic acid; introducing the 1-decene and 9-decanoic acid into a hydrotreating unit and to hydrotreating at least a portion of the 1-decene and 9-decanoic acid to produce decane; and introducing the decane into an isomerization unit and isomerizing at least a portion of the decane to produce iso-decane. Embodiment 2. The method of embodiment 1, wherein the triglyceride stream further comprises at least at least one additional unsaturated fatty acid molecule with a carbon chain length of at least C18 to C32 and at least one unsaturated bond on at least the 9th carbon or greater. Embodiment 3. The method of any of embodiments 1-2, wherein the triglyceride stream further comprises at least one additional triglyceride comprising at least one fatty acid selected from the group consisting of C14 fatty acid, C15 fatty acid, C16 fatty acid, C18:0 fatty acid, C18:2 fatty acid, and combinations thereof, and wherein the method further comprises hydrolyzing the at least one additional triglyceride to produce at least one fatty acid selected from the group consisting of C14 fatty acid, C15 fatty acid, C16 fatty acid, C18:0 fatty acid, C18:2 fatty acid, and combinations thereof. Embodiment 4. The method of embodiment 3, wherein an outlet from the hydrolysis unit comprises the C18:1 free fatty acid and the at least one additional triglyceride, and wherein the method further comprises fractionating the outlet from the hydrolysis unit to produce an overhead stream comprising C16 and lighter fatty acids and a bottoms stream comprising C18:2 and heavier fatty acids. Embodiment 5. The method of embodiment 4, further comprising separating C18:1 free fatty acid from the bottoms stream, wherein the C18:1 free fatty acid separated from the bottoms stream is introduced in the olefin cross-metathesis reactor. Embodiment 6. The method of any of embodiments 4-5, further comprising introducing the overhead stream comprising C16 and lighter fatty acids into the hydrotreating unit and hydrotreating at least a portion of the C16 and lighter fatty acids to produce a saturated paraffin corresponding to the C16 and lighter fatty acids. Embodiment 7. The method of embodiment 6 wherein the saturated paraffin is introduced into the isomerization unit to isomerize at least a portion of the saturated paraffin to produce a corresponding iso-paraffin. Embodiment 8. The method of any of embodiments 1-7, further comprising dehydrating an ethanol stream to produce an ethylene stream and introducing the ethylene stream into the olefin cross-metathesis reactor. Embodiment 9. The method of any of embodiments 1-8, wherein the triglyceride stream is from an algae source. Embodiment 10. A method for producing jet range hydrocarbons comprising: counter-currently contacting a triglyceride stream and steam in a column hydrolysis unit to produce at least a C18:1 free fatty acid stream, wherein the triglyceride stream comprises at least one triglyceride comprising at least one C18:1 fatty acid; introducing the C18:1 free fatty acid stream into an olefin cross-metathesis reactor and reacting at least a portion of the C18:1 free fatty acid with ethylene in the presence of a Grubbs catalyst to produce a 1-decene and 9-decanoic acid stream; introducing the 1-decene and 9-decanoic acid stream into a hydrotreating unit and hydrotreating at least a portion of the 1-decene and 9-decanoic acid to produce a decane stream; introducing the decane stream into an isomerization unit and isomerizing at least a portion of the decane stream to produce an iso-decane stream; and separating at least a portion of the iso-decane stream to produce a jet range hydrocarbon stream. Embodiment 11. The method of embodiment 10, wherein the column hydrolysis unit is operated at about 245° C. to about 270° C. and about 21 to about 35 kg/cm2. Embodiment 12. The method of any of embodiments 10-11, wherein the column hydrolysis unit is operated at a temperature in a range of about 250° C. to about 260° C. and a pressure up to 50 barg, and wherein 95% or greater of the triglyceride stream by weight is converted to a corresponding fatty acid. Embodiment 13. A system for producing jet range hydrocarbons comprising: a triglyceride source comprising at least one C18:1 fatty acid; a hydrolysis unit coupled to the triglyceride source and a steam source, wherein the hydrolysis unit is configured to hydrolyze at least a portion of the triglyceride source to produce a free fatty acid stream comprising free fatty acids corresponding to triglycerides in the triglyceride source, wherein the free fatty acid stream comprises at least C18:1 fatty acid; a separation unit coupled to the free fatty acid stream, wherein the separation unit is configured to separate a majority of the C18:1 fatty acid from the free fatty acid stream to produce a C18:1 fatty acid stream; an olefin cross metathesis reactor coupled to the C18:1 fatty acid stream, wherein the olefin cross metathesis reactor is configured to react the C18:1 fatty acid with ethylene to produce a stream comprising 1-decene and 9-decanoic acid; a hydrotreating unit coupled to the stream comprising 1-decene and 9-decanoic acid, wherein the hydrotreating unit is configured to hydrotreat at least a portion of the 1-decene and 9-decanoic acid to produce a hydrotreated product stream comprising decane; and an isomerization unit coupled to the hydrotreated product stream, wherein the isomerization unit is configured to isomerize at least a portion of the decane to produce an isomerized product stream comprising iso-decane. Embodiment 14. The system of embodiment 13, wherein the triglyceride source further comprises at least one additional triglyceride comprising at least one fatty acid selected from the group consisting of C14 fatty acid, C15 fatty acid, C16 fatty acid, C18:0 fatty acid, C18:2 fatty acid, and combinations thereof. Embodiment 15. The system of any of embodiments 13-14 wherein the steam source comprises steam at a temperature in a range of about 250° C.-260° C. and a pressure up to 50 barg. Embodiment 16. The system of any of embodiments 13-15 wherein the olefin cross metathesis reactor further comprises a Grubbs catalyst. Embodiment 17. The system of any of embodiments 13-16 wherein the separation unit is further configured to produce a stream containing a balance of the fatty acids from the free fatty acid stream which are not the C18:1 fatty acid. Embodiment 18. The system of embodiment 17 wherein the stream containing the balance of the fatty acids is coupled to the hydrotreating unit and where the hydrotreating unit is further configured to hydrotreat at least a portion of the balance of the fatty acids to produce paraffins, wherein the hydrotreated product stream comprises the paraffins. Embodiment 19. The system of embodiment 18 wherein the isomerization unit is further configured to isomerize the paraffins to iso-paraffins, wherein the isomerized product stream further comprises the iso-paraffins. Embodiment 20. The system of any of embodiments 18-19, further comprising a product fractionator configured to separate the isomerized stream into a jet range hydrocarbon stream and diesel range hydrocarbon stream. While the disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the disclosure as disclosed herein. Although individual embodiments are discussed, the present disclosure covers all combinations of all those embodiments. While compositions, methods, and processes are described herein in terms of “comprising,” “containing,” “having,” or “including” various components or steps, the compositions and methods can also “consist essentially of” or “consist of” the various components and steps. The phrases, unless otherwise specified, “consists essentially of” and “consisting essentially of” do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used. All numerical values within the detailed description and the claims herein modified by “about” or “approximately” with respect the indicated value are intended to take into account experimental error and variations that would be expected by a person having ordinary skill in the art. For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. | 39,389 |
11858873 | DETAILED DESCRIPTION OF THE EMBODIMENTS It should be noted that embodiments in the present disclosure and features in the embodiments may be combined with each other in the case without conflicting. The present disclosure is described in detail below in combination with the embodiments. According to a typical embodiment of the present disclosure, a method for continuously synthesizing a propellane compound is provided. The method includes the following steps: 1,1-dibromo-2,2-chloromethylcyclopropane or a derivative thereof as a raw material to form a ring with a lithium metal agent by a continuous reaction, so as to synthesize the propellane compound. A technical scheme of the present disclosure is applied, and a continuous reaction device is used. Continuous feeding, continuous reaction, continuous transfer, and continuous quenching are performed, and the post-treatment may even acquire a separation yield of more than 90%, so the efficient synthesis of the propellane is achieved. In addition, the continuous process is capable of shortening the reaction time, and solving a problem that a product in scale-up production is unstable under an alkaline condition and is deteriorated with the long reaction time; and the use of the continuous process greatly reduces a risk that the lithium reagent is used in the reaction, and it is more beneficial to the scale-up production. Typically, in an embodiment of the present disclosure, 1,1-dibromo-2,2-chloromethylcyclopropane or the derivative thereof has the following structure: wherein R1and R2each represents hydrogen, alkyl, alkoxy, or aryl, the structures represented by R1and R2are the same or different, and R1and R2are preferably —CH3or —C2H5. Preferably, the lithium metal agent is one selected from a group consisting of phenyl lithium, benzyl lithium, methyllithium, ethyllithium, butyllithium, isopropyllithium and dodecyl lithium. These lithium reagents have the characteristics of small metal ion radius, strong polarization ability, strong alkalinity and the like, and may more completely capture hydrogen or bromine. Preferably, the temperature of the continuous reaction is −78˜5° C. In fact, the continuous reaction may be divided into three stages. The first stage of hydrogen extraction needs to be performed at a low temperature, and the lithium reagent may be destroyed at a high temperature; and the second stage and the third stage of the reactions need to be performed at about 0 degrees. According to a typical embodiment of the present disclosure, the method for continuously synthesizing the propellane compound further includes a continuous online quenching reaction after the continuous reaction is completed; and it is convenient for the industrial continuous production. Preferably, a quencher used in the continuous online quenching reaction is aqueous ammonia; the concentration of the aqueous ammonia is 1.0˜3.0 g/g; and more preferably, the concentration of the aqueous ammonia is 1.0 g/g. In a typical embodiment of the present disclosure, the continuous reaction is performed in a continuous stirred tank reactor. Typically, the continuous stirred tank reactor includes a first-stage continuous stirred tank reactor, a second-stage continuous stirred tank reactor, and a third-stage continuous stirred tank reactor that are connected in series. In this way, it may be equivalent to several different reactor units which are connected together, and each reactor unit may have the different temperatures, reaction temperatures, raw material ratios and the like, it is more convenient for the flexible control of the reaction conditions. In a typical embodiment of the present disclosure, the 1,1-dibromo-2,2-chloromethylcyclopropane or the derivative thereof is dissolved in a first solvent to obtain solution A, and the lithium metal agent is dissolved in a second solvent to obtain solution B, the solution A and the solution B are added to the continuous stirred tank reactor for the continuous reaction by an automatic feeding system, this operation is convenient to control the addition amount of the 1,1-dibromo-2,2-chloromethylcyclopropane or the derivative thereof and the lithium metal reagent. Preferably, the first solvent and the second solvent are respectively one or more selected from a group consisting of n-pentane, n-hexane, n-heptane, n-butyl ether, diethyl ether and methyl tert-butyl ether. These solvents are all inert solvents, have no special functional groups, and are stable, not easy to react, relatively cheap in price, and it is conducive to the control of the industrial production cost. According to a typical embodiment of the present disclosure, in the solution A, the molar concentration of the 1,1-dibromo-2,2-chloromethylcyclopropane or the derivative thereof is 0.5˜3.0 M; and in the solution B, the molar concentration of the lithium metal agent is 1.0˜3.0 M. Reactants are fully used in this range. In order to make the reaction proceed fully, preferably, the feeding ratio (the mol ratio of a reaction substrate after conversion) of the solution A and the solution B is 1:2.0˜1:3.0. According to a typical embodiment of the present disclosure, the reaction temperature in the first-stage continuous stirred tank reactor is −75° C. to −51° C., for example, −74° C., −73° C., −71° C., −70° C., −68° C., −66° C.° C., −65° C., −64° C., −62° C., −60° C., −58° C., −56° C., −55° C., −54° C., and −52° C., and the reaction time is 20˜40 min; preferably, the reaction temperature in the second-stage continuous stirred tank reactor is −5° C. to 5° C., for example, −5° C., −4° C., −3° C., −2° C., −1° C., 0° C., 1° C., 2° C., 3° C., 4° C. or 5° C., and the reaction time is 30˜60 min; and preferably, the reaction temperature in the third-stage continuous stirred tank reactor is −5° C. to 5° C., for example, −5° C., −4° C., −3° C., −2° C., −1° C., 0° C., 1° C., 2° C., 3° C., 4° C. or 5° C., and the reaction time is 30˜60 min. The reaction in the first-stage continuous stirred tank reactor belongs to a first-stage temperature-controlled dropwise-adding section, and a dropwise-adding process needs to be performed at a low temperature, otherwise, the raw material may be deteriorated; and the reactions in the second-stage continuous stirred tank reactor and the third-stage continuous stirred tank reactor belong to the second-stage and the third-stage which are reaction sections, after the dropwise-adding is completed, the reaction needs to be performed at about 0° C., so the temperature is controlled in the range of −5 to 5° C. The control of the above reaction time is because the dropwise-adding process releases heat apparently, within the controllable temperature range, the first-stage dropwise-adding section needs 20˜40 min, the second-stage and the third-stage are the reaction time, the total time is 1˜2 h, and the reactants may be converted completely. The beneficial effects of the present disclosure are further described below in combination with the embodiments. Contrast Example 1 (1) Device specifications: a three-stage 1000 mL continuous stirred tank reactor (CSTR, namely a continuous stirred tank reactor), a 50 ml plunger pump, a 5000 g balance, and a 1.0 L feeding bottle. (2) Raw material ratios: Solution A: 5.0 kg 1,1-dibromo-2,2-chloromethylcyclopropane+2.0 vol n-butyl ether, and L1 (feed rate of solution A)=4.5 g/min. Solution B: 2.2 eq phenyl lithium/n-butyl ether solution, and L2 (feed rate of solution B)=4.5 g/min. Solution C: 1.0 g/g aqueous ammonia, and L3 (feed rate of solution C)=1.0 g/min. (3) Reaction conditions: the three-stage CSTR is used, in a first-stage low-temperature section, the temperature is controlled to be −50˜0° C., retention volume: 500 ml, in second-stage and third-stage reaction sections, the temperature is controlled to be 0° C., retention volume: 700 ml, it is overflowed to a receiving bottle in the third-stage, the temperature of the receiving bottle is controlled to be 0° C., the total retention volume is 1200 ml, and retention time (RT)=2.0 h. An automatic feeding system is opened, and fed by two materials, L1=4.5 g/min, L2=4.5 g/min, the two materials are mixed in the first-stage CSTR low-temperature section, after 40 min, it is overflowed to the second-stage and third-stage reaction sections for reaction, and after 70 min, the third-stage CSTR begins to overflow to the receiving bottle, and the feeding system is opened, L3=1.0 g/min, and the aqueous ammonia is continuously fed to quench the reaction. Post-treatment, liquid separation, and low-temperature distillation are performed to obtain 0.761 kg of a product (converted content), and the NMR yield is 68%. Embodiment 1 Raw Material: R1═H, and R2═CH3 Solution A: 0.31 kg 1,1-dibromo-2,2-chloromethylcyclopropane+2.0 vol n-butyl ether. Solution B: 2.2 eq phenyl lithium/n-butyl ether solution. Solution C: 1.0 g/g aqueous ammonia. Reaction conditions: the three-stage CSTR is used, in a first-stage low-temperature section, the temperature is controlled to be −65° C., retention volume: 50 ml, in second-stage and third-stage reaction sections, the temperature is controlled to be 0° C., retention volume: 70 ml, it is overflowed to a receiving bottle in the third-stage, the temperature of the receiving bottle is controlled to be 0° C., the total retention volume is 120 ml, and RT=2.0 h. An automatic feeding system is opened, and fed by two materials, L1=0.48 g/min, L2=0.40 g/min, the two materials are mixed in the first-stage CSTR low-temperature section, after 40 min, it is overflowed to the second-stage and third-stage reaction sections for reaction, and after 70 min, the third-stage CSTR begins to overflow to the receiving bottle, and the feeding system is opened, L3=0.1 g/min, and the aqueous ammonia is continuously fed to quench the reaction. Post-treatment, liquid separation, and low-temperature distillation are performed to obtain 70.5 g of a product (converted content), and the NMR yield is 85%. Embodiment 2 Device specifications are the same as in Embodiment 1, and the differences from Embodiment 1 are as follows: Raw material: R1═H, and R2═C2H5 Solution A: 0.33 kg 1,1-dibromo-2,2-chloromethylcyclopropane+2.0 vol n-butyl ether. Solution B: 2.2 eq phenyl lithium/n-butyl ether solution. Solution C: 1.0 g/g aqueous ammonia. Reaction conditions: the three-stage CSTR is used, in a first-stage low-temperature section, the temperature is controlled to be −65° C., retention volume: 50 ml, in second-stage and third-stage reaction sections, the temperature is controlled to be 0° C., retention volume: 70 ml, it is overflowed to a receiving bottle in the third-stage, the temperature of the receiving bottle is controlled to be 0° C., the total retention volume is 120 ml, and RT=2.0 h. An automatic feeding system is opened, and fed by two materials, L1=0.49 g/min, L2=0.40 g/min, the two materials are mixed in the first-stage CSTR low-temperature section, after 40 min, it is overflowed to the second-stage and third-stage reaction sections for reaction, and after 70 min, the third-stage CSTR begins to overflow to the receiving bottle, and the feeding system is opened, L3=0.1 g/min, and the aqueous ammonia is continuously fed to quench the reaction. Post-treatment, liquid separation, and low-temperature distillation are performed to obtain 84.70 g of a product (converted content), and the NMR yield is 90.06%. Embodiment 3 Device specifications are the same as in Embodiment 1, and the differences from Embodiment 1 are as follows: Methyl lithium is used as a lithium reagent. Raw Material Ratio: Solution A: 0.5 kg 1,1-dibromo-2,2-chloromethylcyclopropane+2.0 vol n-butyl ether. Solution B: 2.2 eq methyl lithium/n-butyl ether solution. Solution C: 1.0 g/g aqueous ammonia. Reaction conditions: the three-stage CSTR is used, in a first-stage low-temperature section, the temperature is controlled to be −65° C., retention volume: 500 ml, in second-stage and third-stage reaction sections, the temperature is controlled to be 0° C., retention volume: 700 ml, it is overflowed to a receiving bottle in the third-stage, the temperature of the receiving bottle is controlled to be 0° C., the total retention volume is 1200 ml, and RT=2.0 h. An automatic feeding system is opened, and fed by two materials, L1=0.46 g/min, L2=0.43 g/min, the two materials are mixed in the first-stage CSTR low-temperature section, after 40 min, it is overflowed to the second-stage and third-stage reaction sections for reaction, and after 70 min, the third-stage CSTR begins to overflow to the receiving bottle, and the feeding system is opened, L3=0.1 g/min, and the aqueous ammonia is continuously fed to quench the reaction. Post-treatment, liquid separation, and low-temperature distillation are performed to obtain 92.67 g of a product (converted content), and the NMR yield is 86%. Embodiment 4 Device specifications are the same as in Embodiment 1, and the differences from Embodiment 1 are as follows: The reaction temperature in the first-stage is −51° C. Raw Material Ratio: Solution A: 0.5 kg 1,1-dibromo-2,2-chloromethylcyclopropane+2.0 vol n-butyl ether. Solution B: 2.2 eq phenyl lithium/n-butyl ether solution. Solution C: 1.0 g/g aqueous ammonia. Reaction conditions: the three-stage CSTR is used, in a first-stage low-temperature section, the temperature is controlled to be −51° C., retention volume: 50 ml, in second-stage and third-stage reaction sections, the temperature is controlled to be 0° C., retention volume: 70 ml, it is overflowed to a receiving bottle in the third-stage, the temperature of the receiving bottle is controlled to be 0° C., the total retention volume is 120 ml, and RT=2.0 h. An automatic feeding system is opened, and fed by two materials, L1=0.46 g/min, L2=0.43 g/min, the two materials are mixed in the first-stage CSTR low-temperature section, after 40 min, it is overflowed to the second-stage and third-stage reaction sections for reaction, and after 70 min, the third-stage CSTR begins to overflow to the receiving bottle, and the feeding system is opened, L3=0.3 g/min, and the aqueous ammonia is continuously fed to quench the reaction. Post-treatment, liquid separation, and low-temperature distillation are performed to obtain 92.88 g of a product (converted content), and the NMR yield is 83%. Embodiment 5 Device specifications are the same as in Embodiment 1, and the differences from Embodiment 1 are as follows. The amount of aqueous ammonia is 3.0 g/g. Raw Material Ratio: Solution A: 0.5 kg 1,1-dibromo-2,2-chloromethylcyclopropane+2.0 vol n-butyl ether. Solution B: 2.2 eq phenyl lithium/n-butyl ether solution. Solution C: 3.0 g/g aqueous ammonia. Reaction conditions: the three-stage CSTR is used, in a first-stage low-temperature section, the temperature is controlled to be −65° C., retention volume: 50 ml, in second-stage and third-stage reaction sections, the temperature is controlled to be 0° C., retention volume: 70 ml, it is overflowed to a receiving bottle in the third-stage, the temperature of the receiving bottle is controlled to be 0° C., the total retention volume is 120 ml, and RT=2.0 h. An automatic feeding system is opened, and fed by two materials, L1=0.46 g/min, L2=0.43 g/min, the two materials are mixed in the first-stage CSTR low-temperature section, after 40 min, it is overflowed to the second-stage and third-stage reaction sections for reaction, and after 70 min, the third-stage CSTR begins to overflow to the receiving bottle, and the feeding system is opened, L3=0.3 g/min, and the aqueous ammonia is continuously fed to quench the reaction. Post-treatment, liquid separation, and low-temperature distillation are performed to obtain 100.7 g of a product (converted content), and the NMR yield is 90%. Embodiment 6 Device specifications are the same as in Embodiment 1, and the differences from Embodiment 1 are as follows. N-hexane is used as a reaction solvent. Raw Material Ratio: Solution A: 0.5 kg 1,1-dibromo-2,2-chloromethylcyclopropane+2.0 vol n-butyl ether. Solution B: 2.2 eq phenyl lithium/n-butyl ether solution. Solution C: 1.0 g/g aqueous ammonia. Reaction conditions: the three-stage CSTR is used, in a first-stage low-temperature section, the temperature is controlled to be −65° C., retention volume: 50 ml, in second-stage and third-stage reaction sections, the temperature is controlled to be 0° C., retention volume: 70 ml, it is overflowed to a receiving bottle in the third-stage, the temperature of the receiving bottle is controlled to be 0° C., the total retention volume is 120 ml, and RT=2.0 h. An automatic feeding system is opened, and fed by two materials, L1=0.44 g/min, L2=0.45 g/min, the two materials are mixed in the first-stage CSTR low-temperature section, after 40 min, it is overflowed to the second-stage and third-stage reaction sections for reaction, and after 70 min, the third-stage CSTR begins to overflow to the receiving bottle, and the feeding system is opened, L3=0.1 g/min, and the aqueous ammonia is continuously fed to quench the reaction. Post-treatment, liquid separation, and low-temperature distillation are performed to obtain 97.7 g of a product (converted content), and the NMR yield is 88%. Embodiment 7 Device specifications are the same as in Embodiment 1, and the differences from Embodiment 1 are as follows. The substrate concentration is changed, and 3.0 vol n-butyl ether is used. Raw Material Ratio: Solution A: 0.5 kg 1,1-dibromo-2,2-chloromethylcyclopropane+3.0 vol n-butyl ether. Solution B: 2.2 eq phenyl lithium/n-butyl ether solution. Solution C: 1.0 g/g aqueous ammonia. Reaction conditions: the three-stage CSTR is used, in a first-stage low-temperature section, the temperature is controlled to be −65° C., retention volume: 50 ml, in second-stage and third-stage reaction sections, the temperature is controlled to be 0° C., retention volume: 70 ml, it is overflowed to a receiving bottle in the third-stage, the temperature of the receiving bottle is controlled to be 0° C., the total retention volume is 120 ml, and RT=2.0 h. An automatic feeding system is opened, and fed by two materials, L1=0.55 g/min, L2=0.33 g/min, the two materials are mixed in the first-stage CSTR low-temperature section, after 40 min, it is overflowed to the second-stage and third-stage reaction sections for reaction, and after 70 min, the third-stage CSTR begins to overflow to the receiving bottle, and the feeding system is opened, L3=0.1 g/min, and the aqueous ammonia is continuously fed to quench the reaction. Post-treatment, liquid separation, and low-temperature distillation are performed to obtain 95.5 g of a product (converted content), and the NMR yield is 86%. Embodiment 8 Device specifications are the same as in Embodiment 1, and the differences from Embodiment 1 are as follows: The ratio of solution A and solution B is changed to 1:3.0. Raw Material Ratio: Solution A: 0.5 kg 1,1-dibromo-2,2-chloromethylcyclopropane+2.0 vol n-butyl ether. Solution B: 3.0 eq phenyl lithium/n-butyl ether solution. Solution C: 1.0 g/g aqueous ammonia. Reaction conditions: the three-stage CSTR is used, in a first-stage low-temperature section, the temperature is controlled to be −65° C., retention volume: 50 ml, in second-stage and third-stage reaction sections, the temperature is controlled to be 0° C., retention volume: 70 ml, it is overflowed to a receiving bottle in the third-stage, the temperature of the receiving bottle is controlled to be 0° C., the total retention volume is 120 ml, and RT=2.0 h. An automatic feeding system is opened, and fed by two materials, L1=0.38 g/min, L2=0.50 g/min, the two materials are mixed in the first-stage CSTR low-temperature section, after 40 min, it is overflowed to the second-stage and third-stage reaction sections for reaction, and after 70 min, the third-stage CSTR begins to overflow to the receiving bottle, and the feeding system is opened, L3=0.1 g/min, and the aqueous ammonia is continuously fed to quench the reaction. Post-treatment, liquid separation, and low-temperature distillation are performed to obtain 93.2 g of a product (converted content), and the NMR yield is 84%. Embodiment 9 Device specifications are the same as in Embodiment 1, and the differences from Embodiment 1 are as follows. The reaction time of each stage is changed. Raw Material Ratio: Solution A: 0.5 kg 1,1-dibromo-2,2-chloromethylcyclopropane+2.0 vol n-butyl ether. Solution B: 2.2 eq phenyl lithium/n-butyl ether solution. Solution C: 1.0 g/g aqueous ammonia. Reaction conditions: the three-stage CSTR is used, in a first-stage low-temperature section, the temperature is controlled to be −65° C., retention volume: 50 ml, in second-stage and third-stage reaction sections, the temperature is controlled to be 0° C., retention volume: 70 ml, it is overflowed to a receiving bottle in the third-stage, the temperature of the receiving bottle is controlled to be 0° C., the total retention volume is 120 ml, and RT=2.0 h. An automatic feeding system is opened, and fed by two materials, L1=0.41 g/min, L2=0.50 g/min, the two materials are mixed in the first-stage CSTR low-temperature section, after 30 min, it is overflowed to the second-stage and third-stage reaction sections for reaction, and after 100 min, the third-stage CSTR begins to overflow to the receiving bottle, and the feeding system is opened, L3=0.1 g/min, and the aqueous ammonia is continuously fed to quench the reaction. Post-treatment, liquid separation, and low-temperature distillation are performed to obtain 100.9 g of a product (converted content), and the NMR yield is 91%. Embodiment 10 Device specifications are the same as in Embodiment 1, and the differences from Embodiment 1 are as follows: The reaction temperature of each stage is changed. Raw Material Ratio: Solution A: 0.5 kg 1,1-dibromo-2,2-chloromethylcyclopropane+2.0 vol n-butyl ether. Solution B: 2.2 eq phenyl lithium/n-butyl ether solution. Solution C: 1.0 g/g aqueous ammonia. Reaction conditions: the three-stage CSTR is used, in a first-stage low-temperature section, the temperature is controlled to be −65° C., retention volume: 50 ml, in second-stage and third-stage reaction sections, the temperature is controlled to be 15° C., retention volume: 70 ml, it is overflowed to a receiving bottle in the third-stage, the temperature of the receiving bottle is controlled to be 15° C., the total retention volume is 120 ml, and RT=2.0 h. An automatic feeding system is opened, and fed by two materials, L1=0.41 g/min, L2=0.50 g/min, the two materials are mixed in the first-stage CSTR low-temperature section, after 40 min, it is overflowed to the second-stage and third-stage reaction sections for reaction, and after 70 min, the third-stage CSTR begins to overflow to the receiving bottle, and the feeding system is opened, L3=0.1 g/min, and the aqueous ammonia is continuously fed to quench the reaction. Post-treatment, liquid separation, and low-temperature distillation are performed to obtain 89.84 g of a product (converted content), and the NMR yield is 81%. Embodiment 11 Device specifications and material parameters are all the same as in Embodiment 1, and the difference from Embodiment 1 is only that the reaction temperature in the first-stage is −55° C., and finally the NMR yield is 89.1%. Embodiment 12 Device specifications and material parameters are all the same as in Embodiment 1, and the difference from Embodiment 1 is only that the reaction temperature in the first-stage is −70° C., and finally the NMR yield is 92.5%. Embodiment 13 Device specifications and material parameters are all the same as in Embodiment 1, and the difference from Embodiment 1 is only that the reaction temperatures in the first-stage and the second-stage are −5° C., and finally the NMR yield is 81.7%. Embodiment 14 Device specifications and material parameters are all the same as in Embodiment 1, and the difference from Embodiment 1 is only that the reaction temperature in the first-stage is 5° C., and finally the NMR yield is 83.1%. Embodiment 15 Device specifications and material parameters are all the same as in Embodiment 1, and the difference from Embodiment 1 is only that the total reaction time of the second-stage and the third-stage is 60 min, and finally the NMR yield is 86.9%. Embodiment 16 Device specifications and material parameters are all the same as in Embodiment 1, and the difference from Embodiment 1 is only that the total reaction time of the second-stage and the third-stage is 120 min, and finally the NMR yield is 91.2%. It may be seen from the above descriptions that the above embodiments of the present disclosure achieve the following technical effects. 1) For the first time, the use of the continuous device is achieved, the 1,1-dibromo-2,2-chloromethylcyclopropane and the derivative thereof are used as the raw materials, through the continuous reaction, it is cycle-closed with the lithium metal agent to prepare the propellane compound. 2) The continuous reaction mode is capable of shortening the unit reaction time, and reducing the contact time between the product and the metal reagent, the damage of the product in the alkaline condition is reduced in the greatest degree. It is changed from the unable scale-up of the batch reaction to the continuous scale-up, and to the continuous high-efficiency scale-up, so the industrialized large-scale production of the propellane compound becomes possible. 3) The continuous process is capable of increasing the separation yield to 90% after the scale-up, and greatly reducing the synthesis cost of the product; and a problem that the modifications of many drugs at present may not be achieved due to the high price of the propellane derivative is solved. 4) The use of the continuous device is capable of reducing a risk factor of using the active metal reagent, and greatly saving the labor cost at the same time, and it is beneficial to the industrial scale-up production. 5) Compared to a traditional reaction, the continuous reaction may be stopped or terminated at any time according to the actual situation. The post-treatment may also be performed in batches or combined as needed, and it is convenient and simple. The above are only preferred embodiments of the present disclosure, and are not used to limit the present disclosure. Various modifications and changes may be made to the present disclosure by those skilled in the art. Any modifications, equivalent replacements, improvements and the like made within the spirit and principle of the present disclosure should be included in a scope of protection of the present disclosure. | 26,818 |
11858874 | REFERENCE NUMERAL 10: Acid Catalyst20: Dimethylbenzyl Alcohol Solution30: Reactor40: Alpha-Methylstyrene and Unreacted Materials50: Second Reaction Product60: Distillation Column70: Condenser80: Trap90: Second Alpha-Methylstyrene and Unreacted Materials100: Water (H2O) DETAILED DESCRIPTION Hereinafter, the present application will be described in more detail. In the present specification, a description of a certain member being placed “on” another member comprises not only a case of the certain member being in contact with the another member but a case of still another member being present between the two members. In the present specification, a description of a certain part “comprising” certain constituents means capable of further comprising other constituents, and does not exclude other constituents unless particularly stated on the contrary. The method for preparing alpha-methylstyrene according to one embodiment of the present application comprises dehydrating a dimethylbenzyl alcohol solution in a reactor under an acid catalyst to prepare alpha-methylstyrene, wherein a reaction product after the dehydration reaction comprises a first reaction product comprising first alpha-methylstyrene; and a second reaction product comprising vapor (H2O), second alpha-methylstyrene and unreacted materials, and after separating the second reaction product from the reactor, separating the second alpha-methylstyrene and the unreacted materials comprised in the second reaction product and recirculating the second alpha-methylstyrene and the unreacted materials to the reactor, a temperature inside the reactor during the dehydration reaction is 135° C. or higher, and a content of the acid catalyst is from 100 ppm to 1,500 ppm based on a total weight of dimethylbenzyl alcohol of the dimethylbenzyl alcohol solution. The method for preparing alpha-methylstyrene according to one embodiment of the present application comprises dehydrating a dimethylbenzyl alcohol solution in a reactor under an acid catalyst to prepare alpha-methylstyrene. As described above, alpha-methylstyrene has been prepared as a by-product of a phenol manufacturing process in the art by preparing phenol and alpha-methylstyrene through oxidation and cleavage processes using cumene as a raw material. More specifically, in the art, cumene, a starting material, is oxidized to prepare a mixture of cumene peroxide and cumyl alcohol, and the mixture of cumene peroxide and cumyl alcohol goes through a cleavage reaction to prepare phenol and acetone from the cumene peroxide and prepare alpha-methylstyrene from the cumyl alcohol. However, such an existing technology is mainly aimed at producing phenol from cumene, and since the alpha-methylstyrene is produced as a by-product of a phenol manufacturing process, there are problems in that the produced amount is small and a yield of the produced alpha-methylstyrene is only about 70% to 80%. However, unlike the above-described existing technology of oxidizing cumene to prepare a mixture of cumene peroxide and cumyl alcohol and then preparing alpha-methylstyrene therefrom through an additional reaction, the method for preparing alpha-methylstyrene according to one embodiment of the present application prepares alpha-methylstyrene by directly dehydrating a dimethylbenzyl alcohol solution, and as a result, selectivity of the alpha-methylstyrene may be enhanced as well as increasing a yield of the alpha-methylstyrene. In one embodiment of the present application, the acid catalyst may be a liquid acid catalyst or a solid acid catalyst. The liquid acid catalyst may be hydrochloric acid, sulfuric acid or nitric acid, and is more preferably sulfuric acid. In addition, the solid acid catalyst may be selected from among Group 4 metal oxides modified by Group 6 metal oxides, sulfated transition metal oxides, mixed metal oxides of cerium oxide and Group 4 metal oxides, and mixtures thereof. In one embodiment of the present application, a content of the acid catalyst may be from 100 ppm to 1,500 ppm, and may be from 150 ppm to 500 ppm based on a total weight of dimethylbenzyl alcohol of the dimethylbenzyl alcohol solution. When the content of the acid catalyst is greater than 1,500 ppm based on a total weight of dimethylbenzyl alcohol of the dimethylbenzyl alcohol solution, the produced alpha-methylstyrene may be converted to an alpha-methylstyrene dimer form reducing a yield of the alpha-methylstyrene. In addition, the content of the acid catalyst being less than 100 ppm based on a total weight of dimethylbenzyl alcohol of the dimethylbenzyl alcohol solution is not preferred as well since the yield of the alpha-methylstyrene may decrease. In one embodiment of the present application, a content of the dimethylbenzyl alcohol in the dimethylbenzyl alcohol solution may be from 8% by weight to 90% by weight, and may be from 20% by weight to 35% by weight. When the content of dimethylbenzyl alcohol is less than 8% by weight or greater than 90% by weight in the dimethylbenzyl alcohol solution, the reaction time for preparing the alpha-methylstyrene increases, and the residence time of the reactants in the reactor may increase. When the residence time of the reactants in the reactor increases as above, a side reaction of converting the alpha-methylstyrene to an alpha-methylstyrene dimer occurs more, which may lower a yield of the alpha-methylstyrene. In addition, there may be a problem of increasing a content of the acid catalyst introduced to reduce the residence time. In addition, the side reaction of converting the alpha-methylstyrene to an alpha-methylstyrene dimer may be further accelerated when an alcohol is present, and therefore, a problem of reducing selectivity of the alpha-methylstyrene may occur when the content of the dimethylbenzyl alcohol is excessively high. The dimethylbenzyl alcohol solution may comprise, in addition to dimethylbenzyl alcohol, acetophenone, cumyl hydroperoxide, alpha-methylstyrene, cumene, dicumyl peroxide, an alpha-methylstyrene dimer, water and the like. In one embodiment of the present application, the dimethylbenzyl alcohol solution may comprise dimethylbenzyl alcohol in 28.6% by weight, acetophenone in 0.2% by weight, cumyl hydroperoxide in 1.0% by weight, alpha-methylstyrene in 0.01% by weight, cumene in 67.0% by weight, dicumyl peroxide in 0.2% by weight, an alpha-methylstyrene dimer in 0.02% by weight and water in 2.97% by weight, based on a total weight of the dimethylbenzyl alcohol solution, however, the content is not limited thereto. In one embodiment of the present application, the reaction product after the dehydration reaction comprises a first reaction product comprising first alpha-methylstyrene; and a second reaction product comprising vapor (H2O), second alpha-methylstyrene and unreacted materials. Water is produced when the dimethylbenzyl alcohol is converted to the alpha-methylstyrene through the dehydration reaction, and by an inner temperature of the reactor, the water, some of the alpha-methylstyrene and the unreacted materials evaporate together. In other words, in one embodiment of the present application, the second reaction product represents the water, some of the alpha-methylstyrene and the unreacted materials evaporating together by an inner temperature of the reactor. In one embodiment of the present application, in order to enhance the yield of the prepared alpha-methylstyrene, water is removed from the second reaction product comprising second alpha-methylstyrene and unreacted materials evaporating with the water, and the second alpha-methylstyrene and the unreacted materials are recirculated to the reactor. In one embodiment of the present application, the unreacted materials may comprise an unreacted dimethylbenzyl alcohol solution, the acid catalyst and the like. In one embodiment of the present application, the method of separating the second alpha-methylstyrene and the unreacted materials comprised in the second reaction product may comprise processes of separating the second reaction product comprising vapor (H2O), the second alpha-methylstyrene and the unreacted materials from the reactor, and then introducing the second reaction product to a distillation column and a condenser sequentially. As the distillation column, distillation columns used in the art may be used. As the distillation column, a single distillation column may be used, and using the single distillation column, the second reaction product may be transferred to the condenser to describe later. As the condenser, condensers used in the art may be used. Examples thereof may comprise a water-cooled condenser, an air-cooled condenser, an evaporative condenser and the like, but are not limited thereto. Inside the condenser may satisfy a temperature of 0° C. to 50° C., preferably 0° C. to 20° C., and a pressure of 0.1 kgf/cm2to 1.0 kgf/cm2, however, the temperature and the pressure are not limited thereto. By the processes of separating the second reaction product from the reactor and introducing the second reaction product to a distillation column and a condenser sequentially, the liquefied second alpha-methylstyrene and unreacted materials, and the water are divided into two levels in a trap. In addition, the water may be separated apart, and the second alpha-methylstyrene and the unreacted materials may be recirculated to the reactor. In one embodiment of the present application, the temperature inside the reactor may be 135° C. or higher, may be 138° C. or higher, and 150° C. or lower during the dehydration reaction. When the temperature inside the reactor is lower than 135° C. during the dehydration reaction, the dehydration reaction, which is an endothermic reaction, may not be readily conducted. In addition, when the temperature inside the reactor is higher than 150° C. during the dehydration reaction, evaporation of cumene may increase since cumene and alpha-methylstyrene have boiling points of 152.4° C. and 166° C., respectively, and an effect of increasing the acid catalyst concentration inside the reactor may reduce a yield of the alpha-methylstyrene. In one embodiment of the present application, the pressure inside the reactor may be from 400 torr to 700 torr, and may be from 450 torr to 650 torr during the dehydration reaction. When the pressure inside the reactor decreases during the dehydration reaction, boiling points of the reactants and the products decrease, and alpha-methylstyrene and unreacted materials evaporating to the distillation column may increase. This leads to an effect of increasing the acid catalyst concentration in the reactor relatively increasing the amount of alpha-methylstyrene converted to an alpha-methylstyrene dimer, and a yield of the alpha-methylstyrene may decrease. Accordingly, the yield of the produced alpha-methylstyrene may be enhanced when satisfying the above-described pressure inside the reactor during the dehydration reaction. In one embodiment of the present application, the reactor is a continuous stirred tank reactor (CSTR), and the dehydration reaction may be conducted for 15 minutes to 60 minutes, and may be conducted for 25 minutes to 50 minutes. When the residence time in the reactor increases, the reaction of converting alpha-methylstyrene to an alpha-methylstyrene dimer occurs more, which may reduce a yield of the alpha-methylstyrene, and an amount of the alpha-methylstyrene produced within the same time period may decrease. Accordingly, the yield of the produced alpha-methylstyrene may be enhanced when satisfying the above-described time during which the dehydration reaction is conducted. In one embodiment of the present application, the method for preparing alpha-methylstyrene may further comprise separating the first reaction product comprising first alpha-methylstyrene and the recirculated second alpha-methylstyrene and unreacted materials from the reactor. A process diagram of the method for preparing alpha-methylstyrene according to one embodiment of the present application is schematically illustrated inFIG.1. As illustrated inFIG.1, the method for preparing alpha-methylstyrene according to one embodiment of the present application comprises dehydrating a dimethylbenzyl alcohol solution (20) in a reactor (30) under an acid catalyst (10) to prepare alpha-methylstyrene, wherein a reaction product after the dehydration reaction comprises a first reaction product comprising first alpha-methylstyrene; and a second reaction product (50) comprising vapor (H2O), second alpha-methylstyrene and unreacted materials, a temperature inside the reactor (30) during the dehydration reaction is 135° C. or higher, and the method comprises, after separating the second reaction product (50) from the reactor (30), separating the second alpha-methylstyrene and the unreacted materials (90) comprised in the second reaction product (50), and recirculating the second alpha-methylstyrene and the unreacted materials (90) to the reactor (30). In addition, the method of separating the second alpha-methylstyrene and the unreacted materials (90) comprised in the second reaction product (50) may comprise processes of separating the second reaction product (50) comprising vapor (H2O), the second alpha-methylstyrene and the unreacted materials from the reactor (30), and then introducing the second reaction product (50) to a distillation column (60) and a condenser (70) sequentially. The method for preparing alpha-methylstyrene according to one embodiment of the present application is capable of enhancing a conversion ratio of dimethylbenzyl alcohol, and capable of increasing a yield of the prepared alpha-methylstyrene. Hereinafter, the present application will be described in detail with reference to examples in order to specifically describe the present application. However, examples according to the present application may be modified to various different forms, and the scope of the present application is not construed as being limited to the examples described below. Examples of the present application are provided in order to more fully describe the present application to those having average knowledge in the art. EXAMPLE Example 1 To a continuous stiffed tank reactor (CSTR), a dimethylbenzyl alcohol solution (300 g) and sulfuric acid (0.0225 g) were introduced. As the dimethylbenzyl alcohol solution, a solution comprising dimethylbenzyl alcohol in 28.6% by weight, acetophenone in 0.2% by weight, cumyl hydroperoxide in 1.0% by weight, alpha-methylstyrene in 0.01% by weight, cumene in 67.0% by weight, dicumyl peroxide in 0.2% by weight, an alpha-methylstyrene dimer in 0.02% by weight and water in 2.97% by weight was used. A content of the sulfuric acid was approximately 262 ppm based on a total weight of the dimethylbenzyl alcohol of the dimethylbenzyl alcohol solution. A residence time of 30 minutes in the reactor was used as a standard, and the reactant was introduced at 10 g/min and the sulfuric acid was introduced at 0.00075 g/min to conduct a dehydration reaction. Herein, a temperature inside the reactor was 140.4° C., a pressure inside the reactor was 550 torr, and a stirring rate of the reactor was 450 rpm. As in the process diagram ofFIG.1, a second reaction product comprising vapor (H2O), second alpha-methylstyrene and unreacted materials was separated from the reactor at 1.17 ml/min, and introduced to a distillation column and a condenser sequentially. A temperature of the distillation column was 94.5° C., and a temperature of the condenser was 5° C. The second alpha-methylstyrene and the unreacted materials separated through the condenser were recirculated to the reactor at 0.68 ml/min. In addition, as in reference numeral40of the process diagram ofFIG.1, a reaction product comprising alpha-methylstyrene and unreacted materials was released from the reactor at 9.5 g/min. Example 2 A process was conducted in the same manner as in Example 1 except that the temperature inside the reactor was adjusted to 140.8° C., and the pressure inside the reactor was adjusted to 650 torr. Herein, a flow rate of the second reaction product separated from the reactor was 0.95 ml/min, a flow rate of the second alpha-methylstyrene and the unreacted materials recirculated to the reactor was 0.55 ml/min, and a released amount of the final reaction product was 9.6 g/min. Comparative Example 1 A process was conducted in the same manner as in Example 1 except that the temperature inside the reactor was adjusted to 128.5° C. Herein, a flow rate of the second reaction product separated from the reactor was 0.7 ml/min, a flow rate of the second alpha-methylstyrene and the unreacted materials recirculated to the reactor was 0.5 ml/min, and a released amount of the final reaction product was 9.8 g/min. Comparative Example 2 A process was conducted in the same manner as in Example 1 except that the temperature inside the reactor was adjusted to 133.4° C. Herein, a flow rate of the second reaction product separated from the reactor was 1.50 ml/min, a flow rate of the second alpha-methylstyrene and the unreacted materials recirculated to the reactor was 1.17 ml/min, and a released amount of the final reaction product was 9.7 g/min. Comparative Example 3 A process was conducted in the same manner as in Example 1 except that the temperature inside the reactor was adjusted to 137.2° C., and the introduced amount of the sulfuric acid was adjusted to 0.00572 g/min. A content of the sulfuric acid was approximately 2,000 ppm based on a total weight of the dimethylbenzyl alcohol of the dimethylbenzyl alcohol solution. Herein, a flow rate of the second reaction product separated from the reactor was 1.03 ml/min, a flow rate of the second alpha-methylstyrene and the unreacted materials recirculated to the reactor was 0.65 ml/min, and a released amount of the final reaction product was 9.6 g/min. Comparative Example 4 A process was conducted in the same manner as in Example 1 except that the temperature inside the reactor was adjusted to 128° C., the introduced amount of the sulfuric acid was adjusted to 0.002808 g/min, and a dimethylbenzyl alcohol solution (solution comprising dimethylbenzyl alcohol in 93.6% by weight, cumyl hydroperoxide in 0.84% by weight, cumene in 3.42% by weight, dicumyl peroxide in 0.89% by weight, an alpha-methylstyrene dimer in 0.39% by weight and water in 0.86% by weight) was used. A content of the sulfuric acid was approximately 300 ppm based on a total weight of the dimethylbenzyl alcohol of the dimethylbenzyl alcohol solution. Herein, a flow rate of the second reaction product separated from the reactor was 0.74 ml/min, a flow rate of the second alpha-methylstyrene and the unreacted materials recirculated to the reactor was 0.41 ml/min, and a released amount of the final reaction product was 9.7 g/min. Comparative Example 5 A process was conducted in the same manner as in Example 1 except that the temperature inside the reactor was adjusted to 135° C., the introduced amount of the sulfuric acid was adjusted to 0.000858 g/min, and the process of recirculating the second alpha-methylstyrene and the unreacted materials was not comprised. A content of the sulfuric acid was approximately 300 ppm based on a total weight of the dimethylbenzyl alcohol of the dimethylbenzyl alcohol solution. Experimental Example Each of the reaction products comprising alpha-methylstyrene prepared in the examples and the comparative examples was analyzed, and the results are shown in the following Table 1. The reaction product comprising alpha-methylstyrene was analyzed by high-performance liquid chromatography (HPLC). Condition of HPLC Analysis Column: Lichrosorb RP-18 (4.6 m×0.2 mm×10 μm) and Guard columnEluent: mobile phase A/mobile phase B=97/3 (v/v, %) to 3 minutesmobile phase A/mobile phase B=10/90 (v/v, %) from 3 minutes to 24 minutesmobile phase A/mobile phase B=97/3 (v/v, %) from 24 minutes to 30 minutesFlow rate: 1 mL/minColumn temperature: 40° C.Run time: 30 minInjection volume: 10 μl In the present application, the ‘yield (%)’ is defined as a value obtained by dividing the number of moles of alpha-methylstyrene, a product, by the number of moles of dimethylbenzyl alcohol, a raw material. For example, the yield may be represented by the following equation. Yield(%)=[(number of moles of produced alpha-methylstyrene)/(number of moles of supplied dimethylbenzyl alcohol)]×100 In the present application, the ‘conversion ratio (%)’ refers to a ratio of a reactant converting to a product, and for example, the conversion ratio of dimethylbenzyl alcohol may be represented by the following equation. Conversion ratio(%)=[(number of moles of reacted dimethylbenzyl alcohol)/(number of moles of supplied dimethylbenzyl alcohol)]×100 In the present application, the ‘selectivity (%)’ is defined as a value obtained by dividing the amount of change in alpha-methylstyrene by the amount of change in dimethylbenzyl alcohol. For example, the selectivity may be represented by the following equation. Selectivity(%)=[(number of moles of produced alpha-methylstyrene)/(number of moles of reacted dimethylbenzyl alcohol)]×100 TABLE 1DMBAAlpha-Alpha-ConversionMethylstyreneMethylstyreneRatio (%)Selectivity (%)Yield (%)Example 197.999.797.6Example 296.8100.297.0Comparative95.998.094.0Example 1Comparative95.798.394.1Example 2Comparative99.5391.0690.63Example 3Comparative99.6685.0284.73Example 4Comparative99.7987.8787.69Example 5 Cumyl hydroperoxide comprised in the dimethylbenzyl alcohol solution may produce dimethylbenzyl alcohol and oxygen under a sulfuric acid catalyst, and the dimethylbenzyl alcohol produced by the cumyl hydroperoxide may further produce alpha-methylstyrene under a sulfuric acid catalyst, and therefore, selectivity of the alpha-methylstyrene may be greater than 100% as in the result of Example 2. As seen from the above-described results, it was identified that, when the constitutions of the method for preparing alpha-methylstyrene according to one embodiment of the present application are not satisfied, a side reaction of converting alpha-methylstyrene to an alpha-methylstyrene dimer is further accelerated reducing selectivity and yield of the alpha-methylstyrene. Accordingly, the method for preparing alpha-methylstyrene according to one embodiment of the present application is capable of enhancing selectivity of the prepared alpha-methylstyrene, and is capable of increasing a yield of the prepared alpha-methylstyrene. | 22,621 |
11858875 | DETAILED DESCRIPTION In view of an increasing demand for environmentally friendly and low toxicity chemical compounds, it is recognized that there exists an ongoing need for new working fluids that provide further reductions in environmental impact and toxicity, and which can meet the performance requirements (e.g., nonflammability, solvency, stability, and operating temperature range) of a variety of different applications (e.g., heat transfer, two-phase immersion cooling, foam blowing agents, solvent cleaning, deposition coating solvents, and electrolyte solvents and additives), and be manufactured cost-effectively. Generally, the present disclosure relates to propenylamine compounds that include at least one catenary nitrogen atom and are highly enriched in the E (or trans) isomer. The present disclosure also describes high yield methods of making such E-enriched compounds. Surprisingly, it has been discovered that the E-enriched propenylamines have significantly shorter atmospheric lifetimes compared to the corresponding Z (or cis) isomers or an equilibrium mixture of E and Z isomers and, therefore, have correspondingly lower global warming potentials. The propenylamines of the present disclosure are also generally non-flammable, have zero ozone depletion potential, and provide low toxicity for safe handling. As used herein, “catenated heteroatom” means an atom other than carbon (for example, oxygen, nitrogen, or sulfur) that is bonded to at least two carbon atoms in a carbon chain (linear or branched or within a ring) so as to form a carbon-heteroatom-carbon linkage. As used herein, “fluoro-” (for example, in reference to a group or moiety, such as in the case of “fluoroalkylene” or “fluoroalkyl” or “fluorocarbon”) or “fluorinated” means (i) partially fluorinated such that there is at least one carbon-bonded hydrogen atom, or (ii) perfluorinated. As used herein, “perfluoro-” (for example, in reference to a group or moiety, such as in the case of “perfluoroalkylene” or “perfluoroalkyl” or “perfluorocarbon”) or “perfluorinated” means completely fluorinated such that, except as may be otherwise indicated, there are no carbon-bonded hydrogen atoms replaceable with fluorine. As used herein, the singular forms “a”, “an”, and “the” include plural referents unless the content clearly dictates otherwise. As used in this specification and the appended embodiments, the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise. As used herein, the recitation of numerical ranges by endpoints includes all numbers subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.8, 4, and 5). Unless otherwise indicated, all numbers expressing quantities or ingredients, measurement of properties and so forth used in the specification and embodiments are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached listing of embodiments can vary depending upon the desired properties sought to be obtained by those skilled in the art utilizing the teachings of the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claimed embodiments, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. In some embodiments, the present disclosure is directed to propenylamines of general formula (1). The propenylamines of general formula (1) can exist in one of two isomeric forms, the E or Z isomer, which are depicted below in general formulas (1A) and 1(B), respectively. Surprisingly, it has been discovered that the E-isomer [general formula (1A)] has a significantly shorter atmospheric lifetime than the Z isomer [Structure (1B)], and correspondingly lower global warming potential (GWP). Therefore, it is advantageous, from an environmental sustainability standpoint, if the propenylamines could be enriched in the lower GWP E-isomer (thus reducing the average GWP of the mixture). In some embodiments, the present disclosure is further directed to methods of making the above-described E-isomer enriched propenylamines of general formula (1). However, heretofore, this has not been possible, since all known methods of preparing such propenylamines lead to a mixture of E and Z isomers, with the thermodynamically more stable Z isomer generally present as the major isomer. Additionally, known processes designed to isomerize the E and Z isomers would tend to favor the thermodynamically more stable Z isomer. Still further, the boiling points of the E and Z isomers are typically very similar (within a few degrees C. or less of each other), thus making separation by distillation either impossible or impractical for achieving any significant level of enrichment of the E isomer. The present disclosure provides a solution to this problem in that it broadly describes propenylamines that are highly enriched in the thermodynamically less stable E isomer and high yield methods for preparing such E-enriched mixtures without sacrificing overall yield and avoiding the need to dispose of the less desirable Z isomer. In some embodiments, the present disclosure is directed to compositions that include the propenylamines of general formula (1), wherein at least 60 wt. %, 70% wt. %, 80 wt. %, 90 wt. %, 95 wt. % or 98 wt. % of the propenylamines are in the form of the E isomer (formula 1A) (the remainder being the Z isomer (formula 1B)), based on the total weight of the propenylamines of general formula (1) in the composition. In illustrative embodiments, Rf1and Rf2in general formula (1) may be, independently, linear or branched perfluoroalkyl groups having 1-8 carbon atoms, 1-6 carbon atoms, or 1-4 carbon atoms. In further embodiments, Rf1and Rf2may be bonded together to form a ring structure having 4-8 carbon atoms, 4-6 carbon atoms, or 4 carbon atoms. Optionally, Rf1and Rf2may include one or more catenated heteroatoms. In some embodiments, if Rf1and Rf2are bonded together to form a ring structure that comprises a second nitrogen heteroatom, said second nitrogen heteroatom may be tertiary and may be bonded to a perfluoroalkyl group having 1-3 or 2-3 carbon atoms. In various embodiments, representative examples of the compounds of general formula (1) include the following: In some embodiments, the E isomer enriched propenylamine compounds of the present disclosure may be hydrophobic, relatively chemically unreactive, and thermally stable. As discussed above, the E isomer enriched propenylamine compounds may have a low environmental impact. In this regard, the E isomer enriched 1-propenylamine compounds may have a global warming potential (GWP, over 100 year ITH)) of less than 500, 300, 200, 100, 80, or less than 60. As used herein, GWP is a relative measure of the global warming potential of a compound based on the structure of the compound. The GWP of a compound, as defined by the Intergovernmental Panel on Climate Change (IPCC) in 1990 and updated in 2007, is calculated as the warming due to the release of 1 kilogram of a compound relative to the warming due to the release of 1 kilogram of CO2over a specified integration time horizon (ITH). GWPi(t′)=∫0ITHai[C(t)]dt∫0ITHaCO2[CCO2(t)]dt=∫0ITHaiCoie-t/τidt∫0ITHaCO2[CCO2(t)]dt In this equation ad is the radiative forcing per unit mass increase of a compound in the atmosphere (the change in the flux of radiation through the atmosphere due to the IR absorbance of that compound), C is the atmospheric concentration of a compound, τ is the atmospheric lifetime of a compound, t is time, and i is the compound of interest. The commonly accepted ITH is 100 years representing a compromise between short-term effects (20 years) and longer-term effects (500 years or longer). The concentration of an organic compound, i, in the atmosphere is assumed to follow pseudo first order kinetics (i.e., exponential decay). The concentration of CO2over that same time interval incorporates a more complex model for the exchange and removal of CO2from the atmosphere (the Bern carbon cycle model). The perfluorinated propenyl amines of general formula (1) can be prepared by electrochemical perfluorination of the appropriate nitrogen containing hydrocarbon carboxylate derivatives followed by decarboxylation of the perfluorinated nitrogen-containing carboxylates, carbonyl fluorides, or esters using procedures that are well known in the art, including those described in T. Abe, JP 01070444A; T. Abe, JP 0107445A; or M. Bulinski, WO 2015/095285, which are herein incorporated by reference in their entirety. However, as discussed above, such methods yield a mixture of perfluorinated E- and Z 1-propenylamines in which the thermodynamically preferred Z isomer is the major component. In some embodiments, the present disclosure is directed to high yield and selective methods of synthesizing the propenyl amines of general formula (1) that are enriched in the E isomer, without resorting to impractical separation methods and the cost and waste associated with disposal of the higher GWP Z isomer. In some embodiments, the method includes selectively isomerizing a perfluorinated allylamine of general formula (2) over an isomerization catalyst to predominantly form the E-1-propenylamine of general formula (1A), while avoiding significant formation of the thermodynamically more stable Z-1-propenylamine of general formula (1B). In some embodiments, the synthesis methods of the present disclosure may include a catalytic isomerization process which provides a mechanism for isomerizing a perfluorinated allylamine of general structure (2) to the corresponding E-1-propenylamine of general structure (1A) with a surprisingly high degree of selectivity. In some embodiments, the process may include catalytically isomerizing the terminal olefin of the perfluorinated allylamine to the corresponding internal olefin, with a surprisingly strong preference for the E (vs. Z) internal olefin isomer (even though the Z isomer is the thermodynamically more stable isomer). In some embodiments, the catalytic isomerization process may be described by the reaction shown in Scheme 1, in which the E-1-propenyl amine is the major isomerization product and the Z-1-propenylamine is the minor isomerization product. In some embodiments, catalysts for use in the catalytic isomerization process shown in Scheme 1 may include Lewis acidic metal fluorides and metalloid fluorides including, for example, any or all of TiF4, ZrF4, NbF5, TaF5, BF3, SbF5. In various embodiments, the catalyst may include any or all of TiF4, NbF5, TaF5, and SbF5. In some embodiments, the catalyst may include any or all of NbF5and TaF5. In illustrative embodiments, in addition or as an alternative to the aforementioned catalysts, catalysts suitable for use in the methods of the present disclosure may include certain other fluorinated Lewis acids (including perfluorinated Lewis acids and certain Lewis acid mixed chlorofluorides), such as any or all of ACF (aluminum chlorofluoride), rare earth metal fluorides (including lanthanide and actinide metal fluorides), antimony chlorofluorides (including SbCl2F3and SbCl4F), as well as the Bronsted acid, HSbF6. In other embodiments, the catalyst may include Lewis acidic metal chlorides and metalloid chlorides, including, for example, any or all of AlCl3, SbCl5, TiCl4, and the like. It is believed that the latter Lewis acid catalysts form mixed chlorofluorides in situ via a halogen exchange reaction with the starting fluorinated allyl amine and it is these mixed chlorofluorides that are the active isomerization catalysts. Surprisingly, it was discovered that the Lewis acidic metal chlorides and metalloid chlorides are as effective as their fluoride counterparts, which is significant because the chlorides may be obtained at an appreciably lower materials cost. The Lewis acidic metal and metalloid fluorides, chlorofluorides, and chlorides useful as catalysts in the processes of the present disclosure may be chosen from groups 3 through 15 of the periodic table (modern IUPAC convention), including the lanthanide and actinides series. In one embodiment the catalysts are chosen from groups 4, 5, 13, and 15 of the periodic table. In some embodiments, the reaction described in Scheme 1 may be carried out neat (i.e., in the absence of solvent), although inert solvents such as perfluorinated hydrocarbons may also be employed, if desired. Reaction temperature and reaction time may be selected based on the catalyst employed. For example, with some catalysts, low temperatures (e.g., ≤0° C.) and short reaction times (e.g., ˜1 hr) may be employed, because at higher temperatures the catalyst will catalyze E/Z isomerization, thus resulting in a loss of selectivity. As an additional example, reaction temperatures between 20-100° C. and higher may be employed to increase the rates of reaction such that the isomerization reaction is complete or nearly complete in a period of approximately 1-20 hours or less. When using the catalysts of the present disclosure, the catalytic isomerization process of Scheme 1 may proceed with negligible side reactions, thus no or relatively few (less than 5%, 3%, 2%, or 1% by weight) detectable side products are formed, which might otherwise contaminate the propenylamine product. In some embodiments, the perfluorinated allylamines of general formula (2) may be prepared by methods that are well known in the art, including those methods described in T. Abe, JP 01070444A; and T. Abe, JP 0107445A, both of which are incorporated herein by reference in their entirety and described in Scheme 2 The first step consists of a Michael addition of a secondary amine (RH1(RH2)NH) to methyl methacrylate. The respective beta-aminoesters undergo electrochemical fluorination to afford the desired perfluorinated acid fluoride intermediates which are subjected to thermolysis in the presence of Na2CO3to give a mixture of perfluorinated allylic amines and perfluorinated 1-aminopropenes. The desired perfluorinated allyl amine products can be purified by distillation and have been used in pure form for fluoropolymer synthesis (Y. Hayakawa et al.Polymer1995, 36, 2807) and for additions by bis(trifluoromethyl)amino-oxyl reagent (G. Newsholme et al.J. Fluorine Chem.1994, 69, 163). In some embodiments, the present disclosure is further directed to working fluids that include the above-described propenylamine compounds as a major component. For example, the working fluids may include at least 25%, at least 50%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% by weight of the above-described propenylamine compounds based on the total weight of the working fluid. In addition to the propenylamine compounds, the working fluids may include a total of up to 75%, up to 50%, up to 30%, up to 20%, up to 10%, or up to 5% by weight of one or more of the following components: alcohols, ethers, alkanes, alkenes, haloalkenes, perfluorocarbons, perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters, ketones, oxiranes, aromatics, siloxanes, hydrochlorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochloroolefins, hydrochlorofluoroolefins, hydrofluoroethers, or mixtures thereof, based on the total weight of the working fluid. Such additional components can be chosen to modify or enhance the properties of a composition for a particular use. In some embodiments, the present disclosure is further directed to an apparatus for heat transfer that includes a device and a mechanism for transferring heat to or from the device. The mechanism for transferring heat may include a heat transfer working fluid that includes a 1-propenylamine compound of the present disclosure. The provided apparatus for heat transfer may include a device. The device may be a component, work-piece, assembly, etc. to be cooled, heated or maintained at a predetermined temperature or temperature range. Such devices include electrical components, mechanical components and optical components. Examples of devices of the present disclosure include, but are not limited to microprocessors, wafers used to manufacture semiconductor devices, power control semiconductors, electrical distribution switch gear, power transformers, circuit boards, multi-chip modules, packaged and unpackaged semiconductor devices, lasers, chemical reactors, fuel cells, heat exchangers, and electrochemical cells. In some embodiments, the device can include a chiller, a heater, or a combination thereof. In yet other embodiments, the devices can include electronic devices, such as processors, including microprocessors. As these electronic devices become more powerful, the amount of heat generated per unit time increases. Therefore, the mechanism of heat transfer plays an important role in processor performance. The heat-transfer fluid typically has good heat transfer performance, good electrical compatibility (even if used in “indirect contact” applications such as those employing cold plates), as well as low toxicity, low (or non-) flammability and low environmental impact. Good electrical compatibility suggests that the heat-transfer fluid candidate exhibit high dielectric strength, high volume resistivity, and poor solvency for polar materials. Additionally, the heat-transfer fluid should exhibit good mechanical compatibility, that is, it should not affect typical materials of construction in an adverse manner. The provided apparatus may include a mechanism for transferring heat. The mechanism may include a heat transfer fluid. The heat transfer fluid may include one or more 1-propenylamine compounds of the present disclosure. Heat may be transferred by placing the heat transfer mechanism in thermal contact with the device. The heat transfer mechanism, when placed in thermal contact with the device, removes heat from the device or provides heat to the device, or maintains the device at a selected temperature or temperature range. The direction of heat flow (from device or to device) is determined by the relative temperature difference between the device and the heat transfer mechanism. The heat transfer mechanism may include facilities for managing the heat-transfer fluid, including, but not limited to pumps, valves, fluid containment systems, pressure control systems, condensers, heat exchangers, heat sources, heat sinks, refrigeration systems, active temperature control systems, and passive temperature control systems. Examples of suitable heat transfer mechanisms include, but are not limited to, temperature controlled wafer chucks in plasma enhanced chemical vapor deposition (PECVD) tools, temperature-controlled test heads for die performance testing, temperature-controlled work zones within semiconductor process equipment, thermal shock test bath liquid reservoirs, and constant temperature baths. In some systems, such as etchers, ashers, PECVD chambers, vapor phase soldering devices, and thermal shock testers, the upper desired operating temperature may be as high as 170° C., as high as 200° C., or even as high as 230° C. Heat can be transferred by placing the heat transfer mechanism in thermal contact with the device. The heat transfer mechanism, when placed in thermal contact with the device, removes heat from the device or provides heat to the device, or maintains the device at a selected temperature or temperature range. The direction of heat flow (from device or to device) is determined by the relative temperature difference between the device and the heat transfer mechanism. The provided apparatus can also include refrigeration systems, cooling systems, testing equipment and machining equipment. In some embodiments, the provided apparatus can be a constant temperature bath or a thermal shock test bath. In some embodiments, the present disclosure is directed to a fire extinguishing composition. The composition may include one or more propenylamine compounds of the present disclosure and one or more co-extinguishing agents. In illustrative embodiments, the co-extinguishing agent may include hydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons, perfluoropolyethers, hydrofluoroethers, hydrofluoropolyethers, chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons, hydrobromocarbons, iodofluorocarbons, fluorinated ketones, hydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons, perfluoropolyethers, hydrofluoroethers, hydrofluoropolyethers, chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons, iodofluorocarbons, hydrobromofluorocarbons, fluorinated ketones, hydrobromocarbons, fluorinated olefins, hydrofluoroolefins, fluorinated sulfones, fluorinated vinylethers, unsaturated fluoro-ethers, bromofluoroolefins, chlorofluorolefins, iodofluoroolefins, fluorinated vinyl amines, fluorinated aminopropenes and mixtures thereof. Such co-extinguishing agents can be chosen to enhance the extinguishing capabilities or modify the physical properties (e.g., modify the rate of introduction by serving as a propellant) of an extinguishing composition for a particular type (or size or location) of fire and can preferably be utilized in ratios (of co-extinguishing agent to propenylamine compound) such that the resulting composition does not form flammable mixtures in air. In some embodiments, the propenylamine compounds and the co-extinguishing agent may be present in the fire extinguishing composition in amounts sufficient to suppress or extinguish a fire. The propenylamine compounds and the co-extinguishing agent can be in a weight ratio of from about 9:1 to about 1:9. In some embodiments, the present disclosure is directed to an apparatus for converting thermal energy into mechanical energy in a Rankine cycle. The apparatus may include a working fluid that includes one or more propenylamine compounds of the present disclosure. The apparatus may further include a heat source to vaporize the working fluid and form a vaporized working fluid, a turbine through which the vaporized working fluid is passed thereby converting thermal energy into mechanical energy, a condenser to cool the vaporized working fluid after it is passed through the turbine, and a pump to recirculate the working fluid. In some embodiments, the present disclosure relates to a process for converting thermal energy into mechanical energy in a Rankine cycle. The process may include using a heat source to vaporize a working fluid that includes one or more propenylamine compounds of the present disclosure to form a vaporized working fluid. In some embodiments, the heat is transferred from the heat source to the working fluid in an evaporator or boiler. The vaporized working fluid may pressurized and can be used to do work by expansion. The heat source can be of any form such as from fossil fuels, e.g., oil, coal, or natural gas. Additionally, in some embodiments, the heat source can come from nuclear power, solar power, or fuel cells. In other embodiments, the heat can be “waste heat” from other heat transfer systems that would otherwise be lost to the atmosphere. The “waste heat,” in some embodiments, can be heat that is recovered from a second Rankine cycle system from the condenser or other cooling device in the second Rankine cycle. An additional source of “waste heat” can be found at landfills where methane gas is flared off. In order to prevent methane gas from entering the environment and thus contributing to global warming, the methane gas generated by the landfills can be burned by way of “flares” producing carbon dioxide and water which are both less harmful to the environment in terms of global warming potential than methane. Other sources of “waste heat” that can be useful in the provided processes are geothermal sources and heat from other types of engines such as gas turbine engines that give off significant heat in their exhaust gases and to cooling liquids such as water and lubricants. In the provided process, the vaporized working fluid may expanded though a device that can convert the pressurized working fluid into mechanical energy. In some embodiments, the vaporized working fluid is expanded through a turbine which can cause a shaft to rotate from the pressure of the vaporized working fluid expanding. The turbine can then be used to do mechanical work such as, in some embodiments, operate a generator, thus generating electricity. In other embodiments, the turbine can be used to drive belts, wheels, gears, or other devices that can transfer mechanical work or energy for use in attached or linked devices. After the vaporized working fluid has been converted to mechanical energy the vaporized (and now expanded) working fluid can be condensed using a cooling source to liquefy for reuse. The heat released by the condenser can be used for other purposes including being recycled into the same or another Rankine cycle system, thus saving energy. Finally, the condensed working fluid can be pumped by way of a pump back into the boiler or evaporator for reuse in a closed system. The desired thermodynamic characteristics of organic Rankine cycle working fluids are well known to those of ordinary skill and are discussed, for example, in U.S. Pat. Appl. Publ. No. 2010/0139274 (Zyhowski et al.) The greater the difference between the temperature of the heat source and the temperature of the condensed liquid or a provided heat sink after condensation, the higher the Rankine cycle thermodynamic efficiency. The thermodynamic efficiency is influenced by matching the working fluid to the heat source temperature. The closer the evaporating temperature of the working fluid to the source temperature, the higher the efficiency of the system. Toluene can be used, for example, in the temperature range of 79° C. to about 260° C., however toluene has toxicological and flammability concerns. Fluids such as 1,1-dichloro-2,2,2-trifluoroethane and 1,1,1,3,3-pentafluoropropane can be used in this temperature range as an alternative. But 1,1-dichloro-2,2,2-trifluoroethane can form toxic compounds below 300° C. and need to be limited to an evaporating temperature of about 93° C. to about 121° C. Thus, there is a desire for other environmentally-friendly Rankine cycle working fluids with higher critical temperatures so that source temperatures such as gas turbine and internal combustion engine exhaust can be better matched to the working fluid. In some embodiments, the present disclosure relates to the use of the propenylamine compounds of the present disclosure as nucleating agents in the production of polymeric foams and in particular in the production of polyurethane foams and phenolic foams. In this regard, in some embodiments, the present disclosure is directed to a foamable composition that includes one or more blowing agents, one or more foamable polymers or precursor compositions thereof, and one or more nucleating agents that include a 1-propenylamine compound of the present disclosure. In some embodiments, a variety of blowing agents may be used in the provided foamable compositions including liquid or gaseous blowing agents that are vaporized in order to foam the polymer or gaseous blowing agents that are generated in situ in order to foam the polymer. Illustrative examples of blowing agents include hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), hydrochlorocarbons (HCCs), iodofluorocarbons (IFCs), hydrocarbons, hydrofluoroolefins (HFOs) and hydrofluoroethers (HFEs). The blowing agent for use in the provided foamable compositions can have a boiling point of from about −45° C. to about 100° C. at atmospheric pressure. Typically, at atmospheric pressure the blowing agent has a boiling point of at least about 15° C., more typically between about 20° C. and about 80° C. The blowing agent can have a boiling point of between about 30° C. and about 65° C. Further illustrative examples of blowing agents that can be used include aliphatic and cycloaliphatic hydrocarbons having about 5 to about 7 carbon atoms, such as n-pentane and cyclopentane, esters such as methyl formate, HFCs such as CF3CF2CHFCHFCF3, CF3CH2CF2H, CF3CH2CF2CH3, CF3CF2H, CH3CF2H(HFC-152a), CF3CH2CH2CF3and CHF2CF2CH2F, HCFCs such as CH3CCl2F, CF3CHCl2, and CF2HCl, HCCs such as 2-chloropropane, and IFCs such as CF3I, and HFEs such as C4F9OCH3and HFOs such as CF3CF═CH2, CF3CH═CHF, CF3CH═CHCl, and CF3CH═CHCF3In certain formulations CO2generated from the reaction of water with foam precursor such as an isocyanate can be used as a blowing agent. In various embodiments, the provided foamable composition may also include one or more foamable polymers or a precursor composition thereof. Foamable polymers suitable for use in the provided foamable compositions include, for example, polyolefins, e.g., polystyrene, poly(vinyl chloride), and polyethylene. Foams can be prepared from styrene polymers using conventional extrusion methods. The blowing agent composition can be injected into a heat-plastified styrene polymer stream within an extruder and admixed therewith prior to extrusion to form foam. Representative examples of suitable styrene polymers include, for example, the solid homopolymers of styrene, α-methylstyrene, ring-alkylated styrenes, and ring-halogenated styrenes, as well as copolymers of these monomers with minor amounts of other readily copolymerizable olefinic monomers, e.g., methyl methacrylate, acrylonitrile, maleic anhydride, citraconic anhydride, itaconic anhydride, acrylic acid, N-vinylcarbazole, butadiene, and divinylbenzene. Suitable vinyl chloride polymers include, for example, vinyl chloride homopolymer and copolymers of vinyl chloride with other vinyl monomers. Ethylene homopolymers and copolymers of ethylene with, e.g., 2-butene, acrylic acid, propylene, or butadiene may also be useful. Mixtures of different types of polymers can be employed. In various embodiments, the foamable compositions of the present disclosure may have a molar ratio of nucleating agent to blowing agent of no more than 1:50, 1:25, 1:9, or 1:7, 1:3, or 1:2. Other conventional components of foam formulations can, optionally, be present in the foamable compositions of the present disclosure. For example, cross-linking or chain-extending agents, foam-stabilizing agents or surfactants, catalysts and fire-retardants can be utilized. Other possible components include fillers (e.g., carbon black), colorants, fungicides, bactericides, antioxidants, reinforcing agents, antistatic agents, and other additives or processing aids. In some embodiments, polymeric foams can be prepared by vaporizing at least one liquid or gaseous blowing agent or generating at least one gaseous blowing agent in the presence of at least one foamable polymer or a precursor composition thereof and a nucleating agent as described above. In further embodiments, polymeric foams can be prepared using the provided foamable compositions by vaporizing (e.g., by utilizing the heat of precursor reaction) at least one blowing agent in the presence of a nucleating agent as described above, at least one organic polyisocyanate and at least one compound containing at least two reactive hydrogen atoms. In making a polyisocyanate-based foam, the polyisocyanate, reactive hydrogen-containing compound, and blowing agent composition can generally be combined, thoroughly mixed (using, e.g., any of the various known types of mixing head and spray apparatus), and permitted to expand and cure into a cellular polymer. It is often convenient, but not necessary, to preblend certain of the components of the foamable composition prior to reaction of the polyisocyanate and the reactive hydrogen-containing compound. For example, it is often useful to first blend the reactive hydrogen-containing compound, blowing agent composition, and any other components (e.g., surfactant) except the polyisocyanate, and to then combine the resulting mixture with the polyisocyanate. Alternatively, all components of the foamable composition can be introduced separately. It is also possible to pre-react all or a portion of the reactive hydrogen-containing compound with the polyisocyanate to form a prepolymer. In some embodiments, the present disclosure is directed to dielectric fluids that include one or more propenylamine compounds of the present disclosure, as well as to electrical devices (e.g., capacitors, switchgear, transformers, or electric cables or buses) that include such dielectric fluids. For purposes of the present application, the term “dielectric fluid” is inclusive of both liquid dielectrics and gaseous dielectrics. The physical state of the fluid, gaseous or liquid, is determined at the operating conditions of temperature and pressure of the electrical device in which it is used. In some embodiments, the dielectric fluids include one or more propenylamine compounds of the present disclosure and, optionally, one or more second dielectric fluids. Suitable second dielectric fluids include, for example, air, nitrogen, helium, argon, and carbon dioxide, or combinations thereof. The second dielectric fluid may be a non-condensable gas or an inert gas. Generally, the second dielectric fluid may be used in amounts such that vapor pressure is at least 70 kPa at 25° C., or at the operating temperature of the electrical device. The dielectric fluids of the present application are useful for electrical insulation and for arc quenching and current interruption equipment used in the transmission and distribution of electrical energy. Generally, there are three major types of electrical devices in which the fluids of the present disclosure can be used: (1) gas-insulated circuit breakers and current-interruption equipment, (2) gas-insulated transmission lines, and (3) gas-insulated transformers. Such gas-insulated equipment is a major component of power transmission and distribution systems. In some embodiments, the present disclosure provides electrical devices, such as capacitors, comprising metal electrodes spaced from each other such that the gaseous dielectric fills the space between the electrodes. The interior space of the electrical device may also comprise a reservoir of the liquid dielectric fluid which is in equilibrium with the gaseous dielectric fluid. Thus, the reservoir may replenish any losses of the dielectric fluid. In some embodiments, the present disclosure relates to coating compositions that include a solvent composition that one or more propenylamine compounds of the present disclosure, and one or more coating materials which are soluble or dispersible in the solvent composition. In various embodiments, the coating materials of the coating compositions may include pigments, lubricants, stabilizers, adhesives, anti-oxidants, dyes, polymers, pharmaceuticals, release agents, inorganic oxides, and the like, and combinations thereof. For example, coating materials may include perfluoropolyether, hydrocarbon, and silicone lubricants; amorphous copolymers of tetrafluoroethylene; polytetrafluoroethylene; or combinations thereof. Further examples of suitable coating materials include titanium dioxide, iron oxides, magnesium oxide, perfluoropolyethers, polysiloxanes, stearic acid, acrylic adhesives, polytetrafluoroethylene, amorphous copolymers of tetrafluoroethylene, or combinations thereof. In some embodiments, the above-described coating compositions can be useful in coating deposition, where the propenylamine compounds function as a carrier for a coating material to enable deposition of the material on the surface of a substrate. In this regard, the present disclosure further relates to a process for depositing a coating on a substrate surface using the coating composition. The process comprises the step of applying to at least a portion of at least one surface of a substrate a coating of a liquid coating composition comprising (a) a solvent composition containing one or more of the 1-propenylamine compounds; and (b) one or more coating materials which are soluble or dispersible in the solvent composition. The solvent composition can further comprise one or more co-dispersants or co-solvents and/or one or more additives (e.g., surfactants, coloring agents, stabilizers, anti-oxidants, flame retardants, and the like). Preferably, the process further comprises the step of removing the solvent composition from the coating by, e.g., allowing evaporation (which can be aided by the application of, e.g., heat or vacuum). In various embodiments, to form a coating composition, the components of the coating composition (i.e., the propenylamine compound(s), the coating material(s), and any co-dispersant(s) or co-solvent(s) utilized) can be combined by any conventional mixing technique used for dissolving, dispersing, or emulsifying coating materials, e.g., by mechanical agitation, ultrasonic agitation, manual agitation, and the like. The solvent composition and the coating material(s) can be combined in any ratio depending upon the desired thickness of the coating. For example, the coating material(s) may constitute from about 0.1 to about 10 weight percent of the coating composition. In illustrative embodiments, the deposition process of the disclosure can be carried out by applying the coating composition to a substrate by any conventional technique. For example, the composition can be brushed or sprayed (e.g., as an aerosol) onto the substrate, or the substrate can be spin-coated. In some embodiments, the substrate may be coated by immersion in the composition. Immersion can be carried out at any suitable temperature and can be maintained for any convenient length of time. If the substrate is a tubing, such as a catheter, and it is desired to ensure that the composition coats the lumen wall, the composition may be drawn into the lumen by the application of reduced pressure. In various embodiments, after a coating is applied to a substrate, the solvent composition can be removed from the coating (e.g., by evaporation). If desired, the rate of evaporation can be accelerated by application of reduced pressure or mild heat. The coating can be of any convenient thickness, and, in practice, the thickness will be determined by such factors as the viscosity of the coating material, the temperature at which the coating is applied, and the rate of withdrawal (if immersion is utilized). Both organic and inorganic substrates can be coated by the processes of the present disclosure. Representative examples of the substrates include metals, ceramics, glass, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene copolymer, natural fibers (and fabrics derived therefrom) such as cotton, silk, fur, suede, leather, linen, and wool, synthetic fibers (and fabrics) such as polyester, rayon, acrylics, nylon, or blends thereof, fabrics including a blend of natural and synthetic fibers, and composites of the foregoing materials. In some embodiments, substrates that may be coated include, for example, magnetic hard disks or electrical connectors with perfluoropolyether lubricants or medical devices with silicone lubricants. In some embodiments, the present disclosure relates to cleaning compositions that include one or more propenylamine compounds of the present disclosure, and one or more co-solvents. In some embodiments, the propenylamine compounds may be present in an amount greater than 50 weight percent, greater than 60 weight percent, greater than 70 weight percent, or greater than 80 weight percent based upon the total weight of the propenylamine compounds and the co-solvent(s). In various embodiments, the cleaning composition may further comprise a surfactant. Suitable surfactants include those surfactants that are sufficiently soluble in the fluorinated olefin, and which promote soil removal by dissolving, dispersing or displacing the soil. One useful class of surfactants are those nonionic surfactants that have a hydrophilic-lipophilic balance (HLB) value of less than about 14. Examples include ethoxylated alcohols, ethoxylatedalkyl phenols, ethoxylated fatty acids, alkylarysulfonates, glycerol esters, ethoxylated fluoroalcohols, and fluorinated sulfonamides. Mixtures of surfactants having complementary properties may be used in which one surfactant is added to the cleaning composition to promote oily soil removal and another added to promote water-soluble oil removal. The surfactant, if used, can be added in an amount sufficient to promote soil removal. Typically, surfactant is added in amounts from about 0.1 to 5.0 wt. %, preferably in amounts from about 0.2 to 2.0 wt. % of the cleaning composition. In illustrative embodiments, the co-solvent may include alcohols, ethers, alkanes, alkenes, haloalkenes, perfluorocarbons, perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters, ketones, oxiranes, aromatics, haloaromatics, siloxanes, hydrochlorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochloroolefins, hydrochlorofluoroolefins, hydrofluoroethers, or mixtures thereof. Representative examples of co-solvents which can be used in the cleaning composition include methanol, ethanol, isopropanol, t-butyl alcohol, methyl t-butyl ether, methyl t-amyl ether, 1,2-dimethoxyethane, cyclohexane, 2,2,4-trimethylpentane, n-decane, terpenes (e.g., a-pinene, camphene, and limonene), trans-1,2-dichloroethylene, cis-1,2-dichloroethylene, methylcyclopentane, decalin, methyl decanoate, t-butyl acetate, ethyl acetate, diethyl phthalate, 2-butanone, methyl isobutyl ketone, naphthalene, toluene, p-chlorobenzotrifluoride, trifluorotoluene, bis(trifluoromethyl)benzenes, hexamethyl disiloxane, octamethyl trisiloxane, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorotributylamine, perfluoro-N-methyl morpholine, perfluoro-2-butyl oxacyclopentane, methylene chloride, chlorocyclohexane, 1-chlorobutane, 1,1-dichloro-1-fluoroethane, 1,1,1-trifluoro-2,2-dichloroethane, 1,1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, 2,3-dihydroperfluoropentane, 1,1,1,2,2,4-hexafluorobutane, 1-trifluoromethyl-1,2,2-trifluorocyclobutane, 3-methyl-1,1,2,2-tetrafluorocyclobutane, 1-hydropentadecafluoroheptane, or mixtures thereof. In some embodiments, the present disclosure relates to a process for cleaning a substrate. The cleaning process can be carried out by contacting a contaminated substrate with a cleaning composition as discussed above. The propenylamine compounds can be utilized alone or in admixture with each other or with other commonly-used cleaning solvents, e.g., alcohols, ethers, alkanes, alkenes, haloalkenes, perfluorocarbons, perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters, ketones, oxiranes, aromatics, haloaromatics, siloxanes, hydrochlorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochloroolefins, hydrochlorofluoroolefins, hydrofluoroethers, or mixtures thereof. Such co-solvents can be chosen to modify or enhance the solvency properties of a cleaning composition for a particular use and can be utilized in ratios (of co-solvent to 1-propenylamine compounds) such that the resulting composition has no flash point. If desirable for a particular application, the cleaning composition can further contain one or more dissolved or dispersed gaseous, liquid, or solid additives (for example, carbon dioxide gas, surfactants, stabilizers, antioxidants, or activated carbon). In some embodiments, the present disclosure relates to cleaning compositions that include one or more propenylamine compounds of the present disclosure and optionally one or more surfactants. Suitable surfactants include those surfactants that are sufficiently soluble in the propenylamine compounds, and which promote soil removal by dissolving, dispersing or displacing the soil. One useful class of surfactants are those nonionic surfactants that have a hydrophilic-lipophilic balance (HLB) value of less than about 14. Examples include ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated fatty acids, alkylaryl sulfonates, glycerol esters, ethoxylated fluoroalcohols, and fluorinated sulfonamides. Mixtures of surfactants having complementary properties may be used in which one surfactant is added to the cleaning composition to promote oily soil removal and another added to promote water-soluble soil removal. The surfactant, if used, can be added in an amount sufficient to promote soil removal. Typically, surfactant may be added in amounts from 0.1 to 5.0 wt. % or from 0.2 to 2.0 wt. % of the cleaning composition. The cleaning processes of the disclosure can also be used to dissolve or remove most contaminants from the surface of a substrate. For example, materials such as light hydrocarbon contaminants; higher molecular weight hydrocarbon contaminants such as mineral oils and greases; fluorocarbon contaminants such as perfluoropolyethers, bromotrifluoroethylene oligomers (gyroscope fluids), and chlorotrifluoroethylene oligomers (hydraulic fluids, lubricants); silicone oils and greases; solder fluxes; particulates; water; and other contaminants encountered in precision, electronic, metal, and medical device cleaning can be removed. The cleaning compositions can be used in either the gaseous or the liquid state (or both), and any of known or future techniques for “contacting” a substrate can be utilized. For example, a liquid cleaning composition can be sprayed or brushed onto the substrate, a gaseous cleaning composition can be blown across the substrate, or the substrate can be immersed in either a gaseous or a liquid composition. Elevated temperatures, ultrasonic energy, and/or agitation can be used to facilitate the cleaning. Various different solvent cleaning techniques are described by B. N. Ellis inCleaning and Contamination of Electronics Components and Assemblies, Electrochemical Publications Limited, Ayr, Scotland, pages 182-94 (1986). Both organic and inorganic substrates can be cleaned by the processes of the present disclosure. Representative examples of the substrates include metals; ceramics; glass; polycarbonate; polystyrene; acrylonitrile-butadiene-styrene copolymer; natural fibers (and fabrics derived therefrom) such as cotton, silk, fur, suede, leather, linen, and wool; synthetic fibers (and fabrics) such as polyester, rayon, acrylics, nylon, or blends thereof; fabrics comprising a blend of natural and synthetic fibers; and composites of the foregoing materials. In some embodiments, the process may be used in the precision cleaning of electronic components (e.g., circuit boards), optical or magnetic media, or medical devices. In some embodiments, the present disclosure further relates to electrolyte compositions that include one or more propenylamine compounds of the present disclosure. The electrolyte compositions may comprise (a) a solvent composition including one or more of the 1-propenylamine compounds; and (b) at least one electrolyte salt. The electrolyte compositions of the present disclosure exhibit excellent oxidative stability, and when used in high voltage electrochemical cells (such as rechargeable lithium ion batteries) provide outstanding cycle life and calendar life. For example, when such electrolyte compositions are used in an electrochemical cell with a graphitized carbon electrode, the electrolytes provide stable cycling to a maximum charge voltage of at least 4.5V and up to 6.0V vs. Li/Li+. Electrolyte salts that are suitable for use in preparing the electrolyte compositions of the present disclosure include those salts that comprise at least one cation and at least one weakly coordinating anion (the conjugate acid of the anion having an acidity greater than or equal to that of a hydrocarbon sulfonic acid (for example, a bis(perfluoroalkanesulfonyl)imide anion); that are at least partially soluble in a selected propenylamine compound (or in a blend thereof with one or more other propenylamine compounds or one or more conventional electrolyte solvents); and that at least partially dissociate to form a conductive electrolyte composition. The salts may be stable over a range of operating voltages, are non-corrosive, and are thermally and hydrolytically stable. Suitable cations include alkali metal, alkaline earth metal, Group IIB metal, Group IIIB metal, transition metal, rare earth metal, and ammonium (for example, tetraalkylammonium or trialkylammonium) cations, as well as a proton. In some embodiments, cations for battery use include alkali metal and alkaline earth metal cations. Suitable anions include fluorine-containing inorganic anions such as (FSO2)2N−, BF4−, PF6−, AsF6−, and SbF6−; CIO4−; HSO4−; H2PO4−; organic anions such as alkane, aryl, and alkaryl sulfonates; fluorine-containing and nonfluorinated tetraarylborates; carboranes and halogen-, alkyl-, or haloalkylsubstituted carborane anions including metallocarborane anions; and fluorine-containing organic anions such as perfluoroalkanesulfonates, cyanoperfluoroalkanesulfonylamides, bis(cyano)perfluoroalkanesulfonylmethides, bis(perfluoroalkanesulfonyl)imides, bis(perfluoroalkanesulfonyl)methides, and tris(perfluoroalkanesulfonyl)methides; and the like. Preferred anions for battery use include fluorine-containing inorganic anions (for example, (FSO2)2N−, BF4−, PF6−, and AsF6−) and fluorine-containing organic anions (for example, perfluoroalkanesulfonates, bis(perfluoroalkanesulfonyl)imides, and tris(perfluoroalkanesulfonyl)methides). The fluorine-containing organic anions can be either fully fluorinated, that is perfluorinated, or partially fluorinated (within the organic portion thereof). In some embodiments, the fluorine-containing organic anion is at least about 80 percent fluorinated (that is, at least about 80 percent of the carbon-bonded substituents of the anion are fluorine atoms). In some embodiments, the anion is perfluorinated (that is, fully fluorinated, where all of the carbon-bonded substituents are fluorine atoms). The anions, including the perfluorinated anions, can contain one or more catenary heteroatoms such as, for example, nitrogen, oxygen, or sulfur. In some embodiments, fluorine-containing organic anions include perfluoroalkanesulfonates, bis(perfluoroalkanesulfonyl)imides, and tris(perfluoroalkanesulfonyl)methides. In some embodiments, the electrolyte salts may include lithium salts. Suitable lithium salts include, for example, lithium hexafluorophosphate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(perfluoroethanesulfonyl)imide, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, lithium tris(trifluoromethanesulfonyl)methide, lithium bis(fluorosulfonyl)imide (Li—FSI), and mixtures of two or more thereof. The electrolyte compositions of the present disclosure can be prepared by combining at least one electrolyte salt and a solvent composition including at least one propenylamine compound of the present disclosure, such that the salt is at least partially dissolved in the solvent composition at the desired operating temperature. The propenylamine compounds (or a normally liquid composition including, consisting, or consisting essentially thereof) can be used in such preparation. In some embodiments, the electrolyte salt is employed in the electrolyte composition at a concentration such that the conductivity of the electrolyte composition is at or near its maximum value (typically, for example, at a Li molar concentration of around 0.1-4.0 M, or 1.0-2.0 M, for electrolytes for lithium batteries), although a wide range of other concentrations may also be employed. In some embodiments, one or more conventional electrolyte solvents are mixed with the propenylamine compound(s) (for example, such that the propenylamine(s) constitute from about 1 to about 80 or 90 percent of the resulting solvent composition). Useful conventional electrolyte solvents include, for example, organic and fluorine-containing electrolyte solvents (for example, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dimethoxyethane, 7-butyrolactone, diglyme (that is, diethylene glycol dimethyl ether), tetraglyme (that is, tetraethylene glycol dimethyl ether), monofluoroethylene carbonate, vinylene carbonate, ethyl acetate, methyl butyrate, tetrahydrofuran, alkyl-substituted tetrahydrofuran, 1,3-dioxolane, alkyl-substituted 1,3-dioxolane, tetrahydropyran, alkyl-substituted tetrahydropyran, and the like, and mixtures thereof). Other conventional electrolyte additives (for example, a surfactant) can also be present, if desired. The present disclosure further relates to electrochemical cells (e.g., fuel cells, batteries, capacitors, electrochromic windows) that include the above-described electrolyte compositions. Such an electrochemical cell may include a positive electrode, a negative electrode, a separator, and the above-described electrolyte composition. A variety of negative and positive electrodes may be employed in the electrochemical cells. Representative negative electrodes include graphitic carbons e.g., those having a spacing between (002) crystallographic planes, d002, of 3.45 A>d002>3.354 A and existing in forms such as powders, flakes, fibers or spheres (e.g., mesocarbon microbeads); Li4/3Ti5/3O4the lithium alloy compositions described in U.S. Pat. No. 6,203,944 (Turner '944) entitled “ELECTRODE FOR A LITHIUM BATTERY” and PCT Published Patent Application No. WO 00103444 (Turner PCT) entitled “ELECTRODE MATERIAL AND COMPOSITIONS”; and combinations thereof. Representative positive electrodes include LiFePO4, LiMnPO4, LiCoPO4, LiMn2O4, LiCoO2and combinations thereof. The negative or positive electrode may contain additives such as will be familiar to those skilled in the art, e. g., carbon black for negative electrodes and carbon black, flake graphite and the like for positive electrodes. The electrochemical devices of the present disclosure can be used in various electronic articles such as computers, power tools, automobiles, telecommunication devices, and the like. Embodiments 1. A composition comprising a perfluorinated propenylamine represented by the following general formula (1): wherein each occurrence of Rf1and Rf2is:(i) independently a linear or branched perfluoroalkyl group having 1-8 carbon atoms and optionally comprises one or more catenated heteroatoms; or(ii) bonded together to form a ring structure having 4-8 carbon atoms and that optionally comprises one or more catenated heteroatoms; andwherein at least 60 wt. % of the perfluorinated propenylamine is in the form of the E isomer, based on the total weight of the perfluorinated propenylamine in the composition.2. The composition of embodiment 1, wherein at least 70 wt. % of the perfluorinated propenylamine is in the form of the E isomer, based on the total weight of the perfluorinated propenylamine in the composition.3. The composition of any one of embodiments 1-2, wherein each occurrence of Rf1and Rf2is independently a linear or branched perfluoroalkyl group having 1-8 carbon atoms and optionally comprises one or more catenated heteroatoms.4. The composition of any one of embodiments 1-2, wherein each occurrence of Rf1and Rf2is bonded together to form a ring structure having 4-8 carbon atoms and that optionally comprises one or more catenated heteroatoms.5. The composition of any one of embodiments 1-4, wherein the perfluorinated propenylamine has a GWP of less than 100.6. A method of making the composition of any one of embodiments 1-5, the method comprising:contacting a perfluorinated allylamine of general formula (2) with an active isomerization catalyst; carrying out a selective catalytic isomerization to form a 1-propenylamine of general formula (1); wherein the selectivity for formation of the E isomer of formula (1) is at least 70% wt. %, based on the total weight of the propenylamine in the composition.7. A working fluid comprising a composition according to any one of embodiments 1-5, wherein the composition is present in the working fluid at an amount of at least 25% by weight based on the total weight of the working fluid.8. An apparatus for heat transfer comprising:a device; anda mechanism for transferring heat to or from the device, the mechanism comprising a heat transfer fluid that comprises the composition or working fluid according to any one of embodiments 1-5 or 7.9. An apparatus for heat transfer according to embodiment 8, wherein the device is selected from a microprocessor, a semiconductor wafer used to manufacture a semiconductor device, a power control semiconductor, an electrochemical cell, an electrical distribution switch gear, a power transformer, a circuit board, a multi-chip module, a packaged or unpackaged semiconductor device, a fuel cell, and a laser.10. An apparatus for heat transfer according to embodiment 8, wherein the mechanism for transferring heat is a component in a system for maintaining a temperature or temperature range of an electronic device.11. A method of transferring heat comprising:providing a device; andtransferring heat to or from the device using a heat transfer fluid that the composition or working fluid according to any one of embodiments 1-5 or 7.12. The composition or working fluid of any one of embodiments 1-5 or 7, wherein at least 95 wt. % of the perfluorinated propenylamine is in the form of the E isomer, based on the total weight of the perfluorinated propenylamine in the composition. The operation of the present disclosure will be further described with regard to the following detailed examples. These examples are offered to further illustrate various embodiments and techniques. It should be understood, however, that many variations and modifications may be made while remaining within the scope of the present disclosure. EXAMPLES Objects and advantages of this disclosure are further illustrated by the following comparative and illustrative examples. List of Materials:NameDescriptionSourceAntimony(V) FluorideSbF5Acros Organics, NewJerseyNiobium(V) FluorideNbF5Oakwood Chemical, W.Columbia, SCTitanium(IV) FluorideTiF4Alfa-Aesar, Ward Hill,MAZirconium(IV) FluorideZrF4Alfa-Aesar, Ward Hill,MATantalum(V) FluorideTaF5Oakwood Chemical, W.Columbia, SCFluoroantimonic acidHSbF6Aldrich, Milwaukee, WIAntimony (V)SbCl2F3Oakwood Chemical, W.dichlorotrifluorideColumbia, SCAntimony (V)SbCl4FOakwood Chemical, W.tetrachloromonofluorideColumbia, SCTriflic Acid (Anhydrous)CF3SO3H (>Aldrich, Milwaukee, WI99%)Hydrogen FluoridePyridine-HFAldrich, Milwaukee, WIPyridine(70% HF)Potassium bifluorideKF-HF (99%)Aldrich, Milwaukee, WIHydrofluoric acidHF(g)Matheson, New(Anhydrous)Brighton, MNCesium FluorideCsF PowderCabot Corp., Boston,(Anhydrous)MAPotassium carbonateK2CO3Aldrich, Milwaukee, WI Comparative Example 1 Propenylamine Isomer Distribution Prepared by Decarboxylation of Perfluorinated Acid Fluorides Over Potassium Carbonate The perfluorinated acid fluorides listed in Table 1 were prepared by electrochemical fluorination of the corresponding hydrocarbon esters, which were in turn prepared by Michael addition of the appropriate secondary hydrocarbon amines to methyl methacrylate using previously described methods that are well known in the art. Thermal decarboxylation of these perfluorinated acid fluorides over excess potassium carbonate according to methods described in WO 2015/095285 resulted in formation of a mixture of perfluorinated propenylamine isomers. Reaction conditions, total yield of propenylamine (sum of all 3 isomers) and the isomer distribution as determined by GC-FID are summarized in Table 1. GC peak assignments were confirmed by GC-MS and NMR spectroscopy. The percent of each isomer present, as determined by GC-FID area percent, is listed in Table 1, below. The results show that the Z-isomer of the internal olefin is consistently the major isomer formed, consistent with our finding that this is the thermodynamically most stable isomer. TABLE 1Reaction Conditions and Isomer Distribution of Comparative Example 1Product Isomer DistributionInput Acid FluorideRxn Temp (° C.)Total Olefin Yield (%)2205040.554.25.22206238.558.23.3 Comparative Example 2 Catalyst Screening for E/Z Isomerization of 2,2,3,3,5,5,6,6-octafluoro-4-(1,2,3,3,3-pentafluoroprop-1-enyl)morpholine and Determination of the Equilibrium E:Z Isomer Ratio 2,2,3,3,5,5,6,6-octafluoro-4-(1,2,3,3,3-pentafluoroprop-1-enyl)morpholine was prepared as a 44:56 ratio of E and Z isomers and an overall purity of 98.5% by GC using the procedure described in Example 2 of WO 2015/095285. Non-equilibrium mixtures of E and Z isomers were then generated by fractional distillation and isolation of the early and late distillation cuts. These high purity mixtures were then used in catalyst screening experiments to determine which catalysts were active for E/Z isomerization at temperatures ranging from 20-88° C. The catalyzed isomerization reactions were run neat (in the absence of solvent) under a dry nitrogen atmosphere to prevent catalyst poisoning by water. The catalysts and conditions used in each experiment and the starting and final E:Z ratios are summarized in Table 2, below. TABLE 2Reaction Conditions and E:Z Ratios-Comparative Example 2CatalystReactionReactionStartingFinalLoadingTimeTempE:ZE:ZActive?Catalyst(Wt %)(Hrs)(° C.)RatioRatio(Y/N)SbF52.8267.02020:8022:78YSbF58.2767.52062:3833:67YSbF55.5524.08820:8032:68YHSbF611.4967.52020:8025:75YHSbF610.3667.52062:3832:68YNbF57.3797.02062:3862:38NTaF59.3097.02062:3862:38NSbCl4F7.3197.02062:3862:38NSbCl2F38.8397.02062:3862:38NTiF47.6797.02062:3862:38NZrF47.0297.02062:3862:38NCsF6.5621.52020:8020:80N(AnhydrousPowder)CF3SO3H22.267.52062:3862:38N(Anhydrous)HF4.8567.02020:8020:80N(Anhydrous)KF-HF4.6967.02020:8020:80NHF-Pyridine12.4267.02020:8020:80N(70% HF) Of the catalysts screened under these conditions, only SbF5and HSbF6showed appreciable catalyst activity for E/Z isomerization. As expected, catalyst activity and rate of isomerization was greater at higher temperatures. Interestingly, in the case of the SbF5or HSbF6catalysts, starting with either E-enriched or Z-enriched starting material resulted in approximately the same final E:Z ratio of 32:68, indicating that this must be the thermodynamic equilibrium ratio of isomers for 2,2,3,3,5,5,6,6-octafluoro-4-(1,2,3,3,3-pentafluoroprop-1-enyl)morpholine. Furthermore, it was noted that the E-enriched starting mixture reached equilibrium more quickly than the Z enriched starting mixture under similar reaction conditions, supporting the conclusion that the Z-isomer is the lower energy and thermodynamically preferred isomer. Thus, the Z isomer must overcome a larger activation barrier during isomerization to the E isomer versus the reverse reaction where E isomerizes to Z. Comparative Example 3 Determination of Thermodynamically Favored Isomer for Various Perfluorinated 1-Propenylamines Non-equilibrium, E-enriched mixtures of high purity perfluorinated 1-propenylamines, prepared by selective catalytic isomerization of the corresponding perfluorinated allyamines according to Example 2, were charged under a N2atmosphere into a dry 25 mL, 2-necked round-bottomed flask equipped with a water-cooled condenser and N2inlet. In the case of low boiling perfluorinated 1-propenylamines, such as 1,2,3,3,3-pentafluoro-N,N-bis(trifluoromethyl)prop-1-en-1-amine, a glass Fischer-Porter bottle equipped with a stainless steel pressure head was employed as the reactor to allow heating above boiling point without evaporative losses. In each case a catalytic amount of SbF5was added via plastic pipette to the neat propenylamine mixture and the flask (or pressure vessel) was immediately sealed and the reaction mixture heated to reaction temperature with stirring under N2and held at this temperature for the period of time indicated in Table 3. At the end of the reaction, the reaction mixture was chilled to less than −10° C. and quenched by gradual addition of methanol followed by excess water. After agitating vigorously, the quenched reaction mixture was allowed to phase separate and the lower fluorochemical phase was isolated and filtered through a 0.2 micron Teflon membrane via syringe to remove insoluble particulates. The clear filtrate was then analyzed neat by GC-FID. The final E:Z isomer ratios in the isolated product, as determined by GC, are summarized in Table 3, and the starting E:Z isomer ratios are provided for comparison. The GC assignments of E and Z isomers were confirmed by GC-MS and19F NMR Spectroscopy. No significant side products were detected by GC, indicating that these catalyzed isomerization reactions are very clean. The results show that all of these isomerization reactions proceed toward an equilibrium ratio of isomers that favors the Z over the E isomer. Thus, this data indicates that for each of the Examples in Table 3, the Z isomer of the 1-propenylamine is the thermodynamically more stable isomer and the E isomer is thermodynamically less stable. Furthermore, this data suggests that the thermodynamic preference for the Z isomer is a general phenomenon for 1-propenylamines of general formula (1). TABLE 3Reaction Conditions and E:Z Ratios - Comparative Example 3CatalystReactionReactionStartingFinalLoadingTimeTempE:ZE:Z1-PropenylamineCatalyst(wt %)(hr)(° C.)RatioRatioSbF518.51157091.3:8.731.1:68.9SbF512.5208099.7:0.333.3:66.7 Example 1 Selective Isomerization of 2,2,3,3,5,5,6,6-octafluoro-4-(perfluoroallyl)morpholine to E-2,2,3,3,5,5,6,6-octafluoro-4-(1,2,3,3,3-pentafluoroprop-1-enyl)morpholine Using Various Transition Metal Fluoride Catalysts Samples of 2,2,3,3,5,5,6,6-octafluoro-4-(perfluoroallyl)morpholine of greater than 98% purity (prepared using the procedure described in Example 2 of WO 2015/095285) were charged to a dry Pyrex round-bottomed flask equipped with a water cooled condenser and nitrogen inlet. The perfluorinated allyl-morpholine starting material was then combined with catalytic amounts of various anhydrous transition metal fluorides under a nitrogen atmosphere and allowed to react with magnetic stirring in the absence of solvent at the temperature and for the period of time indicated in Table 4. At the end of the reaction, the reaction mixture was filtered at ambient temperature through a 0.45 micron Teflon membrane via syringe to remove insoluble catalyst and the clear filtrate was then analyzed neat by GC-FID. The percent conversion of the terminal allyl starting material to internal olefin isomers (E&Z combined) and the E:Z isomer ratio in the final isolated product, as determined by GC, is summarized in Table 4. The GC assignments of E and Z isomers were confirmed by GC-MS and19F NMR Spectroscopy. No significant side products were detected by GC, indicating that these catalyzed isomerization reactions are very clean. The results surprisingly indicate that these isomerization catalysts are highly selective in isomerizing the perfluorinated allylmorpholine to the thermodynamically disfavored E-isomer of the internal olefin. In each case, very little of the thermodynamically favored Z isomer is formed, even at relatively high temperatures, up to 85° C. Thus, this catalyzed isomerization reaction represents a selective and cost effective method of producing highly E-enriched 2,2,3,3,5,5,6,6-octafluoro-4-(1,2,3,3,3-pentafluoroprop-1-enyl)morpholine in high yield and in high overall purity. TABLE 4Reaction Conditions and E:Z Ratios—Example 1CatalystReactionReactionLoadingTimeTemp.% ConversionFinal E:ZCatalyst(Wt %)(Hrs)(° C.)(by GC-FID)Isomer RatioTaF512.6188.52099.6098.1:1.9ZrF48.0618.58584.0996.6:3.4TiF49.7718.58599.8992.9:7.1NbF51.193.08599.9998.3:1.7 Example 2 Selective Isomerization of Various Other Perfluorinated Allylamines to E-1-propenylamines Using NbF5Catalyst High purity samples of the perfluorinated allylamines in Table 5 were independently charged to a dry Pyrex round-bottomed flask equipped with a water cooled condenser and nitrogen inlet. In the case of low boiling perfluorinated allylamines, such as 1,1,2,3,3-pentafluoro-N,N-bis(trifluoromethyl)prop-2-en-1-amine, a glass Fischer-Porter bottle equipped with a stainless steel pressure head was employed as the reactor to allow heating above boiling point without evaporative losses. The perfluorinated allylamine starting material was then combined with a catalytic amount of anhydrous NbF5under a nitrogen atmosphere and allowed to react with stirring in the absence of solvent at the temperature and for the period of time indicated in Table 5. At the end of the reaction, the reaction mixture was filtered at room temperature through a 0.45 micron Teflon membrane via syringe to remove insoluble catalyst and the clear filtrate was then analyzed neat by GC-FID. The percent conversion of the terminal allyl starting material to internal olefin isomers (E&Z combined) and the final E:Z isomer ratio in the isolated product, as determined by GC, is summarized in Table 5. The GC assignments of E and Z isomers was confirmed by GC-MS and19F NMR Spectroscopy. No significant side products were detected by GC, indicating that these catalyzed isomerization reactions are very clean. The results indicate that all of these isomerization reactions are highly selective in forming the thermodynamically disfavored E-isomer of the internal olefin. In each case, very little of the thermodynamically favored Z isomer is formed. Thus, these catalyzed isomerization reactions represent a general method of selectively producing highly E-enriched 1-propenylamines in high yield and in high overall purity. TABLE 5Reaction Conditions and E:Z Ratios - Example 2NbF5%CatalystReactionReactionConversionFinal E:ZLoadingTimeTemp.(by GC-IsomerPerfluorinated Allylamine(Wt %)(Hrs)(° C.)FID)Ratio4.1438099.699.7:0.35.5839099.497.3:2.73.8037599.6791.3:8.7 Example 3 Selective Isomerization of 2,2,3,3,5,5,6,6-octafluoro-4-(1,1,2,3,3-pentafluoroprop-2-enyl)morpholine to 2,2,3,3,5,5,6,6-octafluoro-4-[(E)-1,2,3,3,3-pentafluoroprop-1-enyl]morpholine Using SbF5Catalyst In a 2-neck round bottomed flask equipped with magnetic stir bar, rubber septum, and inlet adapter connected to a dry nitrogen source, neat 2,2,3,3,5,5,6,6-octafluoro-4-(1,1,2,3,3-pentafluoroallyl)morpholine (20 g, 55.3 mmol) was slowly treated at 0° C., with SbF5(0.6 g, 3 mmol). The resulting solution was allowed to stir at 0° C. for 1 h, and the reaction was then quenched by addition of water (10 mL) at 0° C. The lower fluorochemical product phase was separated and dried over Na2SO4. Filtration to remove the desiccating agent yielded 18 g of clear liquid product. Analysis by GC-FID revealed 85+% conversion of terminal allylic double bond to internal double bond and a final E:Z ratio of 97:3 for the 1-propenylamine product produced. The GC assignments of E and Z isomers were confirmed by GC-MS and19F NMR spectroscopy. Example 4 Selective Isomerization of 1,1,2,3,3-pentafluoro-N,N-bis(trifluoromethyl)-prop-2-en-1-amine to (E)-1,1,2,3,3-pentafluoro-N,N-bis(trifluoromethyl)-prop-1-en-1-amine Using SbF5Catalyst In a 2-neck round bottomed flask equipped with magnetic stir bar, rubber septum, and inlet adapter connected to a dry nitrogen source, neat 1,1,2,3,3-pentafluoro-N,N-bis(trifluoromethyl)-prop-2-en-1-amine (25 g, 88.3 mmol) was slowly treated at −50° C., with SbF5(1.0 g, 4.6 mmol). The resulting solution was allowed to slowly warm to 0° C. over 60 min, and was stirred at this temperature for 30 min. The reaction was subsequently quenched by addition of water (10 mL) at 0° C. The lower fluorochemical phase was separated and dried over Na2SO4. Filtration to remove the desiccating agent yielded 20 g of clear liquid product. Analysis of the product by GC-FID revealed 98+% conversion of the terminal allylic double bond to internal double bond and a final E:Z ratio of 93:7 for the 1-propenylamine product produced. The GC assignments of E and Z isomers were confirmed by GC-MS and19F NMR spectroscopy. Example 5 Atmospheric Lifetimes and Estimated GWPs of E and Z-1-Propenylamines The atmospheric lifetimes of 1-propenylamines were determined from their rate of reaction with hydroxyl radicals. The pseudo-first order rates for the reaction of the gaseous 1-propenylamines with hydroxyl radical were measured in a series of experiments relative to reference compounds such as chloromethane and ethane. The measurements were performed in a 5.7 L, heated FTIR gas cell equipped with a polished semiconductor-grade quartz window. An Oriel Instruments UV Lamp, Model 66921 equipped with a 480 W mercury-xenon bulb was used to generate hydroxyl radicals by photolyzing ozone in the presence of water vapor. The concentrations of the 1-propenylamine and the reference compound were measured as a function of reaction time using an I-Series FTIR from Midac Corporation. The atmospheric lifetimes were calculated from the reaction rates for the 1-propenylamines relative to the reference compounds and the reported lifetime of the reference compounds as shown below: τx=τr·krkx where τxis the atmospheric lifetime of the 1-propenylamine, τris the atmospheric lifetime of the reference compound, and kxand krare the rate constants for the reaction of hydroxyl radical with the isomeric 1-propenylamines and the reference compound, respectively. Global warming potentials (GWPs) have been estimated for the 1-propenylamine isomers using these atmospheric lifetimes. The GWPs were calculated according to the Intergovernmental Panel on Climate Change (IPCC) 2013 method using a 100 year integration time horizon (ITH). The radiative efficiencies used in these calculations were based upon the infrared cross-sections measured on the mixture of E and Z isomers for each 1-propenylamine. Results for the E and Z isomers of 1-propenylamines are shown in Table 6. TABLE 6Measured Atmospheric Lifetimes and Estimated GWPs of E and Z-1-PropenylaminesAtmosphericEstimated GWPLifetime (Yrs)(100-yr ITH)1-PropenylamineE-isomerZ-isomerE-isomerZ-isomer(CF3)2N—CF═CFCF30.711.950140C2F5(CF3)N—CF═CFCF31.43.51102700.802.680250 Example 6 Isomerization of 2,2,3,3,5,5,6,6-octafluoro-4-(1,1,2,3,3-pentafluoroprop-2-enyl)morpholine to (E)-2,2,3,3,5,5,6,6-octafluoro-4-(1,2,3,3,3-pentafluoroprop-1-enyl)morpholine with AlCl3 In a 25-mL two-neck round bottom flask equipped with magnetic stir bar, thermocouple, and inlet adapter connected via tubing to a Schlenk line, 2,2,3,3,5,5,6,6-octafluoro-4-(1,1,2,3,3-pentafluoroprop-2-enyl)morpholine (10 g, 27.7 mmol) was introduced under a stream of dry nitrogen followed by AlCl3(5 mol %, 0.18 g, 1.4 mmol). The resulting suspension was stirred at room temperature for 16 h or at 80° C. for 2 h. The reaction was subsequently quenched by addition of water (10 mL) at 4° C. The lower fluorochemical phase was separated and dried over Na2SO4. Filtration to remove the desiccating agent yielded 9.3 g of clear liquid product. Analysis of the product by GC-FID revealed 99.9% conversion of the terminal allylic double bond to internal double bond and a final E:Z ratio of 97:3 for the 1-propenylamine product produced. The GC assignments of E and Z isomers were confirmed by GC-MS and19F NMR spectroscopy. Example 7 Isomerization of 1,1,2,3,3-pentafluoro-N,N-bis(trifluoromethyl)prop-2-en-1-amine to (E)-1,2,3,3,3-pentafluoro-N,N-bis(trifluoromethyl)prop-1-en-1-amine with AlCl3 In a 25-mL two-neck round bottom flask equipped with magnetic stir bar, rubber septum, and inlet adapter connected via tubing to a Schlenk line, 1,1,2,3,3-pentafluoro-N,N-bis(trifluoromethyl)prop-2-en-1-amine (10 g, 35.3 mmol) was introduced under a stream of dry nitrogen followed by AlCl3(5 mol %, 0.23 g, 1.76 mmol). The resulting suspension was stirred at room temperature for 16 h. For high temperature isomerization (i.e.; 80° C.), the substrate and catalyst were placed in a glass pressure vessel and heated for 2 h. The reaction was subsequently quenched by addition of water (10 mL) at 4° C. The lower fluorochemical phase was separated and dried over Na2SO4. Filtration to remove the desiccating agent yielded 9.1 g of clear liquid product. Analysis of the product by GC-FID revealed 99.9% conversion of the terminal allylic double bond to internal double bond and a final E:Z ratio of 97:3 for the 1-propenylamine product produced. The GC assignments of E and Z isomers were confirmed by GC-MS and19F NMR spectroscopy. Example 8 Isomerization of 2,2,3,3,5,5,6,6-octafluoro-4-(1,1,2,3,3-pentafluoroprop-2-enyl)morpholine to (E)-2,2,3,3,5,5,6,6-octafluoro-4-(1,2,3,3,3-pentafluoroprop-1-enyl)morpholine with SbCl5 In a 25-mL two-neck round bottom flask equipped with magnetic stir bar, thermocouple, and inlet adapter connected via tubing to a Schlenk line, 2,2,3,3,5,5,6,6-octafluoro-4-(1,1,2,3,3-pentafluoroprop-2-enyl)morpholine (10 g, 27.7 mmol) was introduced under a stream of dry nitrogen followed by SbCl5(5 mol %, 0.42 g, 1.4 mmol). The resulting solution was stirred at room temperature for 24 h or at 80° C. for 2 h. The reaction was subsequently quenched by addition of water (10 mL) at 4° C. The lower fluorochemical phase was separated and dried over Na2SO4. Filtration to remove the desiccating agent yielded 9.5 g of clear liquid product. Analysis of the product by GC-FID revealed 90% and 99.9% conversion at 25° C. and 80° C., respectively, of the terminal allylic double bond to internal double bond and a final E:Z ratio of 97:3 for the 1-propenylamine product produced in both cases. The GC assignments of E and Z isomers were confirmed by GC-MS and19F NMR spectroscopy. Example 9 Isomerization of 1,1,2,3,3-pentafluoro-N,N-bis(perfluoropropyl)prop-2-en-1-amine to (E)-1,2,3,3,3-pentafluoro-N,N-bis(perfluoropropyl)prop-1-en-1-amine with AlCl3 To an 8 mL vial equipped with a stir bar was charged AlCl3(28 mg, 21 mmol, 5.0 mol %) and 1,1,2,3,3-pentafluoro-N,N-bis(perfluoropropyl)prop-2-en-1-amine (2.0 g, 4.1 mmol). The resultant mixture was allowed to stir at room temperature for 16 h before filtering through a 0.45 μm PVDF syringe filter to give a colorless liquid filtrate (1.95 g). GC analysis of the filtrate confirmed 99% conversion of the starting material and an E:Z-1-aminopropene ratio of 98:2. GC analysis also revealed that at least 96.5% of the filtrate comprised the expected isomerization products, E- and Z-1-aminopropene. All structures were confirmed by GC-MS analysis and19F NMR spectroscopy. Various modifications and alterations to this disclosure will become apparent to those skilled in the art without departing from the scope and spirit of this disclosure. It should be understood that this disclosure is not intended to be unduly limited by the illustrative embodiments and examples set forth herein and that such examples and embodiments are presented by way of example only with the scope of the disclosure intended to be limited only by the claims set forth herein as follows. All references cited in this disclosure are herein incorporated by reference in their entirety. | 79,543 |
11858876 | DETAILED DESCRIPTION OF THE INVENTION Definitions “Addition compound” refers to a complex of two or more complete molecules in which each preserves its fundamental structure and no covalent bonds are made or broken (for example, hydrates of salts, adducts). “Alkyl” refers to a saturated linear monovalent hydrocarbon moiety of one to twelve, typically one to six, carbon atoms or a saturated branched monovalent hydrocarbon moiety of three to twelve, typically three to six, carbon atoms. Exemplary alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, 2-propyl, tert-butyl, pentyl, and the like. “Lower alkyl” refers to a straight or branched hydrocarbon containing 1-4 carbon atoms. “Optionally-substituted alkyl” refers to an alkyl group as defined herein in which one or more hydrogen atom(s) is optionally replaced with a substituent such as halide, hydroxyl, alkoxy, or other heteroatom substituent. “Alkene” refers to an unsaturated linear divalent hydrocarbon moiety of one to twelve, typically one to six, carbon atoms or a saturated branched divalent hydrocarbon moiety of three to twelve, typically three to six, carbon atoms. Exemplary alkene groups include, but are not limited to, methylene, ethylene, propylene, butylene, pentylene, and the like. “Alkenyl” refers to a linear monovalent hydrocarbon moiety of two to ten carbon atoms or a branched monovalent hydrocarbon moiety of three to ten carbon atoms, containing at least one C═C double bond, e.g., ethenyl, propenyl, and the like. “Alkoxy” refers to an alkyl group bonded to an oxygen atom. Alkoxy groups have the general formula: R—O. “Antagonist” refers to a compound or a composition that attenuates the effect of an agonist. The antagonist can bind reversibly or irreversibly to a region of the receptor in common with an agonist. Antagonist can also bind at a different site on the receptor or an associated ion channel. Moreover, the term “antagonist” also includes functional antagonist or physiological antagonist. Functional antagonist refers to a compound and/or compositions that reverse the effects of an agonist rather than acting at the same receptor, i.e., functional antagonist causes a response in the tissue or animal which opposes the action of an agonist. Examples include agents which have opposing effects on an intracellular second messenger, or, on a physiologic state in an animal (for example, blood pressure). A functional antagonist can sometimes produce responses which closely mimic those of the pharmacological kind. “Aryl” refers to a monovalent mono-, bi- or tricyclic aromatic hydrocarbon moiety of 6 to 15 ring atoms. “Optionally-substituted aryl” refers to an aryl group as defined herein in which one or more aryl ring hydrogen is replaced with a non-hydrogen substituent such as halide, alkyl, cyano, hydroxy, alkoxy, etc. When two or more substituents are present in an aryl group, each substituent is independently selected. “Biological activity” as used herein means having an effect on or eliciting a response from a living cell, tissue, organ or physiologic activity, such as but limited to: altering gene and/or protein expression, protein phosphorylation, cellular behavior or organ function. “Biomarker” as used herein means a measurable indicator of the severity or the presence of a particular disease state. More generally a biomarker is anything that can be used as an indicator of a particular disease state or some other physiological state of an organism. “Chiral center” (i.e., stereochemical center, stereocenter, or stereogenic center) refers to an asymmetrically substituted atom, e.g., a carbon atom to which four different groups are attached. The ultimate criterion of a chiral center, however, is nonsuperimposability of its minor image. “Cycloalkyl” refers to a non-aromatic, typically saturated, monovalent mono-, bi- or tri-cyclic hydrocarbon moiety of three to twenty ring carbons. The cycloalkyl can be optionally substituted with one or more, typically one, two, or three, substituents within the ring structure. When two or more substituents are present in a cycloalkyl group, each substituent is independently selected. Exemplary cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, adamantyl, cyclohexyl, cyclooctyl, etc. “Derivative” refers to a compound that is derived from some parent compound where one atom is replaced with another atom or group of atoms and usually maintains its general structure. For example, trichlormethane (chloroform) is a derivative of methane. The terms “halo,” “halogen” and “halide” are used interchangeably herein and refer to fluoro, chloro, bromo, or iodo. “Haloalkyl” refers to an alkyl group as defined herein in which one or more hydrogen atom is replaced by same or different halo atoms. The term “haloalkyl” also includes perhalogenated alkyl groups in which all alkyl hydrogen atoms are replaced by halogen atoms. Exemplary haloalkyl groups include, but are not limited to: —CH2F, —CH2Cl, —CF3, —CH2CF3, —CH2CCl3, and the like. “Hetero-substituted alkyl” refers to an alkyl group as defined herein that contains one or more heteroatoms such as N, O, or S. Such heteroatoms can be hydroxy, alkoxy, amino, mono- or di-alkyl amino, thiol, alkylthiol, etc. “Hydroxyalkyl” refers to an alkyl group having one or more hydroxyl substituent(s). “Enantiomeric excess” refers to the difference between the amounts of enantiomers. The percentage of enantiomeric excess (% ee) can be calculated by subtracting the percentage of one enantiomer from the percentage of the other enantiomer. For example, if the % of (R)-enantiomer is 99% and % of (S)-enantiomer is 1%, the % ee of (R)-isomer is 99%-1% or 98%. “Leaving group” has the meaning conventionally associated with it in synthetic organic chemistry, i.e., an atom or a group capable of being displaced by a nucleophile and includes halo (such as chloro, bromo, and iodo), alkanesulfonyloxy, arenesulfonyloxy, alkylcarbonyloxy (e.g., acetoxy), arylcarbonyloxy, mesyloxy, tosyloxy, trifluoromethanesulfonyloxy, aryloxy (e.g., 2,4-dinitrophenoxy), methoxy, N, O-dimethylhydroxylamino, and the like. “Ligand” as used herein means a biochemical substance in the form of a nucleic acid, protein or peptide that forms a complex with another biomolecule in a cell or tissue to serve a biological purpose. “Moderate” as used herein means to decrease the quality, quantity, intensity or duration of a biological product or process. “Pharmaceutically acceptable excipient” refers to an excipient that is useful in preparing a pharmaceutical composition that is generally safe, non-toxic, and neither biologically nor otherwise undesirable, and includes excipient that is acceptable for veterinary use as well as human pharmaceutical use. “Pharmaceutically acceptable salt” of a compound means a salt that is pharmaceutically acceptable and that possesses the desired pharmacological activity of the parent compound. Such salts include: acid addition salts, formed with inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and the like; or formed with organic acids such as acetic acid, propionic acid, hexanoic acid, cyclopentanepropionic acid, glycolic acid, pyruvic acid, lactic acid, malonic acid, succinic acid, malic acid, maleic acid, fumaric acid, tartaric acid, citric acid, benzoic acid, 3-(4-hydroxybenzoyl)benzoic acid, cinnamic acid, mandelic acid, methanesulfonic acid, ethanesulfonic acid, 1,2-ethane-disulfonic acid, 2-hydroxyethanesulfonic acid, benzenesulfonic acid, 4-chlorobenzenesulfonic acid, 2-naphthalenesulfonic acid, 4-toluenesulfonic acid, camphorsulfonic acid, 4-methylbicyclo[2.2.2]-oct-2-ene-1-carboxylic acid, glucoheptonic acid, 3-phenylpropionic acid, trimethylacetic acid, tertiary butylacetic acid, lauryl sulfuric acid, gluconic acid, glutamic acid, hydroxynaphthoic acid, salicylic acid, stearic acid, muconic acid, and the like. A “pharmaceutically acceptable salt” of a compound also includes salts formed when an acidic proton present in the parent compound is either replaced by a metal ion, e.g., an alkali metal ion, an alkaline earth ion, or an aluminum ion; or coordinates with an organic base such as ethanolamine, diethanolamine, triethanolamine, tromethamine, N-methylglucamine, and the like. Pharmaceutically acceptable vehicle means, a carrier or inert medium used as a solvent (or diluent) in which the medicinally active agent is formulated and or administered. The terms “pro-drug” and “prodrug” are used interchangeably herein and refer to any compound which releases an active parent drug according to Formula I or Formula 2 in vivo when such prodrug is administered to a mammalian subject. Prodrugs of a compound of Formula I or Formula 2 are prepared by modifying one or more functional group(s) present in the compound of Formula I or Formula 2 in such a way that the modification(s) may be cleaved in vivo to release the parent compound. Prodrugs include compounds of Formula I or Formula 2 wherein a hydroxy, amino, or sulfhydryl group in a compound of Formula I or Formula 2 is bonded to any group that may be cleaved in vivo to regenerate the free hydroxyl, amino, or sulfhydryl group, respectively. Examples of prodrugs include, but are not limited to, esters (e.g., acetate, formate, and benzoate derivatives), carbamates (e.g., N,N-dimethylaminocarbonyl) of hydroxy functional groups in compounds of Formula I or Formula 2, and the like. For example, the compound according to Formula 1 that is 4-({5-[ethyl(methyl)amino]-3-oxopentyl}oxy)benzoic acid can be reacted with CH3CH2OH under acidic conditions to produce: ethyl 4-({5-[ethyl(methyl)amino]-3-oxopentyl}oxy)benzoate, an ester prodrug that will be hydrolyzed to ethanol and the starting compound by esterase enzymes in tissues. “Pro-inflammatory cytokine” refers to a type of cytokine (i.e. a protein signaling molecule) that is secreted from leukocytes and certain other cell types that promote inflammation by their biological effect on other cells and tissue in mammalian organisms. Non limiting examples of pro-inflammatory cytokines are: Interleukin 1 (IL-1; IL-1a & IL-1b), Interleukin 6 (IL-6), Interleukin 13 (IL-13), Tumor Necrosis Factor alpha (TNF-alpha), Interferon gamma (IFN-gamma) and Interleukin 8 (IL-8). “Protecting group” refers to a moiety, except alkyl groups, that when attached to a reactive group in a molecule masks, reduces or prevents that reactivity. Examples of protecting groups can be found in T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, 3rd edition, John Wiley & Sons, New York, 1999, and Harrison and Harrison et al., Compendium of Synthetic Organic Methods, Vols. 1-8 (John Wiley and Sons, 1971-1996), which are incorporated herein by reference in their entirety. Representative hydroxy protecting groups include acyl groups, benzyl and trityl ethers, tetrahydropyranyl ethers, trialkylsilyl ethers and allyl ethers. Representative amino protecting groups include, formyl, acetyl, trifluoroacetyl, benzyl, benzyloxycarbonyl (CBZ), tert-butoxycarbonyl (Boc), trimethyl silyl (TMS), 2-trimethylsilyl-ethanesulfonyl (SES), trityl and substituted trityl groups, allyloxycarbonyl, 9-fluorenylmethyloxycarbonyl (FMOC), nitro-veratryloxycarbonyl (NVOC), and the like. “Corresponding protecting group” means an appropriate protecting group corresponding to the heteroatom (i.e., N, O, P, or S) to which it is attached. “Signal transduction” or “signaling pathway activity” refers to a biochemical causal relationship generally initiated by a protein-protein interaction such as binding of a biological active factor to a receptor, resulting in transmission of a signal from one portion of a cell to another portion of a cell. In general, the transmission can involve specific phosphorylation of one or more tyrosine, serine, or threonine residues on one or more protein components such as enzymes or transcription factors (i.e. intracellular secondary messengers) in the series of reactions causing signal transduction (often referred to as a cascade) that results in measurable changes to the cell. Penultimate cellular processes typically include nuclear events, resulting in a change in gene expression. Terminal events of signal transduction cascade result in changes in cellular activity such as but not limited to: alterations in protein products produced and/or secreted by the cell, changes in cellular behavior characteristics of division, motility, adherence, etc. “Stereoisomer” means molecules that have the same molecular formula and sequence of bonded atoms (constitution), but differ in the three-dimensional orientations of their atoms in space. By definition, molecules that are stereoisomers of each other represent the same structural isomer. The chemical definitions and conventions used herein generally follow S. P. Parker, Ed., McGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, New York; and Eliel, E. and Wilen, S., “Stereochemistry of Organic Compounds”, John Wiley & Sons, Inc., New York, 1994. “A therapeutically effective amount” means the amount of a compound that, when administered to an individual for treating a disease, is sufficient to effect such treatment for the disease. The “therapeutically effective amount” will vary depending on the compound, the disease and its severity or affected organ or tissue and the age, weight, etc., of the individual to be treated. “Tautomer” or “tautomeric form” means structural isomers of different energies which are interconvertible via a low energy barrier. For example, proton tautomers (also known as prototropic tautomers) include interconversions via migration of a proton, such as keto-enol and imine-enamine isomerizations. Valence tautomers include interconversions by reorganization of some of the bonding electrons. The compounds of the present invention according to Formula 1 and Formula 2 can exist in different tautomer depend on the environment of the particular compound such as the acidity or alkalinity (i.e. pH) of the solution in which they are dissolved. “Treating” or “treatment” of a disease means inhibiting the disease, i.e., arresting or reducing the pathophysiologic process or processes of the disease or its clinical symptoms; or relieving the disease, i.e., causing regression of the pathophysiologic process or processes of disease or reducing the clinical manifestations of the pathophysiologic process or processes of the specific disease. I. METHODS OF SYNTHESIS The compounds of Formula I or Formula 2 may be prepared by the methods described below, together with synthetic methods known in the art of organic chemistry, or modifications and transformations that are familiar to those of ordinary skill in the art. The starting materials used herein are commercially available or may be prepared by routine methods known in the art, such as those methods disclosed in standard reference books such as the Compendium of Organic Synthetic Methods, Vol. I-XII (eds. John Wiley & Sons, Inc., Hoboken, New Jersey, 2009). Preferred methods include, but are not limited to, those described below. Preparation of the example compounds of Table 1 were prepared with standard procedures well known to those skilled in the art as follows: All synthetic chemistry was performed in standard laboratory glassware unless indicated otherwise in the examples. Commercial reagents were used as received from the manufacturer. Analytical LC/MS was performed on an Agilent 1200 system with a variable wavelength detector and Agilent 6140 single quadrupole mass spectrometer, alternating positive and negative ion scans. Retention times were determined from the extracted 220 nm UV chromatogram. Preparative HPLC was performed on a Wufeng LC120 system (Shanghai Wufeng Scientific Instruments Co., Ltd. Shanghai., China). 1H NMR was performed on a Bruker AVANCE™ 300 at 300 MHz or a Bruker AVANCE™ DRX 500 at 500 MHz. For complicated splitting patterns, the apparent splitting is tabulated. Analytical thin layer chromatography was performed on silica (Macherey-Nagel ALUGRAM® Xtra SIL G, 0.2 mm, UV254 indicator) and was visualized under UV light. Silica gel chromatography was performed manually, or with an Isco COMBIFLASH® for gradient elutions. Analytical LC/MS method: HPLC column: Kinetex, 2.6 μm, C18, 50×2.1 mm, maintained at 40° C. HPLC Gradient: 1.0 mL/min, 95:5:0.1 water:acetonitrile:formic acid to 5:95:0.1 water:acetonitrile:formic acid in 2.0 min, maintaining for 0.5 min. Preparative HPLC method: HPLC Gradient: 100 mL/min, 95:5:0.1 acetonitrile:water:trifluoroacetic acid to 70:30:0.1 acetonitrile:water:trifluoroacetic acid in 9.5 min, maintaining for 0.5 min. Compound 1: 4-[3-[2-(Dimethylamino)ethylamino]-3-oxopropoxy]benzoic acid A solution of 3-(4-(methoxycarbonyl)phenoxy)propanoic acid (150 mg, 0.67 mmol) in thionyl chloride (750 μL, 10.32 mmol) was stirred at 50° C. for 1 h. The reaction mixture was concentrated under a nitrogen stream to remove thionyl chloride. The residue was dissolved in chloroform (1 mL) and evaporated under a nitrogen stream. The residue was dissolved in chloroform (1 mL) and added dropwise to a stirred solution of N,N-dimethylethylenediamine (66 μL, 0.60 mmol) in chloroform (1 mL) at room temperature. The reaction mixture was stirred at room temperature for 18 h. The reaction mixture was washed with saturated sodium bicarbonate (1 mL). The aqueous layer was extracted with chloroform (1 mL). The combined organic layers were dried over sodium sulfate and evaporated to give Methyl 4-[3-[2-(dimethylamino)ethylamino]-3-oxopropoxy]benzoate (107 mg, 55%) as a white crystalline solid. Next, A mixture of methyl 4-(3-((2-(dimethylamino)ethyl)amino)-3-oxopropoxy)benzoate (173 mg, 0.59 mmol) and lithium hydroxide (1 N aqueous solution, 865 μL, 865 mmol) in 1,4-dioxane (865 μL) was stirred at room temperature for 1 h. The reaction mixture was neutralized to pH 7 by addition of acetic acid. The mixture was concentrated to 1 mL, washed with chloroform (1 mL) and evaporated. The crude product was purified by preparative HPLC. The pure fractions were combined and lyophilized. The residue was dissolved in water (20 mL) and to this solution was added 1 N hydrochloric acid (500 μL). The solution was evaporated. The residue was dissolved in water (3×10 mL) and evaporated. The residue was dissolved in water (5 mL) and lyophilized to yield Compound 1: 4-[3-[2-(Dimethylamino)ethylamino]-3-oxopropoxy]benzoic acid (45 mg, 24%) as a white crystalline solid. LCMS: 99%, tR=0.243 min, m/z=281 [M+H]+, Method: BB_LCMS_05_KINETEX. 1H NMR (300 MHz, DMSO-d6) δ 12.61 (br s, 1H), 10.24 (br s, 1H), 8.48-8.32 (m, 1H), 7.88 (d, J=8.8 Hz, 2H), 7.00 (d, J=8.9 Hz, 2H), 4.28 (t, J=6.1 Hz, 2H), 3.52-3.40 (m, 2H), 3.19-3.07 (m, 2H), 2.77 (s, 6H), 2.63 (t, J=6.1 Hz, 2H). Compound 7: N-[2-(Diethylamino)ethyl]-3-(4-methoxyphenoxy)propanamide A mixture of 3-(4-methoxyphenoxy)propanoic acid (100 mg, 0.51 mmol) in thionyl chloride (500 μL, 6.88 mmol) was stirred at room temperature for 1.5 h. The reaction mixture was concentrated under a nitrogen stream to remove thionyl chloride. The residue was dissolved in chloroform (1 mL) and evaporated under a nitrogen stream. The residue was dissolved in chloroform (1 mL) and added dropwise to a stirred solution of N,N-diethylethylenediamine (66 μL, 0.46 mmol) in chloroform (1 mL) at room temperature. The reaction mixture was stirred at room temperature for 30 min. The mixture was washed with saturated sodium bicarbonate (1 mL). The aqueous layer was extracted with chloroform (1 mL) and the combined organic layers were dried over sodium sulfate and evaporated. The crude product (108 mg) was dissolved in 1 N hydrochloric acid (5 mL) and the aqueous layer was washed with diethyl ether (5 mL). The aqueous layer was made basic to pH 8 by addition of sodium bicarbonate and extracted with diethyl ether (5 mL). The organic layer was dried over sodium sulfate and evaporated to give Compound 7: N-[2-(diethylamino)ethyl]-3-(4-methoxyphenoxy)propanamide (89 mg, 59%) as a pale yellow oil. LCMS: 99%, tR=0.728 min, m/z=295 [M+H]+, Method: BB_LCMS_05_KINETEX. 1H NMR (300 MHz, DMSO-d6) δ 7.84 (t, J=5.7 Hz, 1H), 6.87-6.80 (m, 4H), 4.09 (t, J=6.2 Hz, 2H), 3.69 (s, 3H), 3.16-3.06 (m, 2H), 2.53-2.38 (m, 8H), 0.94 (t, J=7.1 Hz, 6H). Compound 12: N-[2-(Diethylamino)ethyl]-N-ethyl-3-(4-methoxyphenoxy)propanamide N-[2-(Diethylamino)ethyl]-N-ethyl-3-(4-methoxyphenoxy)propanamide was prepared by the method used for compound 7 above, starting with 3-(4-methoxyphenoxy)propanoic acid and N,N,N′-triethylenediamine.LCMS: 99%, tR=0.976 min, m/z=323 [M+H]+, Method: BB_LCMS_05_KINETEX. 1H NMR (300 MHz, Chloroform-d) δ 6.90-6.80 (m, 4H), 4.33-4.25 (m, 2H), 3.78 (s, 3H), 3.51-3.33 (m, 4H), 2.81 (t, J=6.7 Hz, 2H), 2.68-2.50 (m, 6H), 1.22 (t, J=7.1 Hz, 3H), 1.06 (t, J=7.3 Hz, 6H). Compound 16: 3-(4-Methoxyphenoxy)-N-[2-(morpholin-4-yl)ethyl]propanamide 3-(4-Methoxyphenoxy)-N-[2-(morpholin-4-yeethyl]propanamide was prepared by the method used for compound 7 above, starting with 3-(4-methoxyphenoxy)propanoic acid and 2-morpholinoethanamine. LCMS: 98%, tR=0.444 min, m/z=309 [M+H]+, Method: BB_LCMS_05_KINETEX.1H NMR (300 MHz, DMSO-d6) δ 7.88 (t, J=5.7 Hz, 1H), 6.88-6.80 (m, 4H), 4.09 (t, J=6.2 Hz, 2H), 3.69 (s, 3H), 3.60-3.49 (m, 4H), 3.24-3.13 (m, 2H), 2.53-2.44 (m, 2H), 2.42-2.29 (m, 6H). Compound 17: N-[2-(Diethylamino)ethyl]-3-(3-fluoro-4-methoxyphenoxy)propanamide A mixture of 3-fluoro-4-methoxyphenol (250 mg, 1.76 mmol), acrylonitrile (1.2 mL, 17.6 mmol), potassium carbonate (12 mg, 0.09 mmol) and tert-butanol (17 μL, 0.18 mmol) was stirred at 75° C. for 16 h in a sealed tube. To the reaction mixture was added potassium carbonate (12 mg, 0.09 mmol) and the stirring was continued at 75° C. for 8 h. The reaction mixture was evaporated. The residue was taken up in toluene (2 mL) and washed with 10% aqueous sodium hydroxide (1 mL). The aqueous layer was extracted with toluene (2 mL). The combined organic layers were washed with 10% aqueous potassium bisulfate (1 mL), dried over sodium sulfate and evaporated to give 3-(3-fluoro-4-methoxyphenoxy)propanenitrile (231 mg, 67%) as an off-white solid. Next, a mixture of 3-(3-fluoro-4-methoxyphenoxy)propanenitrile (222 mg, 1.14 mmol) in concentrated hydrochloric acid (1 mL) and water (500 μL) was stirred at 100° C. for 3 h. The reaction mixture was poured onto ice (5 g) and the mixture was stirred for 15 min. The precipitate was collected, washed with water (2 mL) and dried in air. The crude product (196 mg) was dissolved in 10% aqueous sodium carbonate (10 mL) and the aqueous layer was washed with dichloromethane (10 mL). The aqueous layer was acidified to pH 1 by addition of 1 N hydrochloric acid. The precipitate was collected, washed with water (2×1 mL) and dried in air to give 3-(3-Fluoro-4-methoxyphenoxy)propanoic acid (103 mg, 42%) as an off-white solid. Finally, a mixture of 3-(3-Fluoro-4-methoxyphenoxy)propanoic acid (100 mg, 0.51 mmol) in thionyl chloride (500 μL, 6.88 mmol) was stirred at room temperature for 1.5 h. The reaction mixture was concentrated under a nitrogen stream to remove thionyl chloride. The residue was dissolved in chloroform (1 mL) and evaporated under a nitrogen stream. The residue was dissolved in chloroform (1 mL) and added dropwise to a stirred solution of N,N-diethylethylenediamine (66 μL, 0.46 mmol) in chloroform (1 mL) at room temperature. The reaction mixture was stirred at room temperature for 30 min. The mixture was washed with saturated sodium bicarbonate (1 mL). The aqueous layer was extracted with chloroform (1 mL) and the combined organic layers were dried over sodium sulfate and evaporated. The crude product (108 mg) was dissolved in 1 N hydrochloric acid (5 mL) and the aqueous layer was washed with diethyl ether (5 mL). The aqueous layer was made basic to pH 8 by addition of sodium bicarbonate and extracted with diethyl ether (5 mL). The organic layer was dried over sodium sulfate and evaporated to give Compound 17: N-[2-(diethylamino)ethyl]-3-(3-fluoro-4-methoxyphenoxy)propanamide (54 mg, 59%) as a pale yellow oil. 1H NMR (300 MHz, Chloroform-d) δ 6.89 (t, J=9.2 Hz, 1H), 6.73 (dd, J=12.6, 2.9 Hz, 1H), 6.67-6.60 (m, 1H), 6.67-6.56 (m, 1H), 4.21 (t, J=6.0 Hz, 2H), 3.86 (s, 3H), 3.40-3.30 (m, 2H), 2.66 (t, J=6.0 Hz, 2H), 2.61-2.51 (m, 6H), 1.03 (t, J=7.1 Hz, 6H). II. METHODS OF INHIBITION The compounds and compositions described herein inhibit the biological activity of the CCL2 induced through its binding to CCR2 and subsequent CCL2/CCR2 axis mediated signal transduction in cells and tissues. This is thought to occur by moderation or modification of protein components of the associated signal transduction pathways or inhibition of their production by decreasing expression of their mRNA precursors. In addition to inhibiting the transduction of biochemical signals in cells or tissues caused by the interaction of CCL2 and its CCR2 ligand, the compounds and compositions described also moderate later portions of associated pathophysiological process. Here, this is thought to occur by either decreasing the genetic expression of relevant ligands, protein kinases, and transcription factors or by moderating the physical and/or the chemical interactions of the relevant ligands involved to reduce the cellular activity induced by CCL2 through its interaction with the CCL2 receptor. Non-limiting examples are: down-regulation of ETS-1 (also known as, V-ets erythroblastosis virus E26 oncogene homolog 1) gene expression, inhibition of expression of iNOS, reducing the physical association of two ligands with each other such as dimerization and activation of MMP-14, and remarkably the inhibition of the expression of the CCL2 G-protein-coupled receptor CCR2 itself. The compounds and compositions described are also useful for inhibiting production and/or secretion by target cells of proteins capable of inducing; inflammation, induced by CCL2. Non limiting examples are inhibition of secretion or inhibition of production of INF-gamma, TNF-alpha, IL-1a and IL-6. In addition, the compounds and compositions described are useful in moderating CCL2 induced angiogenesis, leukocyte adhesion and cellular migration through reduction of the production of proteins that are critical to these processes such as, but not limited to; ITGB3, VEGF-A and ICAM-1. III. METHODS OF TREATMENT Because CCL2 is involved in the pro-inflammation response, angiogenesis, leukocyte adhesion and extravasation, and because it acts as a cytokine when secreted by cells, inhibition of CCL2/CCR2 signaling pathways expression and activity has implications for treatment of many disorders with diverse etiologies. Increased tissue or blood levels of CCL2 through its interaction with the CCR2 receptor and subsequent downstream signal transduction pathways is directly contributory to the pathogenesis of: autoimmune diseases; inflammatory diseases; auto-inflammatory conditions; pain conditions; respiratory ailments; airway and pulmonary conditions; gastrointestinal disorders; allergic diseases; atopic disorders, infection-based diseases; trauma and tissue injury-based conditions; fibrotic diseases; ophthalmic/ocular diseases; joint, muscle, and bone disorders; skin/dermatological diseases; renal diseases; genetic diseases; hematopoietic diseases; liver diseases; oral diseases; metabolic diseases, including diabetes (e.g. Type II) and complications thereof; proliferative diseases; cardiovascular conditions; vascular conditions including restenosis; neuro-inflammatory conditions; neurodegenerative conditions; cancer; and pulmonary conditions. CCL2 increases the levels of secreted pro-inflammatory cytokines and chemokines through its interaction with CCR2 receptor and subsequent downstream signaling pathway effects such as, but not limited to: IL-1 beta, TNF-alpha, IL-6, and IFN-gamma. These increased pro-inflammatory cytokines and chemokines induce the pathogenic processes responsible for acute and chronic diseases and their complications such as, but not limited to; Atopic disorders, Autoimmune diseases, Carcinoma, Cardiac disorders, Dermatologic diseases, Fibrosis, Gastrointestinal disorders, Hepatic diseases, Infectious diseases, Inflammatory disorders, Metabolic disorders (e.g. diabetes), Nephropathies, Neoplasia, Neurodegenerative disorders, Ophthalmologic disorders, Osteoporosis, Pulmonary diseases, Vascular conditions including restenosis, and others. Inhibition of the biological activity of CCL2 via CCL2/CCR2 axis signal transduction by the compounds of the present invention reduces the levels of these pro-inflammatory cytokines and chemokines. CCL2 through its interaction with CCR2 receptor also upregulates the expression of genes that produce intracellular intermediate ligands such as, but not limited to: protein kinases, transcription factors, G-Protein Coupled Receptors (GPCRs), and other biological ligands important to downstream initiation and/or maintenance of pathogenic processes such as; inflammation, angiogenesis, leukocyte adherence and extravasation. Examples, of genes affected by the CCL2 signal transduction that are known to be upregulated include, but are not limited to: MAPK3 (Entrez Gene: 5594 & 5595), MCPIP (Entrez Gene: 80149) and ETS-1 (Entrez Gene: 2113). Up regulation and increased expression of these intracellular intermediate ligands lead to pathogenesis responsible for acute and chronic diseases and their complications such as, but not limited to; Atopic disorders, Autoimmune diseases, Carcinoma, Cardiac disorders, Dermatologic diseases, Fibrosis, Gastrointestinal disorders, Hepatic diseases, Infectious diseases, Inflammatory disorders, Metabolic disorders (e.g. diabetes), Nephropathies, Neoplasia, Neurodegenerative disorders, Ophthalmologic disorders, Osteoporosis, Pulmonary diseases, Vascular conditions including restenosis, and others. Inhibition of the biological activity of CCL2 via CCL2/CCR2 axis signal transduction by the compounds of the present invention reduces the level of expression of these intracellular intermediate ligands. The biological activity of CCL2 acting through its binding to the CCR2 receptor also induces increases in gene expression and presence of structural cellular proteins that critical are to downstream initiation and/or maintenance of pathogenic processes such as; inflammation, angiogenesis, leukocyte adherence and extravasation. Examples, of structural cellular proteins known to be upregulated by the CCL2 signal transduction include, but are not limited to: ICAM-1, MMP-2 and VEGF-A, Up regulation and increased expression of these structural cellular proteins lead to pathogenesis responsible for acute and chronic diseases and their complications such as but not limited to; Atopic disorders, Autoimmune diseases, Carcinoma, Dermatologic diseases, Fibrosis, Gastrointestinal disorders, Hepatic diseases, Inflammatory diseases, Nephropathy, Neoplasia, Neurodegenerative disorders, Ophthalmologic disorders, Osteoporosis, Pulmonary Disease and others. Inhibition of the biological activity of CCL2 via CCL2/CCR2 axis signal transduction by the compounds of the present invention reduces the level of expression of these structural cellular proteins. In an embodiment of the present invention the compounds according to Formula 1 and Formula 2 may be used either simultaneously or sequentially in combination with a second compound, including those listed below. Non-steroidal anti-inflammatory drugs, such as but not limited to: aspirin, choline salicylate, celecoxib, acetaminophen, diclofenac, flurbiprofen, ibuprofen, indomethacin, ketoprofen, meclofenamate, mefenamic acid, nabumetone, naproxen, piroxicam, rofecoxib, salicylates, sulindac, tolmetin, and valdecoxib. Immunomodulatory agents, such as but not limited to: methotrexate, azathioprine, mitoxantrone, cladribin, cyclophosphamide, tacrorimus, methotrexate, cyclosporine, and hydroxychloroquine. Antimalarials, such as but not limited to: chloroquine, quinine, amodiaquine, pyrimethamine, proguanil, mefloquine, atovaquone, primaquine, artemisinin, and halofantrine. Antibiotics, such as but not limited to: minocycline, doxycycline, sulfonamides, and clindamycin. Anti-TNF alpha agents, such as but not limited to: infliximab, adalimumab, certolizumab pegol, golimumab, thalidomide, lenalidomide, pomalidomide, and etanercept. Anti-CD20 agents, such as but not limited to: rituximab, obinutuzumab, Ibritumomab tiuxetan, and tositumomab. Antidiarrheals, such as but not limited to: lidamidine, diphenoxylate, loperamide, and quercetin. Antidepressants, such as but not limited to: amitriptyline, clomipramine, doxepin nortriptyline and trimipramine. Antipsychotics, such as but not limited to: droperidol, pimozide, chlorpromazine, thiothixene, loxapine, molindone, quetiapine, risperidone, sertindole and zotepine. Antifungals, such as but not limited to: clotimazole, flucisoconazole, abafungin, micafugin, terbinafine, ciclopirox and tolnaftate. Antihelminthics, such as but not limited to: mebendazole, levamisole, abamectin and suramin T lymphocyte activation inhibitors, such as but not limited to: voclosporin, peroxynitrite, and dasatinib. Anti-IL-1 agents, such as but not limited to: anakinra and IL-1Ra. Glucocorticoids, such as but not limited to: methyl prednisolone, prednisolone, dexamethasone, betamethasone, fluticasone propionate, budesonide, flunisolide, mometasone furoate, triamcinolone acetonide, rofleponide, ciclesonide, and butixocort propionate. Anti-cytokine/chemokine monoclonal antibodies, such as but not limited to: basiliximab, daclizumab and secukinumab. Sex steroids and receptor modulators, such as but not limited to: progesterone, progestins, androgen, estrogen, mifepristone and misoprostil. Anti-cellular surface receptor monoclonal antibodies directed against cell surface receptors such as but not limited: CCR2, CCR5, IL7Ra and TSLPR. Aminosalicylic acid derivatives such as but not limited to: sulfasalazine and mesalazine. Anticholinergic agents, such as but not limited to: ipratropium, oxitropium, tiotropium, dextromethorphan, revatropate, pirenzepine, darifenacin, oxybutynin, mecamylamine, terodiline, tolterodine, otilonium, trospium chloride, and solifenacin. Adrenergic agonists, such as but not limited to: salmeterol, salbutamol, clonidine, oxymetazoline, and dolbutamine. Cholineric agonists, such as but not limited to: carbachol, epibatidine, galantamine, nicotine and varenicline, Corticosteroids, such as but not limited to: cortisone and hydrocortisone. Antineoplastic chemotherapeutic agents, such as but not limited to: cisplatin cyclophosphamide, bleomycin, doxorubicin, etoposide, folinic acid, and vincristine. Phosphodiesterase inhibitors, such as but not limited to: mesembrenone, rolipram, Ibudilast, piclamilast, luteolin, drotaverine, roflumilast, cilomilast, apremilast, and crisaborole. Leukotriene pathway modulators, such as but not limited to: 3-[3-butylsulfanyl-1-[(4-chlorophenyl)methyl]-5-propan-2-yl-indol-2-yl]-2,2-dimethyl-propanoic acid, baicalein, caffeic acid, curcumin, hyperforin, and zileuton. Monoclonal antibodies directed against human immunoglobulins, such as but not limited to: omalizumab. Adrenergic antagonists, such as but not limited to: alfluosin, idazoxan, labetalol, phentolamine, trazadone, propranolol and atenolol. Calcium channel antagonists, such as but not limited to: amelodipine, nifedapine, verapamil, diltiazem, and mibefradil. Dopamine agonists, such as but not limited to: aripiprazole, bromocriptine, bupropion, cabergoline, lisuride, and roxindole. Serotonin agonists, such as but not limited to: cabergoline, cisapride, gepirone, lorcaserin, and naratriptan. Dopamine antagonists, such as but not limited to: amoxipine, bromopride, butaclamol, eticlopride, olanzapine, tiapride, and ziprasidone. Serotonin antagonists, such as but not limited to: cyproheptadine, ketanserin, metergoline, methdilazine, oxetorone, and tropisetron. Monoamine reuptake inhibitors, such as but limited to: amineptine, citalopram, edivoxetine, hyperforin, mazindol, and viloxazine. Protease inhibitors, such as but not limited to: amastatin, bestatin, and gabexate. Histamine receptor antagonists, such as but not limited to: acrivastine, brompheniramine, cetirizine, cimetidine, ciproxifan, clobenprobit, cyclizine, carebastine, cyproheptadine, ebastine, epinastine, efletirizine, fexofenadine, and thioperamide. Proton pump inhibitors, such as but not limited to; omeprazole, lansoprazole, pantoprazole and rabeprazole. HMG-CoA reductase inhibitors, such as but not limited to: atorvastatin, fluastatin, lovastatin, and simvastatin. Administration of the therapeutic agent may be by any suitable means. In some embodiments, the one or more therapeutic agents are administered by oral administration. In some embodiments, the one or more therapeutic agents are administered by transdermal administration. In some embodiments, the one or more therapeutic agents are administered by injection or intravenous infusion. In one embodiment, the one or more therapeutic agents are administered topically to a mucosal, dermal or ocular tissue. If combinations of agents are administered as separate compositions, they may be administered by the same route or by different routes. If combinations of agents are administered in a single composition, they may be administered by any suitable route. In some embodiments, combinations of agents are administered as a single composition by oral administration. In some embodiments, combinations of agents are administered as a single composition by transdermal administration. In some embodiments, the combinations of agent are administered as a single composition by injection. In some embodiments, the combinations of agent are administered as a single composition topically. In one embodiment of the present invention the compounds of Formula 1 and Formula 2 may contain asymmetric or chiral centers, and, therefore, exist in different stereoisomeric forms. For example, N-[2-(diethylamino)ethyl]-N-ethyl-3-(4-methoxyphenoxy)propanamide a compound according Formula 1 that possesses a chiral center at the second nitrogen atom and thus has two stereoisomer forms. It is intended that all stereoisomeric forms of the compounds of Formula I and Formula 2 form part of the present invention, including but not limited to: diastereomers, enantiomers, and atropisomers as well as mixtures thereof such as racemic mixtures. In addition, the present invention embraces all geometric and positional isomers. For example, if a compound of Formula I or Formula 2 incorporates a double bond or a fused ring, both the cis- and trans-forms, as well as mixtures, are embraced within the scope of the invention. Both the single positional isomers and mixture of positional isomers are also within the scope of the present invention. In one embodiment of the present invention, compounds of Formula 1 and Formula 2 may exist in different tautomeric forms, and all such forms are embraced within the scope of the invention, as defined by the claims. In one embodiment of the present invention the therapeutically effective dose is from about 0.01 mg to about 5,000 mg per day of a compound provided herein. The pharmaceutical compositions therefore should provide a dosage of from about 0.01 mg to about 5000 mg of the compound. In certain embodiments, pharmaceutical dosage unit forms are prepared to provide from about 1 mg to about 2000 mg, from about 10 mg to about 1000 mg, from about 20 mg to about 500 mg or from about 25 mg to about 250 mg of the essential active ingredient or a combination of essential ingredients per dosage unit form. In certain embodiments, the pharmaceutical dosage unit forms are prepared to provide about 10 mg, 20 mg, 25 mg, 50 mg, 100 mg, 250 mg, 500 mg, 1000 mg or 2000 mg of the essential active ingredient. In another embodiment of the present invention the pharmaceutical dosage unit forms are prepared to provide a topical solution from about 0.01% to 10% of the compounds. IV. EXAMPLES To determine the ability of compounds according to Formula 1 and Formula 2 to inhibit CCL2 signal transduction through CCL2/CCR2 axis signaling pathway using a functional assay, cultivated human monocytes, PBMCs or endothelial cells were treated with purified human recombinant CCL2 protein (30 ng/mL) and the expression of various cytokines, cell adhesion and angiogenesis promoting proteins and pathway intermediate genes, known to be upregulated by CCL2, were determined by well-known methods as described below. Freshly isolated Human PBMCs or CD14+ monocytes from healthy volunteers were isolated and cultured at 1×106cells/ml in RPMI-1640 medium (GIBCO® Inc. Carlsbad, CA, USA) supplemented with 20% fetal bovine serum and 1% streptomycin/penicillin. Human Aortic Endothelial Cells (catalog number: C0065C), Medium 200PRF and LSGS supplement were obtained from (ThermoFischer Scientific; San Diego, CA, USA) and cultivated according to suppliers protocol. The endothelial cell suspensions were plated in 6-well culture plates and cultured at 1×105cells/ml in Medium 200PRF supplemented with LSGS and incubated in a 37° C., 5% CO2/95% air, humidified cell culture incubator for 72 hours at 37° C. in 5% CO2humidified incubator prior to stimulation. The cultures of PBMC, CD+14 monocytes and endothelial cells were stimulated with 30 ng/ml of CCL2 (R&D SYSTEMS®, Minneapolis, Minnesota USA) for 6-18 hrs. Cell suspensions without CCL2 stimulation were used as a baseline control for the experiments. Cell cultures were treated with various exemplar compounds according to Formula 1 and Formula 2 at several concentrations. As a known positive control for CCL2/CCR2 pathways inhibitory moderation, a blocking antibody to human CCL2 (R&D SYSTEMS®, Minneapolis, Minnesota USA) was used (10 ug/ml) that prevents binding of CCL2 to CCR2 receptor and therefore blocks signal transduction through the CCL2/CCR2 signaling pathways. The expression of specific genes known to be up-regulated by CCL2 through the CCL2/CCR2 signaling pathways were measured by quantitative RNAseq method according to standard protocols (97,98) using the Illumina HiSeq 2000 (Illumina Inc; San Diego, CA) using bar-coded multiplexing and a 75 bp read length with median sequencing reads per replicate sample of 20 million. Cell cultures were incubated for 6-18 hrs with compounds of the invention or with media alone (control cell cultures) prior to extraction of RNA using TRIZOL® reagent (ThermoFisher Scientific; San Diego, CA). Total RNA isolated was isolated according to the manufacturer's protocol (Invitrogen; Carlsbad, CA). RNA quality and quantity were assessed with the RNA 6000 Nano Kit (Agilent; Santa Clara, CA). The cDNA libraries for sequencing were prepared from Poly A selected total RNA. Data were expressed as fragments per kilobase of exon per million fragments mapped (FPKM). FPKM filtering cutoff of 0.5 in at least two of each of the triplicate samples was used to determine expressed transcripts in control cells vs cells treated with test compounds. Upregulated genes were defined as those with increased expression more than 2 fold after treatment of cells with CCL2. Differential transcript expression was then computed using Cuffdiff2 (99). In addition, all sample quantitation assays were standardized to the expression level of known human “housekeeping genes” using Log 2 transformed FPKM values, which are graphically expressed as Relative Expression based on percent of control. The “housekeeping genes,” [e.g. ribosomal protein large P1 (RPLP1) and glyceraldehyde-3-phosphate dehydrogenase (GAPDH), etc.] are constitutively expressed and not upregulated by CCL2. All studies were performed in triplicate. Examples of the results of these experiments are shown inFIGS.2and3. These experiments demonstrate that the increased expression of specific downstream genes associated with CCL2/CCR2 dependent signaling induced by CCL2 in cultivated cells are inhibited by the compounds of the instant invention. The concentration of key proteins known to be associated with inflammation, cell adhesion and vascular proliferation that are increased by CCL2 in monocytes, fibroblasts, endothelial cells and PBMCs through the via CCL2/CCR2 axis signal transduction were measured in control cells vs those treated with the test compounds, using commercially obtained enzyme-linked immunosorbent assay (ELISA) kits (R&D SYSTEMS®, Minneapolis, Minnesota USA) according to the manufacturer's instructions. The levels of the proteins in the cell culture supernatant or cell pellet lysates stimulated with CCL2 alone or treated with CCL2 along with various compounds was measured, as well as with the positive controls. Experiments were performed in triplicate. Examples of the results of these experiments are shown inFIGS.1,4and5. The results of the experiments herein demonstrate that compounds according to Formula 1 and Formula 2 inhibit the biological effects of CCL2, for example by decreasing the production of CCL2 induced pro-inflammatory cytokines, cellular adhesion promoting molecules and proteins inducing vascular proliferation, as well as decreasing the expression of other intermediate genes associated with the CCL2/CCR2 signaling cascades in human cells. Therefore, the compounds according to Formula I and Formula 2 are useful in treatment of various disorders associated with CCL2/CCR2 axis signaling. REFERENCES 1. Charo I F, Ransohoff R M. NEJM 2006 Feb. 9; 354(6):610-212. Yadav A, Saini V, Arora S Clinica chimica acta; 2010 Nov. 11; 411(21-22):1570-93. Ashida N, Arai H, Yamasaki M, Kita T. J Biol Chem 2001 May 11; 276(19):16555-604. Gerszten R E, Friedrich E B, Matsui T, et al. J Biol Chem 2001 Jul. 20; 276(29):26846-515. 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11858877 | DETAILED DESCRIPTION A dynamic and complex network of interacting proteins regulate cellular behavior. Traditional “target-centric” drug development strategies prioritize single-target potency in vitro to modulate key signaling pathway components within the network and produce a desired phenotype. Target-centric strategies use biochemical assays to optimize specificity and affinity of small molecules for a protein class, such as protein kinases, or a specific enzyme. In some cases, an effective inhibitor is comparable with gene knockdown that reduces or completely removes the target protein from the network. However, given that pleiotropy is prevalent among disease-associated proteins, compounds that disrupt specific protein-protein interactions (PPI) while leaving others intact are attractive, especially when complete disruption is detrimental to the cell (Sahni et al.,Curr. Opin. Genet. Dev.,23:649-657 (2013); Sahni et al.,Cell,161:647-660 (2015)). Tumor Necrosis Factor (TNF)-induced NF-kB signaling is an example of a tightly regulated and therapeutically relevant pathway that has resisted target-centric drug discovery. TNF is an inflammatory cytokine that initiates dynamic intracellular signals when bound to its cognate TNF receptor (TNFR1). In response to TNF, the IkB-kinase (IKK) complex is rapidly recruited from the cytoplasm to poly-ubiquitin scaffolds near the ligated receptor where it is activated through induced proximity with its regulatory kinase, TAK1 (Clark et al.,Nat. Rev. Mol. Cell Biol.,14: 673-685 (2013); Haas et al.,Mol. Cell,36: 831-844 (2009); Hayden, M. S. & Ghosh, S.,Cell,132:344-362 (2008); Hsu et al.,Immunity,4:387-396 (1996); Kulathu et al.,Nat. Struct. Mol. Biol.,16:1328-1330 (2009); Ikeda et al.,Nature,471: 637-641 (2011); Ea et al.,Mol. Cell,22:245-257 (2006)). When fully assembled, the mature TNFR1 complex (FIG.1a) is a master regulator of inflammation-dependent Nuclear Factor kB (NF-kB) signaling. Nuclear Factor kB inhibitor proteins (IkB) are degraded soon after phosphorylation by activated IKKs, and the NF-kB transcription factor accumulates in the nucleus to regulate TNF-induced transcription. Since changes in the subcellular localization of IKK and NF-kB transmit stimulus-specific information (Lee et al.,Mol. Cell,53:867-879 (2014); Lee et al.,Sci. Rep.,6:39519 (2016); Tarantino et al.,J. Cell. Biol.,204: 231-245 (2014); Zhang et al.,Cell. Syst.,5:638-645 e635 (2017)), these dynamic features can be used to demonstrate pharmacologic alterations to inflammatory signaling (Behar et al.,Cell,155: 448-461 (2013)). Chemicals that modulate inflammation-dependent IKK and NF-kB signals are of considerable therapeutic interest. Activated NF-kB regulates expression for hundreds of genes that mediate signals for inflammation, proliferation, and survival (Hayden, M. S. & Ghosh, S.Genes Dev18, 2195-2224 (2004); Kasibhatla et al.,Mol. Cell.,1:543-551 (1998); Lawrence, T.,Cold Spring Harb Perspect. Biol.,1: a001651 (2009); Pahl, H. L.,Oncogene,18:6853-6866 (1999); Tak, P. P. & Firestein, G. S.,J. Clin. Invest.,107:7-11 (2001); Wajant, H. & Scheurich, P.,FEBSI J.,278:862-876 (2011)) and its deregulation is linked to chronic inflammation in addition to the development and progression of various cancers (Lewis, C. E. & Pollard, J. W.,Cancer Res.,66: 605-612 (2006); Staudt, L. M.,Cold Spring Harb. Perspect. Biol.,2: a000109 (2010); Marx, J.,Science,306:966-968 (2004); Schottenfeld, D. & Beebe-Dimmer, J.,CA Cancer J. Clin.,56:69-83 (2006)). As pleiotropic proteins, IKK and NF-kB are poor targets for inhibitors because they provide basal activity as survival factors independent of inflammatory signaling (Dave et al.,J. Immunol.,179: 7852-7859 (2007)) and their genetic disruption can be lethal (Li et al.,Science,284: 321-325 (1999); Li, Q. & Verma, I. M.,Nat. Rev. Immunol.,2: 725-734 (2002)). The complexity of the pathway and the difficulty of modulating specific protein-protein interactions in vivo exacerbates the challenges of drugging this pathway in the cell (DiDonato et al.,Immunol. Rev.,246: 379-400 (2012)). Not surprisingly, there are no clinically approved small-molecule inhibitors of NF-kB pathway components. The present disclosure is directed to the surprising discovery of new small-molecule inhibitors of NF-kB pathway components and methods of using the same. I. Compounds Some embodiments include a compound represented by formula (I): or a salt, solvate, hydrate or prodrug thereof, wherein: A is an azinic acid; B is an alkyl sulfonyl; X1and X3are independently selected from O, NOH, NO-alkyl, CF3, and C(CN)2; X2is selected from O, NH, and NF; R1is H or alkyl and R2is an optionally substituted alkyl or cycloalkyl, or R1and R2together form an optionally substituted 5- or 6-membered heterocycle; and R3is selected from H, F, and an optionally substituted alkyl. In some embodiments, the compound represented by formula (I) does not include: In certain embodiments, B is a methyl sulfonyl or ethyl sulfonyl. In some embodiments, —NR1R2is represented by: wherein R4is an optionally substituted alkyl, alkene, alkyne, or —COOR5, where R5is an optionally substituted alkyl or cycloalkyl. and R is a non-H substituent, for example halo, hydroxyl, O-alkyl, alkyl, alkene, alkyne, or —COOR5. Some embodiments, include more than one R substitution (e.g., 2, 3, or 4). In some embodiments, R2is an optionally substituted alkyl or cycloalkyl. For example, certain embodiments include where R2is an optionally substituted cyclopropyl, cyclobutyl, cyclocyclopentyl or cyclohexyl. The cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl may be substituted, for example, with one or more halo, hydroxyl, O-alkyl, alkyl, alkene, alkyne, or —COOR5. Other embodiments include where R2is an optionally substituted alkyl, such as a C1-C10 alkyl or C1-C6 alkyl. The alkyl may be linear or branched, and the alkyl may be substituted, for example, with one or more halo, hydroxyl, O-alkyl, cycloalkyl, alkene, alkyne, or —COOR5. In some embodiments, X1, X2and X3are each O. In other embodiments, one of X1and X3is O and the other is selected from O, NOH, NO-alkyl, CF3, and C(CN)2. In some embodiments, R3is H. In other embodiments, R3is an optionally substituted alkyl, such as a C1-C10 alkyl or C1-C6 alkyl. The alkyl may be linear or branched, and the alkyl may be substituted, for example, with one or more halo, hydroxyl, O-alkyl, cycloalkyl, alkene, alkyne, or —COOR5. Some embodiments include a composition comprising a compound represented by formula (I) and a pharmaceutically acceptable carrier. In some embodiments, the composition is suitable for administration to a mammal, e.g., a human. Dosage Forms. The formulations may conveniently be presented in unit dosage form and may be prepared by any of the methods well known in the art of pharmacy. Any pharmaceutically acceptable dosage form may be employed in the methods of the invention For example, the composition can be formulated into a dosage form (a) selected from the group consisting of liquid dispersions, gels, aerosols, lyophilized formulations, tablets, capsules; and/or (b) into a dosage form selected from the group consisting of controlled release formulations, fast melt formulations, delayed release formulations, extended release formulations, pulsatile release formulations, and mixed immediate release and controlled release formulations; or (c) any combination of (a) and (b). In addition, the composition can be administered via any pharmaceutically acceptable method, such as oral, pulmonary, rectal, colonic, parenteral, intracisternal, intravaginal, intraperitoneal, intravenous, subcutaneous, intramuscular, nebulization, inhalation, ocular, otic, local, buccal, nasal, or topical administration.II. Methods Other embodiments of the present disclosure include a method of preventing formation of mature TNFR1 complex, comprising contacting a cell with an effective compound of formula (I). In some embodiments, the contacting is in vitro. In some embodiments, the contacting is in vivo in a subject suffering from a disease caused by blockade of TNF-induced signaling such as rheumatoid arthritis, ankylosing spondylitis, inflammatory bowel disease (e.g., Crohn's disease or ulcerative colitis), and psoriasis. In some embodiments, the contacting is in vivo in a subject suffering from a disease caused by inflammation-associated cancers that are potentiated by TNF-induces NFkB signaling, such as aggressive diffuse large B-cell lymphoma and metastatic carcinomas including tumors of the colon, lung, pancreas, and brain. Additional embodiments of the present disclosure include a method of inhibiting a TNF-induced nuclear factor kB (NF-kB) inflammation pathway, comprising contacting a cell with a compound of formula (I). In some embodiments, the contacting is in vivo in a subject suffering from a disease caused by blockade of TNF-induced signaling such as rheumatoid arthritis, ankylosing spondylitis, inflammatory bowel disease (e.g., Crohn's disease or ulcerative colitis), and psoriasis. In some embodiments, the contacting is in vivo in a subject suffering from a disease caused by inflammation-associated cancers that are potentiated by TNF-induced NFkB signaling, such as aggressive diffuse large B-cell lymphoma and metastatic carcinomas including tumors of the colon, lung, pancreas, and brain. Some embodiments include methods of treating a subject (e.g., a human) suffering from a disease caused by blockade of TNF-induced signaling, comprising administering to the subject in need thereof a pharmaceutically effective amount a compound of formula (I). In some embodiments, the disease caused by blockade of TNF-induced signaling such as rheumatoid arthritis, ankylosing spondylitis, inflammatory bowel disease (e.g., Crohn's disease or ulcerative colitis), and psoriasis. Some embodiments include methods of treating a subject (e.g., a human) suffering from a disease caused by inflammation-associated cancers that are potentiated by TNF-induced NFkB signaling, comprising administering to the subject in need thereof a pharmaceutically effective amount a compound of formula (I). In some embodiments, the disease caused by inflammation-associated cancers that are potentiated by TNF-induced NFkB signaling, is selected from aggressive diffuse large B-cell lymphoma and metastatic carcinomas including tumors of the colon, lung, pancreas, and brain. Other embodiments include methods for identifying molecules that specifically inhibit a TNF-induced NF-kB inflammation pathway, comprising (1) comparing transcriptional profiles between genetic knockdowns of proteins in the NF-kB signaling pathway and responses of the same cell types to the molecule; (2) calculating a binding mode of the compound through molecular docking calculation. In some embodiments, the method further includes testing inhibitory activity of the compound in vitro. Other embodiments include methods for identifying one or more molecules from a group of molecules that specifically alters a cellular phenotype, comprising (1) comparing transcriptional profiles between genetic knockdowns of proteins in the phenotype and responses of the same cell types to the group of molecules; (2) selecting the one or more molecule from the group of molecules that alters the cellular phenotype. In some embodiments, the method further includes calculating a binding mode of the one or more molecules selected in step (2) through molecular docking calculation with a biding site in a protein of the cellular phenotype. In some embodiments, the method further includes testing inhibitory activity of the one or more molecules selected in step (2) in vitro. In some embodiments, the method further includes testing for the desired cellular phenotype based on the activity of the one or more molecules selected in step (2) in vitro. In some embodiments, the cellular phenotype includes inhibition of a signaling pathway. Thus, embodiments herein include a network-centric strategy is to predict small-molecules that act on rate-limiting PPIs in the signaling pathway in silico, and screen them for phenotypes associated with pathway disruption in vivo. Although complete disruption of IKK and NF-kB can have damaging effects on the cell, their dynamics in response to disease-associated inflammatory signals are influenced by over 50 other proteins. Thus, the broader NF-kB network contains numerous entry points for chemicals to impinge on the pathway. Machine learning may be used with gene expression data to provide a synoptic list of likely small-molecule inhibitors of the NF-kB pathway. For a well-defined molecular network, it is shown that pathway-specific inhibitors can be predicted from transcriptomic alterations that are shared between i) exposure to small molecules and ii) genetic knockdowns of the pathway components. Through molecular docking a reduced list of predicted compounds and a mechanism of action may be provided, and evaluation of bioactivity using live-cell experiments that monitor signaling dynamics in single cells may be used. III. Definitions The terms “pharmacologically effective amount” or “therapeutically effective amount” of a composition or agent, as provided herein, refer to a nontoxic but sufficient amount of the composition or agent to provide the desired response, such as a reduction or reversal of cancer. The exact amount required will vary from subject to subject, depending on the species, age, and general condition of the subject, the severity of the condition being treated, the particular drug or drugs employed, mode of administration, and the like. An appropriate “effective” amount in any individual case may be determined by one of ordinary skill in the art using routine experimentation, based upon the information provided herein. As used in the specification and claims, the singular form “a,” “an” and “the” include plural references unless the context clearly dictates otherwise. For example, the term “a cell” includes a plurality of cells, including mixtures thereof. As used herein, the term “comprising” is intended to mean that the compounds, compositions and methods include the recited elements, but not exclude others. “Consisting essentially of” when used to define compounds, compositions and methods, shall mean excluding other elements of any essential significance to the combination. Thus, a composition consisting essentially of the elements as defined herein would not exclude trace contaminants, e.g., from the isolation and purification method and pharmaceutically acceptable carriers, preservatives, and the like. “Consisting of” shall mean excluding more than trace elements of other ingredients. Embodiments defined by each of these transition terms are within the scope of this technology. All numerical designations, e.g., pH, temperature, time, concentration, and molecular weight, including ranges, are approximations which are varied (+) or (−) by increments of 1, 5, or 10%. It is to be understood, although not always explicitly stated that all numerical designations are preceded by the term “about.” It also is to be understood, although not always explicitly stated, that the reagents described herein are merely exemplary and that equivalents of such are known in the art. The term “about” will be understood by persons of ordinary skill in the art and will vary to some extent depending upon the context in which it is used. If there are uses of the term which are not clear to persons of ordinary skill in the art given the context in which it is used, “about” will mean up to plus or minus 10% of the particular term. For example, in some embodiments, it will mean plus or minus 5% of the particular term. Certain ranges are presented herein with numerical values being preceded by the term “about.” The term “about” is used herein to provide literal support for the exact number that it precedes, as well as a number that is near to or approximately the number that the term precedes. In determining whether a number is near to or approximately a specifically recited number, the near or approximating unrecited number may be a number, which, in the context in which it is presented, provides the substantial equivalent of the specifically recited number. “Optional” or “optionally” means that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not. “Pharmaceutically acceptable excipient or carrier” refers to an excipient that may optionally be included in the compositions of the disclosure and that causes no significant adverse toxicological effects to the patient. “Substantially” or “essentially” means nearly totally or completely, for instance, 95% or greater of some given quantity. In some embodiments, “substantially” or “essentially” means 95%, 96%, 97%, 98%, 99%, 99.5%, or 99.9%. “Optionally substituted” refers to a group selected from that group and a substituted form of that group. A “substituted” group, refers to that group substituted with any substituent described or defined below. Substituted groups are defined herein. In one embodiment, substituents are selected from, deuterium, SF5, CF3, OCF3, halo, haloaryl, alkoxy, aryloxy, haloalkoxy, haloaryloxy, aryl, benzyl, benzyloxy, heteroaryl, nitrile, C1-C6alkyl, C1-C6alkenyl, C1-C6alkynyl, C3-C6cycloalkyl, C1-C6haloalkyl, C1-C6haloalkenyl, C1-C6haloalkynyl, C3-C6halocycloalkyl C1-C10or C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C6-C10aryl, C3-C8cycloalkyl, C2-C10heterocyclyl, C1-C10heteroaryl, —N3, nitro, —CO2H or a C1-C6alkyl ester thereof, haloaryl, alkoxy, aryloxy, haloalkoxy, haloaryloxy, aryl, benzyl, benzyloxy, C1-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, or any of the functional groups described or defined below. “Alkyl” refers to monovalent saturated aliphatic hydrocarbyl groups having from 1 to 10 carbon atoms and preferably 1 to 6 carbon atoms. This term includes, by way of example, linear and branched hydrocarbyl groups such as methyl (CH3—), ethyl (CH3CH2—), n-propyl (CH3CH2CH2—), isopropyl ((CH3)2CH—), n-butyl (CH3CH2CH2CH2—), isobutyl ((CH3)2CHCH2—), sec-butyl ((CH3)(CH3CH2)CH—), t-butyl ((CH3)3C—), n-pentyl (CH3CH2CH2CH2CH2—), and neopentyl ((CH3)3CCH2—). A Cx-Cy alkyl will be understood to have from x to y carbons. “Alkenyl” refers to monovalent straight or branched hydrocarbyl groups having from 2 to 6 carbon atoms and preferably 2 to 4 carbon atoms and having at least 1 and preferably from 1 to 2 sites of vinyl (>C═C<) unsaturation. Such groups are exemplified, for example, by vinyl, allyl, and but-3-en-1-yl. Included within this term are the cis and trans isomers or mixtures of these isomers. “Alkynyl” refers to straight or branched monovalent hydrocarbyl groups having from 2 to 6 carbon atoms and preferably 2 to 3 carbon atoms and having at least 1 and preferably from 1 to 2 sites of acetylenic unsaturation. Examples of such alkynyl groups include acetylenyl (—C≡CH), and propargyl (—CH2≡CH). “Substituted alkyl” refers to an alkyl group having from 1 to 5, preferably 1 to 3, or more preferably 1 to 2 substituents selected from the group consisting of alkoxy, substituted alkoxy, acyl, acylamino, acyloxy, amino, substituted amino, aminocarbonyl, aminothiocarbonyl, aminocarbonylamino, aminothiocarbonylamino, aminocarbonyloxy, aminosulfonyl, aminosulfonyloxy, aminosulfonylamino, amidino, aryl, substituted aryl, aryloxy, substituted aryloxy, arylthio, substituted arylthio, carboxyl, carboxyl ester, (carboxyl ester)amino, (carboxyl ester)oxy, cyano, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, cycloalkylthio, substituted cycloalkylthio, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, cycloalkenylthio, substituted cycloalkenylthio, guanidino, substituted guanidino, halo, hydroxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, heteroarylthio, substituted heteroarylthio, heterocyclic, substituted heterocyclic, heterocyclyloxy, substituted heterocyclyloxy, heterocyclylthio, substituted heterocyclylthio, nitro, SO3H, substituted sulfonyl, substituted sulfonyloxy, thioacyl, thiol, alkylthio, and substituted alkylthio, wherein said substituents are as defined herein. “Substituted alkenyl” refers to alkenyl groups having from 1 to 3 substituents, and preferably 1 to 2 sub stituents, selected from the group consisting of alkoxy, substituted alkoxy, acyl, acylamino, acyloxy, amino, substituted amino, aminocarbonyl, aminothiocarbonyl, aminocarbonylamino, aminothiocarbonylamino, aminocarbonyloxy, aminosulfonyl, aminosulfonyloxy, aminosulfonylamino, amidino, aryl, substituted aryl, aryloxy, substituted aryloxy, arylthio, substituted arylthio, carboxyl, carboxyl ester, (carboxyl ester)amino, (carboxyl ester)oxy, cyano, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, cycloalkylthio, substituted cycloalkylthio, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, cycloalkenylthio, substituted cycloalkenylthio, guanidino, substituted guanidino, halo, hydroxyl, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, heteroarylthio, substituted heteroarylthio, heterocyclic, substituted heterocyclic, heterocyclyloxy, substituted heterocyclyloxy, heterocyclylthio, substituted heterocyclylthio, nitro, SO3H, substituted sulfonyl, substituted sulfonyloxy, thioacyl, thiol, alkylthio, and substituted alkylthio, wherein said substituents are as defined herein and with the proviso that any hydroxyl or thiol substitution is not attached to a vinyl (unsaturated) carbon atom. “Substituted alkynyl” refers to alkynyl groups having from 1 to 3 substituents, and preferably 1 to 2 sub stituents, selected from the group consisting of alkoxy, substituted alkoxy, acyl, acylamino, acyloxy, amino, substituted amino, aminocarbonyl, aminothiocarbonyl, aminocarbonylamino, aminothiocarbonylamino, aminocarbonyloxy, aminosulfonyl, aminosulfonyloxy, aminosulfonylamino, amidino, aryl, substituted aryl, aryloxy, substituted aryloxy, arylthio, substituted arylthio, carboxyl, carboxyl ester, (carboxyl ester)amino, (carboxyl ester)oxy, cyano, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, cycloalkylthio, substituted cycloalkylthio, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, cycloalkenylthio, substituted cycloalkenylthio, guanidino, substituted guanidino, halo, hydroxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, heteroarylthio, substituted heteroarylthio, heterocyclic, substituted heterocyclic, heterocyclyloxy, substituted heterocyclyloxy, heterocyclylthio, substituted heterocyclylthio, nitro, SO3H, substituted sulfonyl, substituted sulfonyloxy, thioacyl, thiol, alkylthio, and substituted alkylthio, wherein said substituents are as defined herein and with the proviso that any hydroxyl or thiol substitution is not attached to an acetylenic carbon atom. “Prodrug,” of a compound, as used herein, refers to a chemical that when metabolized, turns into the compound. An animal, subject or patient for diagnosis, treatment, or administration of the compounds if the disclosure thereto, refers to an animal such as a mammal, or a human, ovine, bovine, feline, canine, equine, simian, etc. Non-human animals subject to diagnosis, treatment, or administration thereto of compounds of the disclosure include, for example, simians, murine, such as, rat, mice, canine, leporid, livestock, sport animals, and pets. A “composition” “pharmaceutical composition” as used herein, intends an active agent, such as a compound as disclosed herein and a carrier, inert or active. The carrier can be, without limitation, solid such as a bead or resin, or liquid, such as phosphate buffered saline. “Cycloalkyl” refers to cyclic alkyl groups of from 3 to 10 carbon atoms having single or multiple cyclic rings including fused, bridged, and spiro ring systems. The fused ring can be an aryl ring provided that the non-aryl part is joined to the rest of the molecule. Examples of suitable cycloalkyl groups include, for instance, adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclooctyl. “Substituted cycloalkyl” and “substituted cycloalkenyl” refers to a cycloalkyl or cycloalkenyl group having from 1 to 5 or preferably 1 to 3 substituents selected from the group consisting of oxo, thioxo, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, alkoxy, substituted alkoxy, acyl, acylamino, acyloxy, amino, substituted amino, aminocarbonyl, aminothiocarbonyl, aminocarbonylamino, aminothiocarbonylamino, aminocarbonyloxy, aminosulfonyl, aminosulfonyloxy, aminosulfonylamino, amidino, aryl, substituted aryl, aryloxy, substituted aryloxy, arylthio, substituted arylthio, carboxyl, carboxyl ester, (carboxyl ester)amino, (carboxyl ester)oxy, cyano, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, cycloalkylthio, substituted cycloalkylthio, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, cycloalkenylthio, substituted cycloalkenylthio, guanidino, substituted guanidino, halo, hydroxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, heteroarylthio, substituted heteroarylthio, heterocyclic, substituted heterocyclic, heterocyclyloxy, substituted heterocyclyloxy, heterocyclylthio, substituted heterocyclylthio, nitro, SO3H, substituted sulfonyl, substituted sulfonyloxy, thioacyl, thiol, alkylthio, and substituted alkylthio. “Heterocycle” or “heterocyclic” or “heterocycloalkyl” or “heterocyclyl” refers to a saturated or partially saturated, but not aromatic, group having from 1 to 10 ring carbon atoms and from 1 to 4 ring heteroatoms selected from the group consisting of nitrogen, sulfur, or oxygen. Heterocycle encompasses single ring or multiple condensed rings, including fused bridged and spiro ring systems. In fused ring systems, one or more the rings can be cycloalkyl, aryl, or heteroaryl provided that the point of attachment is through a non-aromatic ring. In one embodiment, the nitrogen and/or sulfur atom(s) of the heterocyclic group are optionally oxidized to provide for the N-oxide, sulfinyl, or sulfonyl moieties. “Substituted heterocyclic” or “substituted heterocycloalkyl” or “substituted heterocyclyl” refers to heterocyclyl groups that are substituted with from 1 to 5 or preferably 1 to 3 of the same substituents as defined for substituted cycloalkyl. “Pharmaceutically acceptable salt” refers to salts of a compound, which salts are suitable for pharmaceutical use and are derived from a variety of organic and inorganic counter ions well known in the art and include, when the compound contains an acidic functionality, by way of example only, sodium, potassium, calcium, magnesium, ammonium, and tetraalkylammonium; and when the molecule contains a basic functionality, salts of organic or inorganic acids, such as hydrochloride, hydrobromide, tartrate, mesylate, acetate, maleate, and oxalate (see Stahl and Wermuth, eds., “Handbook of Pharmaceutically Acceptable Salts,” (2002), Verlag Helvetica Chimica Acta, Zürich, Switzerland), for a discussion of pharmaceutical salts, their selection, preparation, and use. “Active molecule” or “active agent” as described herein includes any agent, drug, compound, composition of matter or mixture which provides some pharmacologic, often beneficial, effect that can be demonstrated in vivo or in vitro. This includes foods, food supplements, nutrients, nutraceuticals, drugs, vaccines, antibodies, vitamins, and other beneficial agents. As used herein, the terms further include any physiologically or pharmacologically active substance that produces a localized or systemic effect in a patient. In specific embodiments, the active molecule or active agent includes the compound of formula I, or a pharmaceutically acceptable salt or solvate thereof. “Substantially” or “essentially” means nearly totally or completely, for instance, 95% or greater of some given quantity. In some embodiments, “substantially” or “essentially” means 95%, 96%, 97%, 98%, 99%, 99.5%, or 99.9%. Generally, pharmaceutically acceptable salts are those salts that retain substantially one or more of the desired pharmacological activities of the parent compound and which are suitable for in vivo administration. Pharmaceutically acceptable salts include acid addition salts formed with inorganic acids or organic acids. Inorganic acids suitable for forming pharmaceutically acceptable acid addition salts include, by way of example and not limitation, hydrohalide acids (e.g., hydrochloric acid, hydrobromic acid, hydroiodic acid, etc.), sulfuric acid, nitric acid, phosphoric acid, and the like. Organic acids suitable for forming pharmaceutically acceptable acid addition salts include, by way of example and not limitation, acetic acid, trifluoroacetic acid, propionic acid, hexanoic acid, cyclopentanepropionic acid, glycolic acid, oxalic acid, pyruvic acid, lactic acid, malonic acid, succinic acid, malic acid, maleic acid, fumaric acid, tartaric acid, citric acid, palmitic acid, benzoic acid, 3-(4-hydroxybenzoyl) benzoic acid, cinnamic acid, mandelic acid, alkylsulfonic acids (e.g., methanesulfonic acid, ethanesulfonic acid, 1,2-ethane-disulfonic acid, 2-hydroxyethanesulfonic acid, etc.), arylsulfonic acids (e.g., benzenesulfonic acid, 4-chlorobenzenesulfonic acid, 2-naphthalenesulfonic acid, 4-toluenesulfonic acid, camphorsulfonic acid, etc.), glutamic acid, hydroxynaphthoic acid, salicylic acid, stearic acid, muconic acid, and the like. Pharmaceutically acceptable salts also include salts formed when an acidic proton present in the parent compound is either replaced by a metal ion (e.g., an alkali metal ion, an alkaline earth metal ion, or an aluminum ion) or by an ammonium ion (e.g., an ammonium ion derived from an organic base, such as, ethanolamine, diethanolamine, triethanolamine, morpholine, piperidine, dimethylamine, diethylamine, triethylamine, and ammonia). A solvate of a compound is a solid-form of a compound that crystallizes with less than one, one or more than one molecules of a solvent inside in the crystal lattice. A few examples of solvents that can be used to create solvates, such as pharmaceutically acceptable solvates, include, but are not limited to, water, C1-C6 alcohols (such as methanol, ethanol, isopropanol, butanol, and can be optionally substituted) in general, tetrahydrofuran, acetone, ethylene glycol, propylene glycol, acetic acid, formic acid, and solvent mixtures thereof. Other such biocompatible solvents which may aid in making a pharmaceutically acceptable solvate are well known in the art. Additionally, various organic and inorganic acids and bases can be added to create a desired solvate. Such acids and bases are known in the art. When the solvent is water, the solvate can be referred to as a hydrate. In some embodiments, one molecule of a compound can form a solvate with from 0.1 to 5 molecules of a solvent, such as 0.5 molecules of a solvent (hemisolvate, such as hemihydrate), one molecule of a solvent (monosolvate, such as monohydrate) and 2 molecules of a solvent (disolvate, such as dihydrate). An “effective amount” or a “pharmaceutically acceptable amount” is an amount sufficient to effect beneficial or desired results. An effective amount can be administered in one or more administrations, applications or dosages and is determined by the system in which the drug or compound is delivered, e.g., an effective amount for in vitro purposes is not the same as an effective amount for in vivo purposes. For in vivo purposes, the delivery and “effective amount” is dependent on a number of variables including the time period for which the individual dosage unit is to be used, the bioavailability of the therapeutic agent, the route of administration, etc. It is understood, however, that specific dose levels of the therapeutic agents disclosed herein for any particular subject depends upon a variety of factors including the activity of the specific compound employed, bioavailability of the compound, the route of administration, the age of the animal and its body weight, general health, sex, the diet of the animal, the time of administration, the rate of excretion, the drug combination, and the severity of the particular disorder being treated and form of administration. In general, one will desire to administer an amount of the compound that is effective to achieve a serum level commensurate with the concentrations found to be effective in vivo. These considerations, as well as effective formulations and administration procedures are well known in the art and are described in standard textbooks. As used herein, “treating” or “treatment” of a disease in a patient refers to (1) preventing the symptoms or disease from occurring in an animal that is predisposed or does not yet display symptoms of the disease; (2) inhibiting the disease or arresting its development; or (3) ameliorating or causing regression of the disease or the symptoms of the disease. As understood in the art, “treatment” is an approach for obtaining beneficial or desired results, including clinical results. For the purposes of this technology, beneficial or desired results can include one or more, but are not limited to, alleviation or amelioration of one or more symptoms, diminishment of extent of a condition (including a disease), stabilized (i.e., not worsening) state of a condition (including disease), delay or slowing of condition (including disease), progression, amelioration or palliation of the condition (including disease), states and remission (whether partial or total), whether detectable or undetectable. As used herein, the term “contacting” intends bringing the reagents into close proximity with each other so that a chemical or biochemical reaction can occur among the reagents. In one aspect, the term intends admixing the components, either in a reaction vessel or on a plate or dish. In another aspect, it intends in vivo administration to a subject. The term “binding” or “binds” as used herein are meant to include interactions between molecules that may be covalent or non-covalent which, in one embodiment, can be detected using, for example, a hybridization assay. The terms are also meant to include “binding” interactions between molecules. Interactions may be, for example, protein-protein, antibody-protein, protein-nucleic acid, protein-small molecule or small molecule-nucleic acid in nature. This binding can result in the formation of a “complex” comprising the interacting molecules. A “complex” refers to the binding of two or more molecules held together by covalent or non-covalent bonds, interactions or forces. Throughout this disclosure, various publications, patents and published patent specifications are referenced by an identifying citation. The disclosures of these publications, patents and published patent specifications are hereby incorporated by reference into the present disclosure in their entirety to more fully describe the state of the art to which this invention pertains. The practice of the present technology will employ, unless otherwise indicated, conventional techniques of organic chemistry, pharmacology, immunology, molecular biology, microbiology, cell biology and recombinant DNA, which are within the skill of the art. See, e.g., Sambrook, Fritsch and Maniatis,Molecular Cloning: A Laboratory Manual,2ndedition (1989);Current Protocols in Molecular Biology(F. M. Ausubel et al., eds., (1987)); the seriesMethods in Enzymology(Academic Press, Inc.):PCR2:A Practical Approach(M. J. MacPherson, B. D. Hames and G. R. Taylor eds. (1995)), Harlow and Lane, eds. (1988)Antibodies, a Laboratory Manual,andAnimal Cell Culture(R. I. Freshney, ed. (1987)). The following examples are given for the purpose of illustrating various embodiments of the disclosure and are not meant to limit the present disclosure in any fashion. One skilled in the art will appreciate readily that the present disclosure is well adapted to carry out the objects and obtain the ends and advantages mentioned, as well as those objects, ends and advantages inherent herein. The present examples, along with the methods described herein are presently representative of embodiments and are exemplary, and are not intended as limitations on the scope of the disclosure. Changes therein and other uses which are encompassed within the spirit of the disclosure as defined by the scope of the claims will occur to those skilled in the art. EXAMPLES Example 1 Differential Gene Expression Signatures Identify Small Molecules that Correlate with NF-kB Signaling To demonstrate a network-centric strategy for targeting TNF-induced NF-kB signaling, differential gene expression signatures from the NIH Library of Integrated Network-Based Cellular Signatures (LINCS) L1000 dataset (Keenan et al.,Cell Syst.,6:13-24 (2018)) was reviewed. Transcriptional profiles between genetic knockdowns of proteins in the NF-kB signaling pathway and responses of the same cell types to thousands of distinct bioactive compounds were compared. Using a random forest classification model trained using FDA-approved drugs, compounds whose transcriptomic perturbations resembled genetic disruption were identified. For each compound, the probability of a compound-protein interaction was evaluated in terms of ‘direct’ correlation with the knockdown signatures, and ‘indirect’ correlations with knockdown signatures of other proteins in the network for 4 or more cell lines (see Pabon et al.,PLoS Comput. Biol.,14 (2018) for detailed explanation of the approach). Note that disruption of a physical target is expected to cause similar gene expression profiles as downstream or upstream perturbations in the same subnetwork. Hence, a compound that disrupts TRADD or TRAF2 inFIG.1amight have similar signatures to the knockdown of genes in the pathway such as TNFR1, UBC, or NEMO. Here, compounds that suggest chemical inhibition acts broadly within a subnetwork (FIG.6) to drug the NF-kB signaling pathway. A PPI inhibitory peptide that competes with recruitment of catalytic IKK subunits at ubiquitin scaffolds was previously shown to inhibit inflammatory NF-kB activation and disease progression in a murine model for inflammatory-bowel disease (Dave et al.,J. Immunol.,179: 7852-7859 (2007); Shibata et al.,J. Immunol.,179: 2681-2685 (2007)). It was reasoned that any compounds that disrupt the mature TNFR1 complex, particularly at the level of TRADD, TRAF2, and RIP1, will prevent TNF-mediated IKK recruitment and nuclear translocation of NF-kB. Transcriptional signatures for 717 unique compounds showed strong correlations with genetic knockdowns of TRADD, TRAF2, and RIP1. From this initial set, potential pathway inhibitors were identified as compounds that also correlated with genes in the mature TNFR1 complex (FIG.1a). Specifically, candidate inhibitors were ranked by their mean Pearson correlation with NF-kB knockdowns to assist selection of compounds for additional screening (FIG.7). Example 2 Small Molecules are Predicted to Target Core PPIs in the Mature TNFR1 Complex Molecular docking was used to further refine the list of candidate compounds and predict mechanism of action against proteins in the TNFR1 signaling complex. The 717 candidate molecules described above were docked with domain structures available in the PDB for TRAF2, TRADD, and RIPK1. TRAF2 emerged as a promising target because, contrary to the other proteins, co-crystal structures of TRAF2 are available. Namely, the protein-protein interaction between TRAF2 and both TRADD (PDB code 1F3V (Park et al.,Cell,101:777-787 (2000))) and a TNFR2 peptide (PDB code 1CA9 (Park et al.,Nature,398: 533-538 (1999))) have been characterized. Both co-crystals indicate a well-defined binding site, which was used to visually screen the top scoring compounds based on both Pearson correlation and binding scores (n=180 compounds; seeFIG.7). Three compounds whose binding modes replicate native contacts in the TRADD-TRAF2 protein complex were selected for testing: (1) BRD-K43131268, (2) BRD-K95352812, and (3) BRD-A09719808. For compounds 1, 2, and 3 respectively, predicted targets from a genetic knockdown gene expression dataset (Pabon et al.,PLoS Comput. Biol.,14 (2018)) included: TRAF2, UBC, NFKB1, and RIP1; TRAF6, NEMO, TRAF2, NFKB1, UBC, TAB2, and IKKβ; and, NFKB1, TRAF2, UBC, UBB and NEMO. Furthermore, compounds 2 and 3 showed significant correlations with both HOIL, TAK1, clAP1/2 and UbcH5 knockdowns (FIG.1a) and their corresponding transcriptional profiles of genes in the Nf-Kb pathway (FIG.1b). Compounds 2 and 3 also had similar chemical structures (FIG.1c), strongly suggesting a similar mechanism of action. Compounds 2 and 3 formed hydrogen bond contacts with TRAF2 residues S453, S454, S455, and S467, which are predicted to compete with TRADD interface residues Q143, D145, and R146 based on the co-crystal (FIG.1c). Compound 3 is predicted to bind stronger due to the extra hydrogen bond formed by its amide group with TRAF2 residue G468. Of note, all these TRAF2 residues are conserved in TRAF5. Competitive binding should disrupt the native TRADD-TRAF2/5 PPI interface and could prevent maturation of the full TNFR1 signaling complex by promoting dissociation or allosteric stabilization of a non-native conformation. The predicted binding mode of compound 1 is less specific and did not form any of the contacts described above (FIG.8). To test whether the compounds interact with TRAF2 in vitro, the thermal stability of purified TRAF2 in the presence of each compound was measured. Thermal shift assays showed that compounds 2 and 3 respectively exert a subtle to moderate dose-dependent stabilizing effect on full length TRAF2 (FIG.2a, b), suggesting direct compound-protein binding. In contrast, compound 1 did not show a clear trend (FIG.9). The observed thermal shifts are consistent with the relatively small stabilizing effect that the compounds are expected to exert on the stable trimer formed by the soluble full length TRAF2 protein (Park et al.,Nature,398:533-538 (1999)). Together, these data suggest that Compounds 2 and 3 may impinge on TNF-induced signaling. Example 3 Small Molecules Disrupt the TNF-Induced Dynamics of Nuclear NF-kB Localization in Single Cells A determination whether the compounds are effective inhibitors of NF-kB signaling in living cells was pursued. For this example, the endogenous gene locus for the transcriptionally active RelA subunit of NF-kB was modified using CRISPR/Cas9 to encode a fluorescent protein (FP) fusion in U2OS cells (FIG.10), a cell line that forms IKK-recruiting polyubiquitin scaffolds in response to TNF (Tarantino et al.,J. Cell. Biol.,204:231-245 (2014)). Responses of single cells exposed to TNF showed transient and variable translocation of NF-kB into the nucleus when measured from time-lapse images (FIG.3a), comparable with other human cancer cell lines that express FP-RelA fusions (Lee et al.,Mol. Cell.,53:867-879 (2014); Zhang et al.,Cell. Syst.,5:638-645 e6352017); Wong et al.,Cell. Rep.,22:585-599 (2018)). When cells were pre-treated with compounds 2 and 3 before exposure to TNF, nuclear mobilization of NF-kB was reduced with increasing concentration of the inhibitory compound (FIG.3b). To quantify the compounds' effect on NF-kB dynamics, each single-cell trajectory was decomposed into a series of descriptors (FIG.3c) that transmit information within the cell about extracellular cytokine concentrations (Zhang et al.,Cell. Syst.,5:638-645 e635 (2017)). Descriptors of NF-kB dynamics that transmit the most information about TNF, including the ‘area under the fold change curve’ (AUC’) and the ‘Maximum fold change’ (‘Max’), were significantly less when cells were pretreated with 10 μM of compound 2 or 3 before the addition of TNF (FIG.3d). Other descriptors showed a similar pattern of inhibition when exposed to 10 μM of either compound prior to TNF stimulation (FIGS.11and12). By contrast, aside from subtle alterations to the rates of nuclear NF-kB mobilization, compound 1 did not significantly alter the overall TNF-induced dynamics of nuclear NF-kB (FIG.13). These data suggest that compounds 2 and 3 restrict the signaling network upstream of NF-kB activation with low micromolar potency (FIG.14). Compounds 2 and 3 also showed significant correlations (FIG.1b) with ubiquitination machinery and kinases, including IKK, that are common to basal cellular processes and inflammatory responses (Beck et al.,Endocr. Rev.,30:830-882 (2009)). Interleukin-1 (IL1) is one such inflammatory cytokine that activates NF-kB via the functional IKK complex, but independent of interactions between TRADD and TRAF2. Instead, IL1 utilizes TRAF6 which does not share any of the four serines (S453, S454, S455, and S467;FIG.1a) identified as the binding substrate of the compounds. Consistent with this observation and in contrast with the TNF response, IL1-induced dynamics of nuclear NF-kB were indistinguishable between cells pretreated with compounds 2 or 3 and IL1-only control cells (FIGS.4and15). Furthermore, cytotoxicity analysis and assessment of IKKβ kinase activity in vitro demonstrated that compounds 1, 2 and 3 have low cytotoxicity and no direct inhibitory activity over IKKβ kinase activity at the concentrations used in this study (FIGS.16and17). Together the results demonstrate that the IKK and NF-kB systems are intact in cells exposed to the compounds and suggest that the mode of action for both compounds is directed specifically at the level of the mature TNFR1 complex. Example 4 Small Molecules Prevent Formation of the Mature TNFR1 Complex Induced proximity between IKK and other regulatory factors within the mature TNFR1 complex is essential for TNF-induced NF-kB activation and may be perturbed in cells exposed to compounds 2 and 3. To test this hypothesis, and directly observe the penultimate recruitment of IKK to the TNFR1 complex, CRISPR/Cas9 was used to target the γ-subunit of IKK (also known as NEMO) for FP fusion and live-cell imaging in U2OS cells (FIG.18). FP-IKK was diffuse within the cytoplasm of unstimulated cells and rapidly localized to punctate structures near the plasma membrane after exposure to TNF (FIG.5a). Because a key role of the TNFR1 complex is to recruit and activate IKK at ubiquitin scaffolds (Ea et al.,Mol. Cell.,22:245-257 (2006)), detection of FP-IKK puncta can be used to measure maturation of the complex in living cells. The number of FP-IKK puncta in single cells peaked at 15 minutes and dissolved within an hour of TNF stimulation (FIG.5b). Although the recruitment and dissolution dynamics of FP-IKK are prolonged when compared with a previous study that overexpressed a fusion of mouse IKγ in U2OS cells (Tarantino et al.,J. Cell. Biol.,204:231-245 (2014)), they are otherwise qualitatively similar. Consistent with observations for NF-kB, the number of TNF-induced puncta were greatly reduced in cells that were pretreated with compounds 2 or 3 before exposure to TNF (FIG.5b). Unexpectedly, the compounds also reduced the overall expression level of IKKγ (FIG.19) through an unknown mechanism that may relate to TRAF-dependent ubiquitination cascades that regulate the ambient stability of other NF-kB-inducing kinases (Zarnegar et al.,Nat. Immunol.,9:1371-1378 (2008)). Overall, the absence of IKKγ mobilization in TNF-stimulated cells indicate that micromolar concentrations of compounds 2 and 3 prevent a key proximity-induced mechanism provided otherwise through assembly of the mature TNFR1 complex. Example 5 Analysis of Gene Expression Data Preparation and analysis of gene expression (GE) data was performed as described previously (Pabon et al.,PLoS Comput. Biol.,14 (2018)). Briefly, gene knockdown (KD) and compound treatment GE signatures were extracted from the LINCS L1000 Phase I and Phase II datasets (GEO accession IDs: GSE70138 and GSE92742). Signatures for the 1680 small molecules and 3104 gene KD experiments that had been performed in at least four of the seven most common LINCS cells lines (A549, MCF7, VCAP, HA1E, A375, HCC515, HT19) were collected. For each compound—KD signature pair in the dataset, several cell-specific quantitative features were computed, most importantly: Direct correlation: the Pearson correlation coefficient between the compound treatment and the gene KD expression signatures in the given cell line, and Indirect correlation: the fraction of the KD protein's interaction partners, as defined by BioGrid (Chatr-Aryamontri, A. et al.Nucleic Acids Res43, D470-478 (2015)), whose respective KD signatures were highly correlated with the compound signature. Three additional features, quantifying baseline drug activity in the cell and the maximum & average compound-induced differential expression levels of NF-kB pathway proteins (Pabon et al.,PLoS Comput. Biol.,14 (2018)), were also calculated and used in subsequent classification. Using a Random Forest (RF) classifier trained the expression signatures of 152 FDA-approved drugs with known mechanism(s) of action, features for every compound-KD pair (n=5,214,720) were used to predict the probability that the compound would inhibit the KD protein's interaction network. The top-100 predicted interactions for each compound were extracted, and compounds whose predicted targets were enriched in TNF-induced NF-kB signaling genes (n=360) were collected for structural analysis. Example 6 Structural Analysis Structural docking of RF—predicted inhibitors proceeded as previously described (Pabon et al.,PLoS Comput. Biol.,14 (2018)). Briefly, representative crystal structures of TNF-inducible NF-kB signaling proteins (FIG.6) were mined from the PDB (Berman et al.,Nucleic Acids Res.,28:235-242 (2000)), optimizing for sequence coverage, structural resolution, and structural diversity. Domain structures were available for all proteins inFIG.1awith the exception of IKKα. Potential small-molecule binding sites on each protein structure were identified by clustering the output of computational solvent mapping software FTMap (Kozakov et al.,Nature Protocols,10:733-755 (2015)). RF-predicted inhibitors were docked to predicted binding sites on each protein structure using smina (Koes et al.,J. Chem. Inf. Model.,53:1893-1904 (2013)), and a prospectively validated pipeline (Ye et al.,J. Comput. Aided Mol. Des.,30:695-706 (2016); Baumgartner, M. P. & Camacho, C. J.,J. Chem. Inf. Model.,56:1004-1012 (2016)). Generic versions of the three promising candidate inhibitors of TRAF2, which showed both biophysical complementarity and broad spectrum transcriptomic correlations with knockdowns in the pathway, were purchased from MolPort for experimental validation. Molport IDs MolPort-000-763-757, MolPort-004-495-831, MolPort-004-588-414 for compounds 1, 2, 3 respectively. Molport versions of compounds 2 and 3 had minor modifications (seeFIG.20) that did not alter their predicted binding profiles. Example 7 Thermal Shift Assay and Analysis TRAF2—compound interactions were measured by fluorescence-based thermal shift using an Applied Biosystems ABI QuantStudio(TM) 6 Flex System. All assay experiments used 1 uM GST-TRAF2 (Rockland) per well and 2 X Sybro Orange (Invitrogen) in a buffer containing 50 mM HEPES, pH 7.5, 150 Mm NaCl in a total reaction volume of 15 ul in 384 well plates. Compounds were diluted with DMSO, and each reaction had a final DMSO concentration of 1.5%. PCR plates were covered with optical seal, shaken, and centrifuged after protein and compounds were added. The instrument was programmed in the Melt Curve mode and the Standard speed run. The reporter was selected as Rox and None for the quencher. Each melt curve was programmed as follows: 25° C. for 2 min, followed by a 0.05° C. increase per second from 25° C. to 99° C., and finally 99° C. for 2min. Fluorescence intensity was collected continuously. In the Melt Curve Filter section, X4 (580 ±10)-M4 (623±14) was selected for the Excitation Filter-Emission Filter. The raw data was extracted in MS-Excel format. Each melt curve was normalized between 0 and 1 and the midpoint of the curve was used to determine the melting temperature. Example 8 Establishing EGFP-RELA/IKKγ CRISPR Knock-in Cells Construction of Repair Templates for EGFP-IKKγ CRISPR Knock-in: The RelA repair template consisted of DNA sequences for a left homology arm (LHA −544bp, chromosome 11_65663376-chromosome 11_65662383) followed by an EGFP coding sequence with a start codon but no stop codon and a sequence encoding 3x GGSG linker (SEQ ID NO: 1) followed by a right homology arm (RHA +557bp, chromosome 11_65662829-chromosome 11_65662276) were assembled from plasmids synthesized by GeneArt. Synonymous mutations that are not recognized guide RNAs were introduced to prevent interaction the repair template and Cas9. IKBKG DNA sequences for left homology arm (LHA −861bp, chromosome X 154551142-chromosome X 154552002) and right homology arm (RHA +797bp, chromosome X_154552006-chromosome X 154552798) were amplified from Hela genomic DNA using the following primer pairs: IKBKG_LHA_F: 5′GGG CGA ATT GGG CCC GAC GTC GTT TCA CCG TGT TAG CCA GG3′ (SEQ ID NO: 2), IKBKG_LHA_R: 5′ CAC ATC CTT ACC CAG CAG A3′ (SEQ ID NO: 3); IKBKG_RHA_F: 5′AGA GTC TCC TCT GGG GAA GC3 (SEQ ID NO: 4), IKBKG_RHA_R: 5′CCG CCA TGG CGG CCG GGA GCA TGC GAC GTC AGT CTA GGA AAG AAC TCC CCA GTC3′ (SEQ ID NO: 5). To generate the fragment containing EGFP overlapping with LHA and RHA, the sequence was synthesized from GeneArt, then amplified the sequence containing EGFP with the primer pairs: IKBKG_EGFP_F 5′ TCT GCT GGG TAA GGA TGT G3′ (SEQ ID NO: 6), IKBKG_EGFP_R 5′ GCT CTT GAT TCT CCT CCA GGC AG 3′ (SEQ ID NO: 7). After PCR products were purified, the fragments LHA, RHA, EGFP were cloned to pMK plasmid that was digested with AatII by gibson assembly from NEB. Construction of Guide RNA: The guide RNAs were designed by the CRISPR Design Tool. Oligonucleotide pairs Rel A sg1 (top): 5′-CACCGCTCGTCTGTAGTGCACGCCG-3′ (SEQ ID NO: 8), Rel A sg1 (bottom): 5′-AAACCGGCGTGCACTACAGACGAGC-3′ (SEQ ID NO: 9); RELA Sg2 (top) 5′-CACCGAGAGGCGGAAATGCGCCGCC-3′ (SEQ ID NO: 10), RELA Sg2 (bottom) 5′-AAACCGCGGCGCATTTCCGCCTCTC-3′ (SEQ ID NO: 11); IKBKG Sg1 (top) 5′-CACCGGCAGCAGATCAGGACGTAC-3′ (SEQ ID NO: 12), IKBKG Sg1 (bottom) 5′-AAACGTACGTCCTGATCTGCTGCC-3′ (SEQ ID NO: 13); and IKBKG Sg2 (top) 5′-CACCGCTGCACCATCTCACACAGT-3′ (SEQ ID NO: 14), IKBKG Sg2 (bottom) 5′-AAACACTGTGTGAGATGGTGCAGC-3′ (SEQ ID NO: 15) were cloned into the vector pSpCas9n (BB)-2A-Puro (PX462) (Addgene). The pSpCas9n (BB)-2A-Puro-IKKγ_gRNAs vector encoded the guide RNA and the Cas9 nuclease with D10A nickase mutant. Transfection and Clone Isolation: U2OS cells (2×105 cells per well) were seeded in 6-well plates in complete growth medium. The following day, with pSpCas9n (BB)-2A-Puro-RELA/IKKγ_gRNAs and repair template donor plasmids were linearized using BGLII, and cells were transfected using FuGENE HD (Promega) with a transfection reagent to DNA ratio of 3.5 to 1 and a total DNA amount of 4 μg. After two weeks, cells were subjected to single cell sorting into 96-well plates using Beckman Coulter MoFlo Astrios High Speed. Cells underwent clonal isolation and a positive clone was identified via western blot and confirmed by live-cell imaging. Example 9 Western Blot Analysis U2OS cells (parental and expressing EGFP-RelA/IKKγ via CRISPR Knock-in) were cultured for 24 hrs in complete growth medium. After treatments, cells were lysed in SDS-based lysis buffer consisting of 120 mM Tris-Cl, pH 6.8, 4% SDS supplemented with protease and phosphatase inhibitors at 4° C. for 30 min. Protein extracts were clarified by centrifugation at 4° C. at 12,000×g for 10 min. Lysate protein levels were quantified by BCA assay (Pierce). Samples were separated by SDS-PAGE, 25 μg total protein per lane, then transferred to PVDF membranes. Blocking was done in 5% milk in TBS for 1 hour. Primary antibodies directed at RelA and β-actin (#4764 and #3700 respectively; Cell Signaling Technology), IKKγ and GAPDH (sc-8330 and sc25778 respectively; Santa Cruz) were diluted in 5% milk in TBS-T and incubated overnight at 4° C. Alexa 680/800-conjugated secondary antibodies (LICOR) were used in combination with an Odyssey (LI-COR) scanner for detection and quantification of band intensities. Example 10 Live-Cell Imaging and Analysis Live cells were imaged in an environmentally controlled chamber (37° C., 5% CO2) on a DeltaVision Elite microscope equipped with a pco.edge sCMOS camera and an Insight solid-state illumination module (GE). U2OS cells expressing FP-RelA/IKKγ were seeded at a density of 25000 cells/well 24 hours prior to live-cell imaging experiments on no. 1.5 glass bottom 96 well imaging plates (Matriplate). For imaging of FP-RelA nuclear translocation, live-cells were pre-treated with DMSO or indicated concentrations of compounds for 2 hours before exposure to either 100 ng/ml recombinant human TNF (Peprotech) or 100 ng/ml recombinant human IL1β (Peprotech). Wide-field epifluorescence and DIC images were collected using a 20× LUCPLFLN objective (0.45NA; Olympus). Cells were imaged for at least 30 minutes prior to addition of compounds. For detection of IKKγ puncta, live-cells were pre-treated with DMSO or indicated concentration of compounds for 2 hours before exposure to 100 ng/ml TNF. Wide-field epifluorescence and DIC images were collected using a 60× LUCPLFLN objective. For all treatments, cytokine mixtures were prepared and pre-warmed so that addition of 120 uL added to wells results in a final concentration as indicated. Time-lapse images were collected over at least 4 fields per condition with a temporal resolution of 5 minutes per frame. Quantification of nuclear FP-RelA localization and the formation IKKγ puncta from flat-field and background corrected images was performed using customized scripts in Matlab and ImageJ. Example 11 Fixed-Cell Immunofluorescence and Analysis For fixed-cell measurement of endogenous RelA (FIG.10), U2OS cells were seeded into plastic bottom 96 well imaging plates (Fisher) at 6000 cell/well 24 hours prior to treatment. On the day of the experiment, media containing TNF was prepared at 15× the desired concentration for each well. Timing of TNF treatment was planned so fixation (0, 10, 30, 60, 90, 120 minutes) occurred simultaneously for all time points at the same time. Pre-warmed 15× cytokine mixture was spiked into wells and mixed. Between treatments the cells remained in environmentally controlled conditions (37° C. and 5% CO2). At time zero, media was removed from the wells, 185 μL of PBS was used to wash the wells, and wells were incubated at room temp in 120 μL of 4% paraformaldehyde (PFA) in 1× PBS for 10 minutes. Wells were then washed 3× three minutes with 185 μL 1× PBS and then incubated in 120 μL 100% methanol for 10 min at room temp. Next wells were washed 3× three minutes in PBS-T (1×PBS 0.1% Tween 20) followed by 120 μL of primary antibody solution (3% BSA PBS-T, 1 μg/mL NF-κB p65 F-6 (sc-8008; Santa Cruz)). Plates were wrapped in para-film and left to incubate at 4° C. overnight. The following morning, wells were washed 3× five minutes in 185 μL PBS-T followed by incubation for 1 hour in 120 μL of the secondary antibody solution (3% BSA PBS-T, 4 μg/mL Goat anti-Mouse IgG Alexa Fluor 647 (Thermo Fisher)). 185 μL PBS-T was used to wash the wells for 5 minutes and they were put into 120 ul Hoechst solution (PBS-T, 200 ng/mL Hoechst) for 20 min. Finally, wells were washed five minutes with PBST and then 185 μL PBS was used to fill the wells and keep the cells hydrated during imaging. Cells were imaged using Delta Vision Elite imaging system at 20× magnification with a LUCPLFLN objective (0.45NA; Olympus). Analysis was done using Cell Profiler to segment cells and quantify median nuclear intensity values. Further analysis was performed using custom scripts in MATLAB. Example 12 Permutation Tests to Assess Statistical Significance between Descriptors For permutation tests, data from the TNF-only and the indicated experimental condition were combined and randomly distributed into ‘Permuted control’ and ‘Permuted experimental’ bins without replacement, preserving the size of the original control and experimental data sets. 106permutations were performed and the difference between the means of permuted control and experimental data were calculated for each condition to generate a histogram. Two-tailed p-values were determined by computing the fraction of permuted data sets where Δmeanpermuted≥Δmeanunpermuted(FIGS.12,13, and15). Example 13 In Vitro IKKβ Kinase Assay Recombinant activated IKKβ and the IKKtide substrate (Promega, V4502) with the ADP-Glo bioluminescence assay (Promega, V7001) was used to evaluate the effects of compounds 1, 2 and 3 on IKKβ kinase activity. 1× kinase buffer A (40 mM Tris-HCl pH 7.4, 20 mM MgCl2, 0.1 mg/mL BSA, supplemented with 2 mM MnCl2, 2 mM DTT and 100 μM Sodium vanadate) was used to prepare all components of the reaction. All components were prepared in a 96-well plate and transferred to every other well of a 384-well opaque plate (Sigma-Aldrich, CLS3825-10EA) using a multichannel pipet. A 2.5× ATP/IKKtide substrate mix (62.5 μM ATP mixed with 0.5 μg/μL IKKtide) was prepared, and a 5× concentration of the indicated concentration of compounds in 0.5% DMSO, maintaining a final DMSO concentration of 0.1% in all reactions. The components of this kinase reaction were added to each well in the following order: 1 μL of 5× compound or buffer only, 2 μL of 100 ng/μL of IKKβ Kinase or buffer, and 2 μL of 2.5× ATP/IKKtide substrate mix. The plate was briefly spun, and the reaction incubated at room temperature for 1 h. Next, 5 μL of ADP-Glo reagent were added to each well, spun and incubated for 40 minutes at room temperature. Finally, 10 μL of Kinase Detection Reagent were added to each well and incubated for 30 minutes at room temperature. Luminescence from each well was measured using an integration time of 500 ms in a M4 microplate reader (SpectraMax). Data from triplicate reactions were extracted and plotted. Example 14 Compound Toxicity Comparison Cytotoxicity of the three compounds was compared with Bay 11-7082 (Cayman, 10010266), an inhibitor of the NF-κB pathway at working concentrations of 1-10 μM, using the LIVE/DEAD Cell Imaging Kit (488/570) (Invitrogen, R37601). For each condition, 15,000 U2OS cells were seeded in 200 μL of growth medium in each well of 96-well plate 48 h before microscopy. Next, medium was changed to medium containing either DMSO, 10 μM of indicated compound, or 10 μM of Bay 11-7082 for the indicated duration (2 h, 16 h, or 24 h). Before imaging, medium was changed to phenol red-free FluoBrite DMEM (Gibco, A18967-01) containing 300 ng/mL of Hoechst 33342, and 1:10000 of both Live Green and Dead Red dyes of the LIVE/DEAD Cell Imaging Kit. Cells were incubated for 60 minutes and imaged on the Delta Vision Elite imaging system at 20× magnification with a LUCPLFLN objective (0.45NA; Olympus). Analysis was done using Cell Profiler to segment cells and quantify median nuclear intensity values. Further analysis was performed using custom scripts in MATLAB. Data from biological triplicates were plotted as the mean ± SD. It will be apparent to those skilled in the art that various modifications and variations can be made in the methods and compositions of the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention, provided they come within the scope of the appended claims and their equivalents. | 64,239 |
11858878 | DETAILED DESCRIPTION OF THE INVENTION The invention concerns a genus of synthesized amido-amine-based cationic gemini surfactants with flexible or rigid central spacers between nitrogen-atom-containing head groups and hydrophobic tails. These gemini surfactants were prepared by modified procedure through amidation of long chain carboxylic acids followed by treatment of halohydrocarbons as exemplified by Scheme 1 below. The effects of a gemini surfactant containing either a trans or cis conformation of the spacer double bond on critical micelle concentration, surface tension reduction, and thermal stabilities were determined. The short-term thermal stability of the gemini surfactants was assessed using thermogravimetric analysis (TGA) and the long-term thermal stability was examined by a unique approach based on structure characterization techniques including NMR (1H and13C) and FTIR analysis. TGA results exhibited excellent short-term thermal stability and no structure degradation was observed up to 200° C. Structural characterization revealed impressive long-term thermal stability of the gemini surfactants with no structure decomposition after exposing them to 90° C. for 10 days. The critical micelle concentration results of gemini surfactants were found to be in the range of 0.77×10−4mol L−1to 3.61×10−4mol L−1and corresponding surface tension (γcmc) results were ranged from 30.34 mN m−1to 38.12 mN m−1. The surface properties of the trans conformation of spacer double bond found to be predominant compared to cis conformation. The gemini surfactants showed excellent thermal stability and surface properties which made them good candidates for various oilfield applications such as enhanced oil recovery. The gemini surfactants of the invention generally conform to Formula (I): wherein:R1 and R2 are C8-C30alkyl or C10-C30alkenyl, preferably C12-C18alkyl or C12-C18alkenyl,S is a linear C4, C6or C8alkylene or linear C4, C6or C8alkenylene spacer, andn and n′ are C2-C5alkylene. The substituents on either side of the spacer S may be linked to it in cis or in trans. Six exemplary gemini surfactants according to Formula (I) were synthesized and designated amido-amine-based cationic gemini surfactants (1)-(6) These exemplary gemini surfactants conforming to Formula (I) were designed with different spacer groups and different hydrophobic tails and allowed the inventors to assess and compare the functional properties of gemini surfactants of Formula (I). The inventors determined the effects of spacer length, spacer rigidity, trans and cis conformation of the spacer double bond, and hydrophobic tail length with regard to thermal stability, surface tension, and other functional properties. Gemini surfactants (1) and (3) and gemini surfactants (2) and (4) were designed to have similar trans- or cis-linked spacer groups but to differ in their hydrophobic tail groups. Three amido-amine based cationic gemini surfactants (3)-(5) were produced which a similar hydrophobic tail group but which had differed with regard to rigidity and flexibility of the spacer. For engineering these surfactants, two spacer lengths C4and C6were selected to determine whether these lengths would produce noticeable changes in surfactant properties; Laschewsky A, Lunkenheimer K, Rakotoaly R H, Wattebled L (2005)Spacer effects in dimeric cationic surfactants. Colloid Polym. Sci. 283 (5):469-479, incorporated herein by reference in its entirety. A dodecyl group was selected as a hydrophobic tail to determine whether it would deliver useful functional properties to a gemini surfactant; and an olea tail was chosen to determine whether it would confer a decrease critical micelle concentration (“cms”) with an increase of the chain length; Huang Z, Zhong H, Wang S, Xia L, Zou W, Liu G (2014)Investigations on reverse cationic flotation of iron ore by using a Gemini surfactant: Ethane-1,2-bis(dimethyl-dodecyl-ammonium bromide). Chemical Engineering Journal 257:218-228. doi:http://dx.doi.org/10.1016/j.cej.2014.07.057; and Lee M-T, Vishnyakov A, Neimark A V (2013)Calculations of critical micelle concentration by dissipative particle dynamics simulations: the role of chain rigidity, Journal of Physical Chemistry B 117 (35):10304-10310, each incorporated herein by reference in their entirety. The gemini surfactants of the invention contain two hydrophobic tails which may be derived from saturated or unsaturated fatty acid precursors. These tails comprise R1 and R2 in Formula (I). R1 and R2, may be the same or different, preferably the same, and can comprise C8to C30alkyl or C8to C30alkenyl. In some embodiments R1 and R2 comprise C8, C9, C10, C11, C12, C13, C14, C15or C16alkyl or alkenyl and will not exceed C16. In other embodiments R1 and R2 may comprise C17-C27alkyl or C17-C27alkenyl. Preferably, the fatty acid precursors of R1 and R2 are unbranched. Examples of saturated fatty acid substrates for production of R1 and R2 (e.g., by steps similar to those described by Scheme 1) include, but are not limited to, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid and cerotic acid. Examples of unsaturated fatty acid substrates for production of R1 and R2 include, but are not limited to, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid. As shown herein for gemini surfactants (1)-(4), 3-(dimethylamino)-1-propylamine (9) is used to provide a linkage of three carbons between the nitrogen atoms in the polar head groups separated by the central spacers. In other embodiments, shorter or longer analogs of (9) can be used to adjust spacing between the nitrogen atoms, for example, compounds of the formula, H2N—(CH2)m—N(CH3)2, where m is 2-5. Similarly, the central spacer may be produced using substrates such as halogen-(CH2)o-halogen where o is 4-8 or with halogen-alkenyl-halogen, wherein the alkenyl has 4 to 8 carbon atoms. Compositions containing Gemini surfactants. The gemini surfactants of the invention may be added to one or more fluids used to recover petroleum, gas or other hydrocarbons, for example, to an injected fluid, to produced water, injected fluid or to flowback water. These compositions may be prepared as emulsions and may include ingredients besides water and a gemini surfactant. Produced water describes water that is produced as a byproduct along with the oil and gas. Oil and gas reservoirs often have water as well as hydrocarbons, sometimes in a zone that lies under the hydrocarbons, and sometimes in the same zone with the oil and gas. Injected fluid/Fracturing fluid. Fracturing or “fracking” fluid is typically primarily water containing sand or other proppants suspended with a thickening agent. It is usually injected at high pressure into a wellbore to create cracks in the deep-rock formations through which natural gas, petroleum, and brine can flow more freely. When the hydraulic pressure is removed from the well, small grains of hydraulic fracturing proppants, such as sand, silica sand, resin-coated sand, or aluminum oxide, bauxite, or man-made ceramics, hold the fractures open. Flow back water. During hydrocarbon recovery procedures like fracking less than half of injected water may be recovered as flowback or later production brine and in many cases recovery is <30%. As a fracturing fluid flows back through the well it may contain spent fluids and dissolved constituents such as minerals and brine waters. Gemini surfactant applications. The gemini surfactants and compositions of the invention may be used in various methods in the fields of oil drilling and petrochemistry such as for increased recovery of crude oil or other hydrocarbons from a subterranean hydrocarbon-containing formation or during hydraulic fracturing. The compositions are thermally stable when subjected to underground conditions including temperatures of about 70, 80, 90, 100, 110, 120 130, 140, 150, 160, 170, 180, 190, 200 and >200° C. and/or to water sources having a high content of dissolved solids, such as water with greater than 500, 1,000, 2,000, 10,000, 20,000, 50,000 or 100,000 ppm dissolved salts, metals and/or minerals. Preferably, the compositions are stable for periods of at least 72 hours at a temperature of 100° C. such that the amount of the gemini surfactants (1)-(6) remains at least 95%, preferably 98%, 99% or 99.5% of the starting amount. The cmc of gemini surfactants (1)-(6) preferably ranges from 1.0×10−4mol/L to 5×10−4mol/L, preferably more from 0.77×10−4mol/L to 3.61×10−4for improved oil recovery. Injection of a gemini surfactant containing composition of the invention into an oil-containing reservoir, causes rock contacted by the composition to change from oil-wettable to water-wettable rock. However, the components of the compositions exhibit a low tendency to adsorb onto the rock and also inhibit formation of emulsions in underground fracturing fluid flows. The compositions substantially increase the yield of hydrocarbons from underground reservoirs when injected and are particularly useful for increasing yield of hydrocarbons in reservoirs comprising high temperature water sources, high total dissolved solids water sources, or high temperature/high total dissolved solids water sources including from tight shale reservoirs. Other applications include use of the gemini surfactants as corrosion inhibitors or biocides. Methods of use include those contacting one or more gemini surfactants with metal surfaces of tools or drilling equipment exposed to corrosive fluids in amounts sufficient to inhibit or prevent corrosion and methods of contacting tools or drilling equipment with a concentration of gemini surfactant sufficient to prevent, inhibit or remove biofilms. Suitable concentrations of a gemini surfactant for these purposes may range from 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1 or >1 mM or any intermediate values within this range. The gemini surfactants of the invention may also be used as demulsifiers for breaking water-in-crude oil emulsions, for example, to increase water separation efficiency or decrease water separation time from crude oil emulsions. The gemini surfactants of the invention may also be used a defoaming or emulsifying agents in a variety of different products include those used to provide coatings or inks for paper, wood, plastic, ceramics, glass or metals. They may be incorporated into architectural coatings; printing inks, overprint varnishes and fountain solutions; adhesives, dye and pigment synthesis, pigment grinding, oil and gas processing, cleaning products, semiconductor cleaning and processing fluids, metalworking fluids, cements, mortars and grouts, and personal care products, such as soaps, shampoos, body washes, lotions, and other cosmetics, in amounts ranging from 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1 or >1 mM or any intermediate value within this range. Embodiments of the invention include, but are not limited to those described below. One embodiment of the invention is a gemini surfactant described by formula (I): wherein:R1 and R2 are C8-C30alkyl or C10-C30alkenyl, preferably C12-C18alkyl or C12-C18alkenyl,S is a C4, C6or C8linear alkylene or C4, C6or C8linear alkenylene spacer bonded on each end to a nitrogen atom, andn and n′ are C2-C5alkylene. In some embodiments R1 and R2 may be the same or different. In some embodiments, R1 and R2 may contain cis or trans double bonds to other portions of the gemini surfactant structure. The gemini surfactants of the invention comprise counteranions to the charged nitrogen groups. These are typically, halide ions, such as two bromide anions or two chloride anions. However, in other embodiments, they may contain one or more or a mixture of different anions, such as other halogen anions like F−, Cl−, I−or As−or other anions such as NO3−, SO42−, alkylsulfate such as methyl or ethylsulfate, alkylphosphate such as methylphosphate, and the like. Mixtures of 2, 3, 4, 5 or 6 or more of these gemini surfactants may be made. Advantageously, a gemini surfactant according to this embodiment is selected from the group consisting of gemini surfactants (1), (2), (3), (4), (5), and (6) comprising the structures depicted below and anion(s) having a total charge of −2, for example, comprising two bromide or two chloride anions: The gemini surfactants of the invention comprise counter anions having a total charge of −2. These counterions include halides such as Br−, F−, Cl−, I−or As−as well as other anions such as NO3−, SO42−, alkylsulfate such as methyl or ethylsulfate, alkylphosphate such as methylphosphate, and the like. As synthesized in Scheme 1 gemini surfactants (1), (3), (5) and (6) contain two bromide anions and gemini surfactants (2) and (4) contain two chloride anions. A gemini surfactant composition may contain other surfactants such as monomeric cationic, monomeric nonionic, or monomeric anionic surfactants conventionally used in petroleum recovery. Cationic surfactants used for petroleum recovery include cetyl trimethyl ammonium bromide (CTAB), coco alkyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide (DTAB), ethoxylated alkyl amine, and cationic surfactants with quaternary ammonium surfactants having an amide linkage such as: Other conventional cationic, nonionic and anionic surfactants that may be admixed with or used in conjunction with a gemini surfactant according to the invention includes those described by Raffa, et al., J. Petroleum Sci. 145:723-733 (2016), or by Negin, et al., Petroleum 3(2): 197-211 (2017), which are incorporated by reference. Such a composition can have a weight ratio of the at least one gemini surfactant to the monomeric or non-dimeric surfactant of about 3:1, 2:1, 1:1, 1:2 to 1:3 (or any intermediate ratio within this range). A gemini surfactant composition may contain a demulsifier to prevent emulsion formation within the subterranean reservoir. When injected into a well the compositions containing the gemini surfactants are preferably not in the form of an emulsion and instead in the form of a single phase organic or aqueous solution. When present, a demulsifier may be selected from the group comprising, consisting essentially of, or consisting of polyethylenimine alkoxylates, alkoxylated alkylphenol formaldehyde resins, alkoxylated amine-modified alkylphenol formaldehyde resins, ethylene oxide/propylene oxide copolymers, crosslinked ethylene oxide/propylene oxide copolymers, and mixtures of these. When employed in a composition for petroleum recovery, the demulsifier may be present in an amount ranging from 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5 or >5 wt % based on the total weight of the composition for injection. In some embodiments a composition containing a gemini surfactant of the invention will also include coupling agent. A coupling agent may be selected from the group consisting of one or more of a linear, branched, or cyclic aliphatic alcohol having 1, 2, 3, 4, 5 to 6 carbon atoms, diols having 1, 2, 3, 4, 5 to 6 carbon atoms, alkyl ethers of alkylene glycols wherein the alkyl moiety has 1, 2, 3, 4, 5 to 6 carbon atoms, polyalkylene glycols, and mixtures of two or more thereof. When employed in a composition for petroleum recovery, the coupling agent may be present in an amount ranging from 0.001, 0.002, 0.005, 0.01, 0.02, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5 or >0.5 wt % based on the total weight of the composition for injection. This range includes all intermediate values and subranges. In some embodiments, the compositions further include one or more additives, wherein the additives are selected from clay stabilizers, corrosion inhibitors, scale inhibitors, viscosifying agents, solvents, flow back aids, friction reducers, proppants (e.g. silica sand, aluminum oxide), biocides, or mixtures thereof. Preferably, the gemini surfactants are injected as a single component fluid into wells without any co-surfactant or co-solvent. During use in oil field operations, a gemini surfactant is admixed with water such as produced water or water having a high content of dissolved solids. In some embodiments the water source is a high temperature water source, a high total dissolved solids water source, or a high temperature, high total dissolved solids water source, such as water with greater than 500, 1,000, 2,000, 10,000, 20,000, 50,000 or 100,000 ppm dissolved solids. This range includes all intermediate values and subranges. Dissolved solids include salts, metals and minerals. In some embodiments, the water source is contacted with a concentrated gemini surfactant composition at a temperature of about 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190,200, 210, 220, 230, 240, or about 250° C., preferably around 60 to 200° C. A gemini surfactant composition of the invention may be prepared in concentrated form or in a form more concentrated than that used during oil field operations such as fracking. A concentrate may contain 1, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 95 to >95 wt % actives based on the weight of the concentrate, where actives represent a total of the combined gemini surfactants, monomer surfactants, and demulsifiers based on the weight of the concentrate. Some examples of a degree of concentration range from >1, 2, 5, 10, 20, 50 or 100× (or any intermediate value) the diluted strength of the composition as injected into a wellbore. A preferred range of concentration of a gemini surfactant in the injectate, is from to 0.5 wt %, preferably 0.2-0.4 wt % based on the total weight of the injectate fluid. A concentrate containing one or more gemini surfactants of the invention may be storage stable, for example, ten days, two weeks, 1, 2, 3, 4, 5, 6 or >6 months under ambient temperatures such as between 0, 5, 10, 15, 20, 25, 30, 35 and 40° C. Aqueous solutions containing the gemini surfactants may be stable at 90° C. for a week, ten days, two weeks or more than two weeks and were also determined to be stable to temperatures up to 200° C. Aqueous solutions of the gemini surfactants of the invention have higher storage life and thermal stability compared to other surfactants used in petroleum industry. For example, sodium dodecyl sulfate (SDS) undergoes hydrolysis at high temperature and prolonged heating at 40° C. or higher causes decomposition of SDS. Aqueous solutions of the gemini surfactants can be heated at 50° C., 75° C. or 100° C. under the same conditions without showing more than 5%, 4%, 1% or 0.5% decomposition of the gemini surfactants based on the total weight of the gemini surfactants before and after heating. An injectate may be prepared from a concentrate or from its individual ingredients. For purposes of increasing hydrocarbon recovery an injectate may comprise <0.001, 0.001, 0.002, 0.005, 0.01, 0.01, 0.02, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9 10 or >10 wt % of a gemini surfactant (or any intermediate value within this range). In some embodiments an injectate comprises about 99, 99.9, 99.99 to 99.999 wt % of a water source and about 0.001, 0.01, 0.1 to 1 wt % of actives, such as one or more gemini surfactants or a mixture of gemini surfactant with other conventional actives. Another embodiment of the invention is directed to a method for increasing a recovery of crude oil or other hydrocarbon from a subterranean hydrocarbon-containing formation, such as during hydraulic fracturing. This method includes those directed to recovering hydrocarbons from a subterranean hydrocarbon-containing formation that is a carbonate reservoir or otherwise contains carbonates, or a sandstone reservoir as well as from tight shale reservoirs formed by hydraulic fracturing or “fracking”. This method includes injecting or otherwise contacting a composition comprising the gemini surfactant as disclosed herein with a subterranean hydrocarbon-containing formation. The injected composition contains at least one gemini surfactant of the invention and optionally, a cationic monomer surfactant, a demulsifier, a water source, and/or a coupling agent, or a combination of two or more thereof. The method proceeds by injecting the composition into a hydrocarbon-containing subterranean fractured rock formation; and collecting a hydrocarbon from the hydrocarbon-containing subterranean fractured rock formation. Any water source may be used to produce the composition for injection including produced water or flowback water. As disclosed above, a composition for injection will contain an amount of one or more gemini surfactants of the invention sufficient to enhance the recovery of a hydrocarbon, for example, it may contain the at least one gemini surfactant at a concentration of <0.001, 0.001, 0.002, 0.005, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1, 2, 5, 10, 20 or >20 wt. This range includes all intermediate values and subranges. The preferred range of concentration is ranged from 0.1 to 0.5 wt % used as a single component in an injectate. The method may be performed by injecting the composition into a first wellbore connected to the subterranean hydrocarbon-containing fractured rock formation and then recovering hydrocarbon from a second wellbore that is connected to the subterranean hydrocarbon-containing fractured rock formation; or by injecting the composition into a wellbore connected to the subterranean hydrocarbon-containing fractured rock formation, and then recovering the hydrocarbon from the same wellbore. In some embodiments, the composition will be produced from a concentrate containing the at least one gemini surfactant and other actives, such as monomeric surfactants and other ingredients described herein or known in the art for incorporation into an injectate or fracturing solution. Some examples of a degree of concentration range from >1, 2, 5, 10, 20, 50, 100, 200 or >200× (or any intermediate value) the diluted strength of the composition injected into a wellbore. In some embodiments, a concentrate may be injected simultaneously with water, such as produced water into a wellbore in an amount sufficient to produce the desired dilution. In other embodiments, the composition for injection will be premixed with water to its final strength prior to injection. In some embodiments, a concentrated or diluted gemini surfactant containing composition is first injected into a first wellbore connected to the subterranean hydrocarbon-containing formation, and the collecting is from a second wellbore that is connected to the subterranean hydrocarbon-containing formation. In other embodiments, the injecting and the collecting are carried out in the same wellbore. Examples Gemini surfactants according to the invention were synthesized and tested as described below. Materials. Dodecanoic acid (98%, Sigma), oleic acid (92%, biochemical), 3-(dimethylamino)-1-propylamine (99%, GC, Aldrich), 1,4-dibromobutane (99%, Aldrich), trans-1,4-dibromo-2-butene (99%, Aldrich), cis-1,4-dichloro-2-butene (95%, Aldrich), 1,6-dibromohexane (96%, Aldrich), aluminum oxide (fluka) were utilized as obtained. Distilled solvents were used for the synthesis of the gemini surfactants. Synthesis and spectral characterization of amido-amine intermediate (10 and 11). The synthesis of amido-amine intermediate compound (10) was achieved using improved method described by Chu and co-workers as outlined in Scheme 1 which describes the synthesis of amido-amine-based cationic gemini surfactants (1)-(6) (FIG.11); see Chu Z, Feng Y (2009)A facile route towards the preparation of ultra-long-chain amidosulfobetaine surfactants.Synlett (16):2655-2658, incorporated herein by reference in its entirety. Dodecanoic acid (7) (20.00 g, 99.84 mmol), 3-(dimethylamino)-1-propylamine (9) (20.40 g, 200 mmol), and sodium fluoride (NaF) (0.42 g, 9.98 mmol) were added in a 100 mL flask connected with reflux condenser and the condenser was further connected with bent distilling adapter filled with Al2O3in order to absorb the byproduct H2O. The experiment was continued under reflux at 160° C. for six-hour in an argon atmosphere. After six hours, further 3-(dimethylamino)-1-propylamine (15.30 g, 150 mmol) was introduced into the flask and the reaction was left to progress under the same experimental conditions for another five hours. After completion, the unreacted 3-(dimethylamino)-1-propylamine was separated and the residue was washed three times with a mixture of cold water: acetone (7:93) then vacuumed to form intermediate (10); Ghumare A K, Pawar B V, Bhagwat S S (2013)Synthesis and antibacterial activity of novel amido-amine-based cationic Gemini surfactants. Journal of Surfactants and Detergents 16 (1):85-93, incorporated herein by reference in its entirety. Intermediate (11) was prepared by adopting same method of intermediate (10). These procedures produced compounds (10) and (11) as described below. N-dodecanamidopropyl-N,N-dimethylamine (10): White solid (25.90 g, 91% yield)1H NMR (500 MHz, CDCl3) δ (ppm): 0.83 (t, J=6.7 Hz, 3H), 1.15-1.25 (m, 16H), 1.51-1.58 (m, 2H), 1.64-1.73 (m, 2H), 2.11 (t, J=7.6 Hz, 2H), 2.30 (s, 6H), 2.47 (t, J=6.4 Hz, 2H), 3.29 (pent, J=5.8 Hz, 2H), 6.99 (s, 1H (NH).13C NMR (125 MHz, CDCl3) δ (ppm): 14.0, 22.6, 25.7, 29.2, 29.3, 29.4, 29.5, 31.8, 36.8, 38.5, 44.8, 58.0, 173.3. N-oleamidopropyl-N,N-dimethylamine (11): Pale yellow viscous liquid (22.7 g, 87% yield).1H NMR (500 MHz, CDCl3) δ (ppm): 0.83 (t, J=6.7 Hz, 3H), 1.18-1.28 (m, 20H), 1.52-1.59 (m, 2H), 1.62-1.69 (m, 2H), 1.91-1.98 (m, 4H), 2.10 (t, J=7.6 Hz, 2H), 2.26 (s, 6H), 2.42 (t, J=6.4 Hz, 2H), 3.28 (pent, J=5.8 Hz, 2H), 5.25-5.31 (m, 2H), 7.0 (s, 1H (NH).13C NMR (125 MHz, CDCl3) δ (ppm): 14.0, 22.6, 25.7, 25.8, 27.1, 29.1, 29.2, 29.4, 29.6, 29.7, 31.8, 36.8, 38.7, 44.9, 58.0, 129.7, 129.9, 173.2. Synthesis and spectral characterization of amido-amine cationic Gemini surfactants (1) and (2). The amido-amine intermediate compound (10) (10.0 g, 35.15 mmol) was treated with trans-1,4-dibromo-2-butene (12) (3.0 g, 14.06 mmol) in dry ethanol (5 mL) under reflux (80° C.) for 48 h (Scheme 1). After completion, the product was separated and recrystallized using solvent mixture acetone/ethyl acetate to form the required gemini surfactant 1 as a white solid; Zana R et al. (1991). Gemini surfactant (2) was synthesized by adopting the same procedure of (1). Resulting surfactants (1) and (2) are described below. (E)-dodecanoic acid [3-({4-[(3-dodecanoylamino-propyl)-dimethyl-amino]but-2-enyl}-dimethyl-amino)-propyl]-amide dibromide (1): White solid (9.70 g, 88% yield based on trans-1,4-dibromo-2-butene).1H NMR (500 MHz, CDCl3) δ (ppm): 0.82 (t, J=6.7 Hz, 6H), 1.16-1.26 (m, 32H), 1.52-1.58 (m, 4H), 2.06-2.12 (m, 4H), 2.26-2.33 (m, 4H), 3.31 (s, 12H), 3.32-3.36 (m, 4H), 3.64-3.72 (m, 4H), 4.41-4.49 (m, 4H), 6.77-6.85 (m, 2H), 8.16 (s, 2H (NH).13C NMR (125 MHz, CDCl3) δ (ppm): 14.0, 22.6, 22.8, 25.9, 29.3, 29.4, 29.5, 29.6, 29.7, 31.8, 36.1, 36.6, 51.0, 62.6, 65.0, 130.2, 175.3. FTIR (KBr pellet) υ (cm−1) 3441 (υN—H, secondary amine), 2922 and 2850 (υC—H, aliphatic asymmetric and symmetric respectively), 1641 (amide I band), 1555 (amide II band). Anal. Calcd for C38H78O2N4Br2(782.86): C, 58.30; H, 10.04; N, 7.16. Found: C, 58.17; H, 10.19; N, 7.08. (Z)-dodecanoic acid [3-({4-[(3-dodecanoylamino-propyl)-dimethyl-amino]but-2-enyl}-dimethyl-amino)-propyl]-amide dichloride (2): White solid (11.85 g, 71% yield based on cis-1,4-dichloro-2-butene).1H NMR (500 MHz, CDCl3) δ (ppm): 0.83 (t, J=6.7 Hz, 6H), 1.18-1.28 (m, 32H), 1.55-1.61 (m, 4H), 2.06-2.12 (m, 4H), 2.28-2.34 (m, 4H), 3.29 (s, 12H), 3.30-3.36 (m, 4H), 3.63-3.71 (m, 4H), 4.67-4.73 (m, 4H), 6.38-6.44 (m, 2H), 8.52 (s, 2H (NH).13C NMR (125 MHz, CDCl3) 3 (ppm): 14.1, 22.7, 22.9, 26.0, 29.3, 29.4, 29.5, 29.6, 29.7, 31.9, 35.9, 36.6, 50.5, 60.8, 62.3, 128.1, 175.5. FTIR (KBr pellet) υ (cm−1) 3475 (υN—H, secondary amine), 2924 and 2852 (σC—H, aliphatic asymmetric and symmetric respectively), 1642 (amide I band), 1545 (amide II band). Anal. Calcd for C38H78O2N4Cl2(693.96): C, 65.77; H, 11.33; N, 8.07. Found: C, 65.65; H, 11.41; N, 8.02. Synthesis and spectral characterization of amido-amine cationic Gemini surfactants (3)-(6). The amido-amine intermediate compound (11) (10.0 g, ×27.28 mmol) was treated with trans-1,4-dibromo-2-butene (12) (2.33 g, 10.91 mmol) in dry ethanol (5 mL) for 48 h under reflux (80° C.). After completion, the reaction product was purified using silica gel column chromatography with methanol:acetone (3:7) as eluent to afford required gemini surfactant (3); Zana R et al. (1991). Gemini surfactants (4)-(6) of this series were synthesized by adopting the same procedure of (3). The resulting surfactants are described below. (E)-oleic acid [3-({4-[(3-oleamidopropyl)-dimethyl-amino]but-2-enyl}-dimethyl-amino)-propyl]-amide dibromide (3): Pale yellow viscous oil (8.49 g, 82% yield based on trans-1,4-dibromo-2-butene).1H NMR (500 MHz, CDCl3) δ (ppm): 0.82 (t, J=6.7 Hz, 6H), 1.18-1.28 (m, 40H), 1.49-1.55 (m, 4H), 1.91-1.97 (m, 8H), 2.0-2.06 (m, 4H), 2.21 (t, J=7.6 Hz, 4H), 3.23 (s, 12H), 3.24-3.30 (m, 4H), 3.52-3.58 (m, 4H), 4.27-4.33 (m, 4H), 5.23-5.33 (m, 4H), 6.62-6.68 (m, 2H), 7.79 (s, 2H (NH).13C NMR (125 MHz, CDCl3) δ (ppm): 14.0, 22.6, 23.0, 25.7, 27.2, 29.3, 29.4, 29.5, 29.7, 29.8, 31.8, 36.4, 51.1, 62.6, 64.9, 129.5, 129.9, 130.2, 174.8. FTIR (KBr pellet) υ (cm−1) 3445 (υN—H, secondary amine), 2926 and 28547 (υC—H, aliphatic asymmetric and symmetric respectively), 1643 (amide I band), 1551 (amide II band). Anal. Calcd for C50H98O2N4Br2(947.15): C, 63.40; H, 10.43; N, 5.92. Found: C, 63.32; H, 10.57; N, 5.82. (Z)-oleic acid [3-({4-[(3-oleamidopropyl)-dimethyl-amino]but-2-enyl}-dimethyl-amino)-propyl]-amide dichloride (4): Pale yellow viscous oil (12.80 g, 80% yield based on cis-1,4-dichloro-2-butene).1H NMR (500 MHz, CDCl3) δ (ppm): 0.83 (t, J=6.7 Hz, 6H), 1.17-1.27 (m, 40H), 1.47-1.55 (m, 4H), 1.91-1.97 (m, 8H), 1.99-2.05 (m, 4H), 2.20 (t, J=7.6 Hz, 4H), 3.23 (s, 12H), 3.24-3.30 (m, 4H), 3.53-3.59 (m, 4H), 4.52-4.58 (m, 4H), 5.22-5.32 (m, 4H), 6.32-6.38 (m, 2H), 8.0 (s, 2H (NH).13C NMR (125 MHz, CDCl3) δ (ppm): 14.0, 22.6, 23.0, 25.9, 27.2, 29.3, 29.4, 29.5, 29.7, 29.8, 31.8, 36.3, 50.6, 60.6, 62.3, 127.7, 129.5, 129.9, 174.8. FTIR (KBr pellet) υ (cm−1) 3431 (υN—H, secondary amine), 2924 and 2853 (υC—H, aliphatic asymmetric and symmetric respectively), 1642 (amide I band), 1552 (amide II band). Anal. Calcd for C50H98O2N4Cl2(858.24): C, 69.97; H, 11.51; N, 6.53. Found: C, 69.84; H, 11.57; N, 6.63. Oleic acid [3-({4-[(3-oleamidopropyl)-dimethyl-amino]butyl}-dimethyl-amino)-propyl]-amide dibromide (5): Pale yellow gel (9.3 g, 91% yield based on 1,4-dibromobutane).1H NMR (500 MHz, CDCl3) δ (ppm): 0.83 (t, J=6.7 Hz, 6H), 1.18-1.28 (m, 40H), 1.50-1.56 (m, 4H), 1.91-1.97 (m, 12H), 1.99-2.05 (m, 4H), 2.21 (t, J=7.6 Hz, 4H), 3.19 (s, 12H), 3.25-3.31 (m, 4H), 3.44-3.50 (m, 4H), 3.54-3.60 (m, 4H), 5.23-5.33 (m, 4H), 7.81 (s, 2H (NH).13C NMR (125 MHz, CDCl3) δ (ppm): 14.1, 19.6, 22.6, 22.9, 25.9, 27.2, 29.3, 29.4, 29.5, 29.7, 29.8, 31.8, 36.4, 51.4, 62.3, 63.2, 129.6, 129.9, 174.9. FTIR (KBr pellet) υ (cm−1) 3439 (υN—H, secondary amine), 2923 and 2851 (υC—H, aliphatic asymmetric and symmetric respectively), 1632 (amide I band), 1548 (amide II band). Anal. Calcd for C50H100O2N4Br2(949.16): C, 63.27; H, 10.62; N, 5.90. Found: C, 63.21; H, 10.57; N, 5.87. Oleic acid [3-({6-[(3-oleamidopropyl)-dimethyl-amino]hexyl}-dimethyl-amino)-propyl]-amide dibromide (6): White solid (8.7 g, 93% yield based on 1,6-dibromohexane).1H NMR (500 MHz, CDCl3) δ (ppm): 0.82 (t, J=6.7 Hz, 6H), 1.17-1.27 (m, 40H), 1.46-1.52 (m, 4H), 1.54-1.60 (m, 4H), 1.91-1.97 (m, 12H), 2.02-2.08 (m, 4H), 2.33 (t, J=7.6 Hz, 4H), 3.26 (s, 12H), 3.33-3.39 (m, 4H), 3.53-3.59 (m, 4H), 3.69-3.75 (m, 4H), 5.23-5.33 (m, 4H), 8.40 (s, 2H (NH).13C NMR (125 MHz, CDCl3) δ (ppm): 14.1, 21.6, 22.6, 22.7, 24.6, 25.9, 27.1, 29.1, 29.2, 29.3, 29.4, 29.6, 29.7, 31.8, 35.8, 51.1, 62.3, 65.0, 129.6, 129.9, 175.3. FTIR (KBr pellet) υ (cm−1) 3440 (υN—H, secondary amine), 2924 and 2852 (υC—H, aliphatic asymmetric and symmetric respectively), 1633 (amide I band), 1549 (amide II band). Anal. Calcd for C52H104O2N4Br2(977.22): C, 63.91; H, 10.73; N, 5.73. Found: C, 63.78; H, 10.80; N, 5.64. Analytical Equipment. The structures of the amido-amine-based cationic gemini surfactants (1)-(6) were established by using NMR, FTIR, and elemental analysis. The NMR data was acquired on 500 MHz NMR instrument (Jeol 1500 model). Deuterated chloroform was used as a solvent, TMS as an internal standard, and chemical shifts in NMR spectra were recorded in ppm. The FTIR (fourier transform infrared) spectroscopy was done using FTIR spectrophotometer (Perkin-Elmer 16F model) and spectra were recorded in wave numbers (cm−1). Elemental analysis was obtained using Perkin Elmer Series 11 (CHNS/O) Analyzer 2400. Thermogravimetric Analysis. Thermogravimetric analysis (TGA) was conducted using SDT Q600 apparatus from TA instruments with a constant heating rate of 20° C./min and the temperature range was 30-500° C. The experiment was run using an aluminum sample pan with nitrogen flow rate of 100 mL/min. Long-Term Thermal Stability. Long-term thermal stability was assessed using a novel approach based on an aging technique. Aqueous solutions of gemini surfactants (1)-(6) were aged in a sealed tube for 10 days at 90° C. NMR (1H,13C) and FTIR instruments were used to identify the changes in the structure of the surfactants after aging. Surface Properties. Surface tensions were identified with the help of pendant drop method at 20° C. using Biolin Scientific Attension instrument. Water was used as a solvent for all surface tension experiments. The reported data points of all surface tension measurements are average equilibrium values. The critical micelle concentration (cmc) was measured from the intersection point of two lines in the plot of surface tension versus concentration. The synthesis of amido-amine-based cationic gemini surfactants (1)-(6) was achieved using an improved method outlined in scheme 1. The condensation of commercially available carboxylic acid (7) and (8) with 3-(dimethylamino)-1-propylamine (9) generated the amide intermediates (10) and (11). The reaction was followed by quaternization reaction with halohydrocarbons (12-15) yielding the desired amido-amine cationic gemini surfactants (1)-(6) with high yield; Ghumare A K (2013); and Zana R, Benrraou M, Rueff R (1991)Alkanediyl-.alpha.,. omega.-bis(dimethylalkylammonium bromide)surfactants.1. Effect of the spacer chain length on the critical micelle concentration and micelle ionization degree. Langmuir 7 (6):1072-1075, each incorporated herein by reference in their entirety. Structures of gemini surfactants and corresponding intermediates were confirmed by characterization techniques such as NMR, FTIR, and elemental analysis. The six amido-amine-based cationic gemini surfactants exhibited nearly same peak pattern, therefore, the spectral characterization of gemini surfactant (1) and its intermediate (10) were highlighted as examples. According to1H NMR spectra of the intermediate compound (10), the terminal methyl protons [—(CH2)n—CH3)] resonated at δ=0.83 ppm and the methylene protons [—(CH2)n—CH3)] in the hydrophobic tail resonated at δ=1.15-1.25 ppm. The disappearance of hydroxyl proton in the carboxylic acid (—CH2—C═O—OH) (8) at δ=10.25 ppm and the appearance of the amide proton (—CH2—C═O—NH) (10) at δ=6.99 ppm were observed. The appearance of the methyl proton directly attached to the tertiary nitrogen [—CH2—N—(CH3)2] at δ=2.30 confirmed the formation of intermediate compound (10). According to13C NMR spectra of intermediate compound (10), the terminal methyl carbon [—(CH2)n—CH3)] resonated at δ=14.0 ppm and the methylene carbons [—(CH2)n—CH3)] in the hydrophobic tail resonated at δ=22.6-36.8 ppm. The two methyl carbon directly attached to the tertiary nitrogen [—CH2—N—(CH3)2] resonated at δ=44.8 ppm. The methylene carbon next to tertiary nitrogen [—CH2—CH2—N—(CH3)2] in compound (10) resonated at δ=58.0 ppm. The appearance of the carbonyl carbon of fatty acid (7) (—CH2—C═O—OH) resonated at δ=180.4 ppm and then clear up field shift of the same carbonyl carbon in amide (10) (—CH2—C═O—NH—) at δ=173.3 ppm confirmed the formation of intermediate (10). According to1H NMR spectra of gemini surfactant (1), the terminal methyl protons [—(CH2)n—CH3)] resonated at δ=0.82 ppm and the methylene protons [—(CH2)n—CH3)] in the hydrophobic tail resonated at δ=1.16-1.26 ppm. The methyl protons directly attached to the nitrogen [—CH2—N—(CH3)2] that previously appeared at δ=2.30 ppm in intermediate (10) has shifted downfield to δ=3.31 ppm in the gemini surfactant (1) [—CH2—N—(CH3)2—CH2—]. The downfield shift of the amide proton (—CH2—C═O—NH) from δ=6.99 ppm in compound 10 to δ=8.16 ppm in gemini surfactant 1 has been also detected. The olefinic protons in the spacer group [—N—CH2—CH═CH—CH2—N—] appeared at δ=6.77-6.85 ppm which further confirmed the formation of the gemini surfactant 1. According to13C NMR spectra of the gemini surfactant (1), the terminal methyl carbon [—(CH2)n—CH3)] resonated at δ=14.0 ppm and the methylene carbons [—(CH2)n—CH3)] in the hydrophobic tail resonated at δ=22.6-36.6 ppm. The two methyl carbons of the tertiary nitrogen [—CH2—N—(CH3)2] that were resonated at δ=44.8 ppm in the intermediate (10) have shifted downfield to δ=51.0 ppm as evidence of the formation of the gemini surfactant 1. The two new peaks that appeared at δ=62.6 ppm and 65.0 ppm correspond to 2 methylene groups connected with nitrogen [—CH2—N—(CH3)2—CH2—]. The olefinic carbon in spacer group [—N—CH2—CH═CH—CH2—N-] resonated at δ=130.2 ppm. The carbonyl carbon (—CH2—C═O—NH—) peak was detected at δ=175.3 ppm. In general, the NMR (1H and13C) spectral data appeared to be compatible with the proposed structures of the gemini surfactant 1. In FTIR spectra of the gemini surfactant 1, a disappearance of the hydroxyl group of fatty acid (7) (—CH2—C═O—OH) ranged from 2400 to 3400 cm−1and an existence of amide (—CH2—C═O—NH) at 3441 cm−1as well as a shifting of the band of carbonyl stretching (—C═O—) from the region of acid (—CH2—C═O—OH) at 1710 cm−1to the region of amide (—CH2—C═O—NH—) at 1641 cm−1were observed. Amide I band resonated at 1641 cm−1and amide II band resonated at 1555 cm−1; Ghumare A K (2013). The two stretching vibrations at 2922 cm−1(CH aliphatic symmetric) and 2850 cm−1(CH aliphatic asymmetric) were also detected which confirmed the formation of the gemini surfactant (1); Dardir M, Mohamed D, Farag A, Ramdan A, Fayad M (2016)Preparation and evaluation of cationic bolaform surfactants for water-based drilling fluids. Egyptian Journal of Petroleum; Shaban S M, Aiad I, Fetouh H A, Maher A (2015)Amidoamine double tailed cationic surfactant based on dimethylaminopropylamine: Synthesis, characterization and evaluation as biocide. Journal of Molecular Liquids 212:699-707; and El-Lateef H M A, Abo-Riya M A, Tantawy A H (2016),Empirical and quantum chemical studies on the corrosion inhibition performance of some novel synthesized cationic Gemini surfactants on carbon steel pipelines in acid pickling processes. Corrosion Science 108:94-110, each incorporated herein by reference in their entirety. Thermal Stability of Gemini Surfactants (1)-(6). Thermal stability is an essential property of surfactants for various oilfield applications. A surfactant, which designed to be used in surfactant flooding, should be thermally stable at high reservoir temperature (≥90° C.) because it may stay inside oil reservoir for many days. The high temperature in a reservoir can cause surfactant precipitation due to thermal degradation and the surfactant ability to reduce interfacial tension between water and oil can be decreased significantly. The short-term and long-term thermal stability of the synthesized gemini surfactants (1)-(6) were investigated. The short-term stability was assessed with the help of TGA instrument and the graph exhibited excellent thermal stability of the gemini surfactants (1-6) with no thermal degradation up to 200° C. (FIG.2). The long-term thermal stability of the gemini surfactants (1)-(6) was examined using a novel approach based on aging technique where the aqueous solutions of surfactants were aged in a sealed tube at 90° C. for 10 days. NMR (1H,13C) and FTIR instruments were used to study the change in the structure of the surfactants after aging at a different period. However, only FTIR and NMR spectra of the 10 days aged surfactants were presented. The six amido-amine cationic gemini surfactants (1)-6) exhibited excellent long-term thermal stability with no thermal degradation after 10 days aging. Spectral characterization of the 10 days aged sample of gemini surfactant (1) and (6) were highlighted as examples. The1H NMR spectra of the 10 days aged samples of the gemini surfactants (1) and (6) (FIGS.3and5) demonstrated the appearance of the protons of the terminal methyl group [—(CH2)n—CH3)] as well as protons of the methylene group [—(CH2)n—CH3)] of the surfactant hydrophobic tail. The olefinic protons in the hydrophobic tail of the gemini surfactants 6 (FIG.5) were also revealed. Similarly, the olefinic protons in the spacer group of 10 days aged sample of gemini surfactants 1 (FIG.3) were also detected. Likewise, the methylene protons in the spacer group of gemini surfactants 6 (FIG.5) equally appeared. The protons of methyl group directly attached with quaternary nitrogen [—CH2—N+—(CH3)2—CH2-] clearly observed. In addition, the appearance of the amide proton (—CH2—C═O—NH—) confirmed the survival of Gemini surfactants (1) and (6) in harsh conditions. An additional peak at δ=4-5 ppm appeared in after aging sample correspond to residual water; Fulmer G R, Miller A J, Sherden N H, Gottlieb H E, Nudelman A, Stoltz B M, Bercaw J E, Goldberg K I (2010)NMR chemical shifts of trace impurities: common laboratory solvents, organics, and gases in deuterated solvents relevant to the organometallic chemist. Organometallics 29 (9):2176-2179, incorporated herein by reference in its entirety. According to13C NMR spectra of the 10 days aged samples of gemini surfactants (1) and (6)(FIGS.4and6), the methyl [—(CH2)n—CH3)] and methylene carbon in hydrophobic tail of gemini surfactants (1) and (6) were clearly identified. The two methyl carbon [—CH2—N+—(CH3)2—CH2-] and two methylene carbon [—CH2—N+(CH3)2—CH2-] directly attached to the quaternary nitrogen were similarly observed in both surfactants (1) and (6) (FIGS.4and6). The olefinic carbon in hydrophobic tail of gemini surfactant (6) (FIG.6) as well as the olefinic carbon in spacer group of gemini surfactant 1 (FIG.4) were also detected. The carbonyl carbon of amide group [—CH2—C═O—NH] was clearly shown in both surfactants. In general, the NMR (1H and13C) spectra of the aged samples of gemini surfactants (1 and 6) confirmed that no structural changes occurred. According to the FTIR spectra of 10 days aged samples of gemini surfactants (1) and (6) (FIGS.7and8), the two clear stretching bands in the region of 2921 cm−1and 2850 cm−1were detected and they correspond to CH aliphatic symmetric and CH aliphatic asymmetric respectively. The carbonyl stretching and C—N stretching were also observed which confirmed the structure of gemini surfactants (1) and (6) and showed the thermal stability of amido-amine cationic gemini surfactants. There was no cloudiness and phase separation before and after aging at 90° C.; therefore, the cloud points of the surfactants were >90° C. Surface Tension Measurements. The synthesized gemini surfactants (1)-(6) showed good water solubility and surface tension was identified at 25° C.FIGS.9and10exhibited surface tension of all surfactants at different concentrations, while other surface properties are given in Table 1. The surface tension remarkably decreased upon addition of more surfactant up to the breakpoint at cmc. Further addition of surfactant above cmc showed no change in the surface tension. The surfactant 2 showed the highest surface tension while the surfactant 6 showed the least surface tension at all investigated concentrations. The surface properties can be related to the different chain length, spacer length, spacer rigidity, and to the presence of different counterions in the gemini surfactants. TABLE 1Surface properties of Gemini surfactants (1)-(6)cmcγcmcπcmcΓmax× 106AminSurfactants(mol L−1)(mN m−1)(mN m−1)(mol m−2)(nm2)12.56 × 10−436.2335.771.810.9123 61 × 10−438.1233.881.601.0531.58 × 10−435.6736.331.920.8642.91 × 10−437.2334.771.641.0151.05 × 10−432.9239.082.260.7360.77 × 10−430.3441.662.380.70 FIG.9shows the effect of the spacer length and rigidity on the surface tension of the gemini surfactants. By comparing the surfactant (5) and (6), it was observed that the surfactant with a larger spacer (6) showed lower cmc which could be associated to the hydrophobic nature of longer spacer; Chavda S, Bahadur P Aswal V K (2011)Interaction between nonionic and Gemini(cationic)surfactants: effect of spacer chain length. Journal of Surfactants and Detergents 14 (3):353-362, incorporated herein by reference in its entirety. The rigidity of spacer is another important parameter in determining the aggregation morphologies of the gemini surfactants. Surfactant (3) and surfactant (5) possess almost similar structures but the spacer of surfactant (3) is more rigid compared to the surfactant (5). The gemini surfactant (3) with more rigid spacer demonstrated a higher cmc and corresponding surface tension at cmc (γcmc). The cmc and γcmcof gemini surfactant (3) were 1.58×10−4mol L−1and 35.67 mN m−1, respectively, which is much higher as compared to the surfactant 5 that has a relatively flexible spacer. The gemini surfactants containing rigid spacer usually make vesicles. On the other hand, the gemini surfactants without rigidity can form a mixture of vesicles and micelles; Zhu D-Y et al. (2012). Chain length of a surfactant is another critical parameter that affects the surface properties of surfactant.FIG.10compares the surface tension of the gemini surfactants with different chain length and spacer orientation. By comparing the surfactants (1) and (3), the cmc and the corresponding γcmcwere decreased when the hydrophobic tail was increased from 12 carbons (1) to 18 carbons (3). A similar trend was observed with the surfactants (2) and (4), which also have the same spacer and counterions but differ with each other by the length of the hydrophobic tail. The double bond in spacer of the surfactant (1) and (3) was in trans conformation with bromide counterions while the double bond in spacer of surfactant (2) and (4) was in cis conformation with chloride counterions. The cmc and the γcmcof the surfactant 2 and 4 were higher as compared to the analogous surfactant (1) and (3) respectively. The difference of surface properties between the surfactants (1), (2) and (3), (4) may be associated with the different conformation of spacer double bond and counters ions. It has been reported previously that the presence of different counterions in the spacer can alter the cmc value; Menger F. et al., (2000). In summary, high cmc and γcmcwas observed for the surfactant (2) while the surfactant (6) showed the least cmc and γcmc. The gemini surfactant ability to lower the surface tension of water (πcmc), highest surface access (rmax) at the interface of air-water, as well as nominal surface area per molecule (Amin) was given in Table 1. The method used to calculate these properties was also given in our previous publication; Hussain S S, Animashaun M A, Kamal M S, Ullah N, Hussein I A, Sultan A S (2016)Synthesis, Characterization and Surface Properties of Amidosulfobetaine Surfactants Bearing Odd-Number Hydrophobic Tail. J Surfactants Deterg 19 (2):413-420, incorporated herein by reference in its entirety. The nominal surface area per molecule decreased by increasing the hydrophobic tail, spacer length and increased by increasing the spacer rigidity. The highest surface access at the air-water interface increased by increasing the hydrophobic tail and spacer length. As shown herein, the inventors synthesized amido-amine-based cationic gemini surfactants (1)-(6) with excellent yields and at high purity from the commercially available carboxylic acids. These gemini surfactants exhibited excellent short-term and long-term thermal stabilities, impressive surface activities and excellent surface tensions. Thermogravimetric analysis demonstrated excellent thermal stabilities of the synthesized surfactants (1)-(6) with no structural degradation up to 200° C. Moreover, the inventors noticed that the thermal stability increased with increase of the chain length of the surfactants. Long-term thermal stability was assessed using novel approach based on structure characterization before and after aging. The NMR and FTIR results revealed excellent long-term thermal stability of the gemini surfactants (1)-(6) with no change in the structures even after aging for 10 days at 90° C. These gemini surfactants show a great potential in lowering the surface tension values with quite low cmc. Gemini surfactant (2) demonstrated the highest cmc and corresponding surface tension values, however, gemini surfactant (6) displayed the least cmc and corresponding surface tension values among all the investigated surfactants. Surfactants with a trans conformation were found to be predominant as compared to surfactants with a cis conformation. The great tolerance to high temperature and unique surface activities of the synthesized gemini surfactants (1)-(6) permits their use for many oilfield applications. | 50,121 |
11858879 | DETAILED DESCRIPTION OF THE INVENTION I. Definitions The abbreviations used herein have their conventional meaning within the chemical and biological arts. The chemical structures and formulae set forth herein are constructed according to the standard rules of chemical valency known in the chemical arts. Where substituent groups are specified by their conventional chemical formulae, written from left to right, they equally encompass the chemically identical substituents that would result from writing the structure from right to left, e.g., —CH2O— is equivalent to —OCH2—. The term “alkyl,” by itself or as part of another substituent, means, unless otherwise stated, a straight (i.e., unbranched) or branched carbon chain (or carbon), or combination thereof, which may be fully saturated, mono- or polyunsaturated and can include mono-, di- and multivalent radicals. The alkyl may include a designated number of carbons (e.g., C1-C10means one to ten carbons). Alkyl is an uncyclized chain. Examples of saturated hydrocarbon radicals include, but are not limited to, groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, methyl, homologs and isomers of, for example, n-pentyl, n-hexyl, n-heptyl, n-octyl, and the like. An unsaturated alkyl group is one having one or more double bonds or triple bonds. Examples of unsaturated alkyl groups include, but are not limited to, vinyl, 2-propenyl, crotyl, 2-isopentenyl, 2-(butadienyl), 2,4-pentadienyl, 3-(1,4-pentadienyl), ethynyl, 1- and 3-propynyl, 3-butynyl, and the higher homologs and isomers. An alkoxy is an alkyl attached to the remainder of the molecule via an oxygen linker (—O—). An alkyl moiety may be an alkenyl moiety. An alkyl moiety may be an alkynyl moiety. An alkyl moiety may be fully saturated. An alkenyl may include more than one double bond and/or one or more triple bonds in addition to the one or more double bonds. An alkynyl may include more than one triple bond and/or one or more double bonds in addition to the one or more triple bonds. In embodiments, the term “cycloalkyl” means a monocyclic, bicyclic, or a multicyclic cycloalkyl ring system. In embodiments, monocyclic ring systems are cyclic hydrocarbon groups containing from 3 to 8 carbon atoms, where such groups can be saturated or unsaturated, but not aromatic. In embodiments, cycloalkyl groups are fully saturated. Examples of monocyclic cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, and cyclooctyl. Bicyclic cycloalkyl ring systems are bridged monocyclic rings or fused bicyclic rings. In embodiments, bridged monocyclic rings contain a monocyclic cycloalkyl ring where two non adjacent carbon atoms of the monocyclic ring are linked by an alkylene bridge of between one and three additional carbon atoms (i.e., a bridging group of the form (CH2)w, where w is 1, 2, or 3). Representative examples of bicyclic ring systems include, but are not limited to, bicyclo[3.1.1]heptane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, bicyclo[3.2.2]nonane, bicyclo[3.3.1]nonane, and bicyclo[4.2.1]nonane. In embodiments, fused bicyclic cycloalkyl ring systems contain a monocyclic cycloalkyl ring fused to either a phenyl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, a monocyclic heterocyclyl, or a monocyclic heteroaryl. In embodiments, the bridged or fused bicyclic cycloalkyl is attached to the parent molecular moiety through any carbon atom contained within the monocyclic cycloalkyl ring. In embodiments, cycloalkyl groups are optionally substituted with one or two groups which are independently oxo or thia. In embodiments, the fused bicyclic cycloalkyl is a 5 or 6 membered monocyclic cycloalkyl ring fused to either a phenyl ring, a 5 or 6 membered monocyclic cycloalkyl, a 5 or 6 membered monocyclic cycloalkenyl, a 5 or 6 membered monocyclic heterocyclyl, or a 5 or 6 membered monocyclic heteroaryl, wherein the fused bicyclic cycloalkyl is optionally substituted by one or two groups which are independently oxo or thia. In embodiments, multicyclic cycloalkyl ring systems are a monocyclic cycloalkyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic aryl, a bicyclic heteroaryl, a bicyclic cycloalkyl, a bicyclic cycloalkenyl, and a bicyclic heterocyclyl; or (ii) two other ring systems independently selected from the group consisting of a phenyl, a bicyclic aryl, a monocyclic or bicyclic heteroaryl, a monocyclic or bicyclic cycloalkyl, a monocyclic or bicyclic cycloalkenyl, and a monocyclic or bicyclic heterocyclyl. In embodiments, the multicyclic cycloalkyl is attached to the parent molecular moiety through any carbon atom contained within the base ring. In embodiments, multicyclic cycloalkyl ring systems are a monocyclic cycloalkyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic aryl, a bicyclic heteroaryl, a bicyclic cycloalkyl, a bicyclic cycloalkenyl, and a bicyclic heterocyclyl; or (ii) two other ring systems independently selected from the group consisting of a phenyl, a monocyclic heteroaryl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, and a monocyclic heterocyclyl. Examples of multicyclic cycloalkyl groups include, but are not limited to tetradecahydrophenanthrenyl, perhydrophenothiazin-1-yl, and perhydrophenoxazin-1-yl. In embodiments, a cycloalkyl is a cycloalkenyl. The term “cycloalkenyl” is used in accordance with its plain ordinary meaning. In embodiments, a cycloalkenyl is a monocyclic, bicyclic, or a multicyclic cycloalkenyl ring system. In embodiments, monocyclic cycloalkenyl ring systems are cyclic hydrocarbon groups containing from 3 to 8 carbon atoms, where such groups are unsaturated (i.e., containing at least one annular carbon carbon double bond), but not aromatic. Examples of monocyclic cycloalkenyl ring systems include cyclopentenyl and cyclohexenyl. In embodiments, bicyclic cycloalkenyl rings are bridged monocyclic rings or a fused bicyclic rings. In embodiments, bridged monocyclic rings contain a monocyclic cycloalkenyl ring where two non adjacent carbon atoms of the monocyclic ring are linked by an alkylene bridge of between one and three additional carbon atoms (i.e., a bridging group of the form (CH2)w, where w is 1, 2, or 3). Representative examples of bicyclic cycloalkenyls include, but are not limited to, norbomenyl and bicyclo[2.2.2]oct 2 enyl. In embodiments, fused bicyclic cycloalkenyl ring systems contain a monocyclic cycloalkenyl ring fused to either a phenyl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, a monocyclic heterocyclyl, or a monocyclic heteroaryl. In embodiments, the bridged or fused bicyclic cycloalkenyl is attached to the parent molecular moiety through any carbon atom contained within the monocyclic cycloalkenyl ring. In embodiments, cycloalkenyl groups are optionally substituted with one or two groups which are independently oxo or thia. In embodiments, multicyclic cycloalkenyl rings contain a monocyclic cycloalkenyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic aryl, a bicyclic heteroaryl, a bicyclic cycloalkyl, a bicyclic cycloalkenyl, and a bicyclic heterocyclyl; or (ii) two ring systems independently selected from the group consisting of a phenyl, a bicyclic aryl, a monocyclic or bicyclic heteroaryl, a monocyclic or bicyclic cycloalkyl, a monocyclic or bicyclic cycloalkenyl, and a monocyclic or bicyclic heterocyclyl. In embodiments, the multicyclic cycloalkenyl is attached to the parent molecular moiety through any carbon atom contained within the base ring. In embodiments, multicyclic cycloalkenyl rings contain a monocyclic cycloalkenyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic aryl, a bicyclic heteroaryl, a bicyclic cycloalkyl, a bicyclic cycloalkenyl, and a bicyclic heterocyclyl; or (ii) two ring systems independently selected from the group consisting of a phenyl, a monocyclic heteroaryl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, and a monocyclic heterocyclyl. In embodiments, a heterocycloalkyl is a heterocyclyl. The term “heterocyclyl” as used herein, means a monocyclic, bicyclic, or multicyclic heterocycle. The heterocyclyl monocyclic heterocycle is a 3, 4, 5, 6 or 7 membered ring containing at least one heteroatom independently selected from the group consisting of O, N, and S where the ring is saturated or unsaturated, but not aromatic. The 3 or 4 membered ring contains 1 heteroatom selected from the group consisting of O, N and S. The 5 membered ring can contain zero or one double bond and one, two or three heteroatoms selected from the group consisting of O, N and S. The 6 or 7 membered ring contains zero, one or two double bonds and one, two or three heteroatoms selected from the group consisting of O, N and S. The heterocyclyl monocyclic heterocycle is connected to the parent molecular moiety through any carbon atom or any nitrogen atom contained within the heterocyclyl monocyclic heterocycle. Representative examples of heterocyclyl monocyclic heterocycles include, but are not limited to, azetidinyl, azepanyl, aziridinyl, diazepanyl, 1,3 dioxanyl, 1,3 dioxolanyl, 1,3 dithiolanyl, 1,3 dithianyl, imidazolinyl, imidazolidinyl, isothiazolinyl, isothiazolidinyl, isoxazolinyl, isoxazolidinyl, morpholinyl, oxadiazolinyl, oxadiazolidinyl, oxazolinyl, oxazolidinyl, piperazinyl, piperidinyl, pyranyl, pyrazolinyl, pyrazolidinyl, pyrrolinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl, thiadiazolinyl, thiadiazolidinyl, thiazolinyl, thiazolidinyl, thiomorpholinyl, 1,1 dioxidothiomorpholinyl (thiomorpholine sulfone), thiopyranyl, and trithianyl. The heterocyclyl bicyclic heterocycle is a monocyclic heterocycle fused to either a phenyl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, a monocyclic heterocycle, or a monocyclic heteroaryl. The heterocyclyl bicyclic heterocycle is connected to the parent molecular moiety through any carbon atom or any nitrogen atom contained within the monocyclic heterocycle portion of the bicyclic ring system. Representative examples of bicyclic heterocyclyls include, but are not limited to, 2,3 dihydrobenzofuran 2 yl, 2,3 dihydrobenzofuran 3 yl, indolin 1 yl, indolin 2 yl, indolin 3 yl, 2,3 dihydrobenzothien 2 yl, decahydroquinolinyl, decahydroisoquinolinyl, octahydro 1H indolyl, and octahydrobenzofuranyl. In embodiments, heterocyclyl groups are optionally substituted with one or two groups which are independently oxo or thia. In certain embodiments, the bicyclic heterocyclyl is a 5 or 6 membered monocyclic heterocyclyl ring fused to a phenyl ring, a 5 or 6 membered monocyclic cycloalkyl, a 5 or 6 membered monocyclic cycloalkenyl, a 5 or 6 membered monocyclic heterocyclyl, or a 5 or 6 membered monocyclic heteroaryl, wherein the bicyclic heterocyclyl is optionally substituted by one or two groups which are independently oxo or thia. Multicyclic heterocyclyl ring systems are a monocyclic heterocyclyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic aryl, a bicyclic heteroaryl, a bicyclic cycloalkyl, a bicyclic cycloalkenyl, and a bicyclic heterocyclyl; or (ii) two other ring systems independently selected from the group consisting of a phenyl, a bicyclic aryl, a monocyclic or bicyclic heteroaryl, a monocyclic or bicyclic cycloalkyl, a monocyclic or bicyclic cycloalkenyl, and a monocyclic or bicyclic heterocyclyl. The multicyclic heterocyclyl is attached to the parent molecular moiety through any carbon atom or nitrogen atom contained within the base ring. In embodiments, multicyclic heterocyclyl ring systems are a monocyclic heterocyclyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic aryl, a bicyclic heteroaryl, a bicyclic cycloalkyl, a bicyclic cycloalkenyl, and a bicyclic heterocyclyl; or (ii) two other ring systems independently selected from the group consisting of a phenyl, a monocyclic heteroaryl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, and a monocyclic heterocyclyl. Examples of multicyclic heterocyclyl groups include, but are not limited to 10H-phenothiazin-10-yl, 9,10-dihydroacridin-9-yl, 9,10-dihydroacridin-10-yl, 10H-phenoxazin-10-yl, 10,11-dihydro-5H-dibenzo[b,f]azepin-5-yl, 1,2,3,4-tetrahydropyrido[4,3-g]isoquinolin-2-yl, 12H-benzo[b]phenoxazin-12-yl, and dodecahydro-1H-carbazol-9-yl. The term “alkylene,” by itself or as part of another substituent, means, unless otherwise stated, a divalent radical derived from an alkyl, as exemplified, but not limited by, —CH2CH2CH2CH2— Typically, an alkyl (or alkylene) group will have from 1 to 24 carbon atoms, with those groups having 10 or fewer carbon atoms being preferred herein. A “lower alkyl” or “lower alkylene” is a shorter chain alkyl or alkylene group, generally having eight or fewer carbon atoms. The term “alkenylene,” by itself or as part of another substituent, means, unless otherwise stated, a divalent radical derived from an alkene. The term “heteroalkyl,” by itself or in combination with another term, means, unless otherwise stated, a stable straight or branched chain, or combinations thereof, including at least one carbon atom and at least one heteroatom (e.g., O, N, P, Si, and S), and wherein the nitrogen and sulfur atoms may optionally be oxidized, and the nitrogen heteroatom may optionally be quaternized. The heteroatom(s) (e.g., N, S, Si, or P) may be placed at any interior position of the heteroalkyl group or at the position at which the alkyl group is attached to the remainder of the molecule. Heteroalkyl is an uncyclized chain. Examples include, but are not limited to: —CH2—CH2—O—CH3, —CH2—CH2—NH—CH3, —CH2—CH2—N(CH3)—CH3, —CH2—S—CH2—CH3, —CH2—S—CH2, —S(O)—CH3, —CH2—CH2—S(O)2—CH3, —CH═CHO—CH3, —Si(CH3)3, —CH2—CH═N—OCH3, —CH═CH—N(CH3)—CH3, —O—CH3, —O—CH2—CH3, and —CN. Up to two or three heteroatoms may be consecutive, such as, for example, —CH2—NH—OCH3and —CH2—O—Si(CH3)3. A heteroalkyl moiety may include one heteroatom (e.g., O, N, S, Si, or P). A heteroalkyl moiety may include two optionally different heteroatoms (e.g., O, N, S, Si, or P). A heteroalkyl moiety may include three optionally different heteroatoms (e.g., O, N, S, Si, or P). A heteroalkyl moiety may include four optionally different heteroatoms (e.g., O, N, S, Si, or P). A heteroalkyl moiety may include five optionally different heteroatoms (e.g., O, N, S, Si, or P). A heteroalkyl moiety may include up to 8 optionally different heteroatoms (e.g., O, N, S, Si, or P). The term “heteroalkenyl,” by itself or in combination with another term, means, unless otherwise stated, a heteroalkyl including at least one double bond. A heteroalkenyl may optionally include more than one double bond and/or one or more triple bonds in additional to the one or more double bonds. The term “heteroalkynyl,” by itself or in combination with another term, means, unless otherwise stated, a heteroalkyl including at least one triple bond. A heteroalkynyl may optionally include more than one triple bond and/or one or more double bonds in additional to the one or more triple bonds. Similarly, the term “heteroalkylene,” by itself or as part of another substituent, means, unless otherwise stated, a divalent radical derived from heteroalkyl, as exemplified, but not limited by, —CH2—CH2—S—CH2—CH2— and —CH2—S—CH2—CH2—NH—CH2—. For heteroalkylene groups, heteroatoms can also occupy either or both of the chain termini (e.g., alkyleneoxy, alkylenedioxy, alkyleneamino, alkylenediamino, and the like). Still further, for alkylene and heteroalkylene linking groups, no orientation of the linking group is implied by the direction in which the formula of the linking group is written. For example, the formula —C(O)2R′— represents both —C(O)2R′— and —R′C(O)2—. As described above, heteroalkyl groups, as used herein, include those groups that are attached to the remainder of the molecule through a heteroatom, such as —C(O)R′, —C(O)NR′, —NR′R″, —OR′, —SR′, and/or —SO2R′. Where “heteroalkyl” is recited, followed by recitations of specific heteroalkyl groups, such as —NR′R″ or the like, it will be understood that the terms heteroalkyl and —NR′R″ are not redundant or mutually exclusive. Rather, the specific heteroalkyl groups are recited to add clarity. Thus, the term “heteroalkyl” should not be interpreted herein as excluding specific heteroalkyl groups, such as —NR′R″ or the like. The terms “cycloalkyl” and “heterocycloalkyl,” by themselves or in combination with other terms, mean, unless otherwise stated, cyclic versions of “alkyl” and “heteroalkyl,” respectively. Cycloalkyl and heterocycloalkyl are not aromatic. Additionally, for heterocycloalkyl, a heteroatom can occupy the position at which the heterocycle is attached to the remainder of the molecule. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-cyclohexenyl, 3-cyclohexenyl, cycloheptyl, and the like. Examples of heterocycloalkyl include, but are not limited to, 1-(1,2,5,6-tetrahydropyridyl), 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-morpholinyl, 3-morpholinyl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, 1-piperazinyl, 2-piperazinyl, and the like. A “cycloalkylene” and a “heterocycloalkylene,” alone or as part of another substituent, means a divalent radical derived from a cycloalkyl and heterocycloalkyl, respectively. The terms “halo” or “halogen,” by themselves or as part of another substituent, mean, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom. Additionally, terms such as “haloalkyl” are meant to include monohaloalkyl and polyhaloalkyl. For example, the term “halo(C1-C4)alkyl” includes, but is not limited to, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 4-chlorobutyl, 3-bromopropyl, and the like. The term “acyl” means, unless otherwise stated, —C(O)R where R is a substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. The term “aryl” means, unless otherwise stated, a polyunsaturated, aromatic, hydrocarbon substituent, which can be a single ring or multiple rings (preferably from 1 to 3 rings) that are fused together (i.e., a fused ring aryl) or linked covalently. A fused ring aryl refers to multiple rings fused together wherein at least one of the fused rings is an aryl ring. The term “heteroaryl” refers to aryl groups (or rings) that contain at least one heteroatom such as N, O, or S, wherein the nitrogen and sulfur atoms are optionally oxidized, and the nitrogen atom(s) are optionally quaternized. Thus, the term “heteroaryl” includes fused ring heteroaryl groups (i.e., multiple rings fused together wherein at least one of the fused rings is a heteroaromatic ring). A 5,6-fused ring heteroarylene refers to two rings fused together, wherein one ring has 5 members and the other ring has 6 members, and wherein at least one ring is a heteroaryl ring. Likewise, a 6,6-fused ring heteroarylene refers to two rings fused together, wherein one ring has 6 members and the other ring has 6 members, and wherein at least one ring is a heteroaryl ring. And a 6,5-fused ring heteroarylene refers to two rings fused together, wherein one ring has 6 members and the other ring has 5 members, and wherein at least one ring is a heteroaryl ring. A heteroaryl group can be attached to the remainder of the molecule through a carbon or heteroatom. Non-limiting examples of aryl and heteroaryl groups include phenyl, naphthyl, pyrrolyl, pyrazolyl, pyridazinyl, triazinyl, pyrimidinyl, imidazolyl, pyrazinyl, purinyl, oxazolyl, isoxazolyl, thiazolyl, furyl, thienyl, pyridyl, pyrimidyl, benzothiazolyl, benzoxazoyl benzimidazolyl, benzofuran, isobenzofuranyl, indolyl, isoindolyl, benzothiophenyl, isoquinolyl, quinoxalinyl, quinolyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 2-imidazolyl, 4-imidazolyl, pyrazinyl, 2-oxazolyl, 4-oxazolyl, 2-phenyl-4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-benzothiazolyl, purinyl, 2-benzimidazolyl, 5-indolyl, 1-isoquinolyl, 5-isoquinolyl, 2-quinoxalinyl, 5-quinoxalinyl, 3-quinolyl, and 6-quinolyl. Substituents for each of the above noted aryl and heteroaryl ring systems are selected from the group of acceptable substituents described below. An “arylene” and a “heteroarylene,” alone or as part of another substituent, mean a divalent radical derived from an aryl and heteroaryl, respectively. A heteroaryl group substituent may be —O— bonded to a ring heteroatom nitrogen. Spirocyclic rings are two or more rings wherein adjacent rings are attached through a single atom. The individual rings within spirocyclic rings may be identical or different. Individual rings in spirocyclic rings may be substituted or unsubstituted and may have different substituents from other individual rings within a set of spirocyclic rings. Possible substituents for individual rings within spirocyclic rings are the possible substituents for the same ring when not part of spirocyclic rings (e.g. substituents for cycloalkyl or heterocycloalkyl rings). Spirocylic rings may be substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkylene, substituted or unsubstituted heterocycloalkyl or substituted or unsubstituted heterocycloalkylene and individual rings within a spirocyclic ring group may be any of the immediately previous list, including having all rings of one type (e.g. all rings being substituted heterocycloalkylene wherein each ring may be the same or different substituted heterocycloalkylene). When referring to a spirocyclic ring system, heterocyclic spirocyclic rings means a spirocyclic rings wherein at least one ring is a heterocyclic ring and wherein each ring may be a different ring. When referring to a spirocyclic ring system, substituted spirocyclic rings means that at least one ring is substituted and each substituent may optionally be different. The symbol “” denotes the point of attachment of a chemical moiety to the remainder of a molecule or chemical formula. The term “oxo,” as used herein, means an oxygen that is double bonded to a carbon atom. The term “alkylarylene” as an arylene moiety covalently bonded to an alkylene moiety (also referred to herein as an alkylene linker). In embodiments, the alkylarylene group has the formula: An alkylarylene moiety may be substituted (e.g. with a substituent group) on the alkylene moiety or the arylene linker (e.g. at carbons 2, 3, 4, or 6) with halogen, oxo, —N3, —CF3, —CCl3, —CBr3, —CI3, —CN, —CHO, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SO2CH3—SO3H, —OSO3H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, substituted or unsubstituted C1-C5alkyl or substituted or unsubstituted 2 to 5 membered heteroalkyl). In embodiments, the alkylarylene is unsubstituted. Each of the above terms (e.g., “alkyl,” “heteroalkyl,” “cycloalkyl,” “heterocycloalkyl,” “aryl,” and “heteroaryl”) includes both substituted and unsubstituted forms of the indicated radical. Preferred substituents for each type of radical are provided below. Substituents for the alkyl and heteroalkyl radicals (including those groups often referred to as alkylene, alkenyl, heteroalkylene, heteroalkenyl, alkynyl, cycloalkyl, heterocycloalkyl, cycloalkenyl, and heterocycloalkenyl) can be one or more of a variety of groups selected from, but not limited to, —OR′, ═O, ═NR′, ═N—OR′, —NR′R″, —SR′, -halogen, —SiR′R″R′″, —OC(O)R′, —C(O)R′, —CO2R′, —CONR′R″, —OC(O)NR′R″, —NR″C(O)R′, —NR′—C(O)NR″R′″, —NR″C(O)2R′, —NR—C(NR′R″R′″)═NR″″, —NR—C(NR′R″)═NR′″, —S(O)R′, —S(O)2R′, —S(O)2NR′R″, —NRSO2R′, —NR′NR″R′″, —ONR′R″, —NR′C(O)NR″NR′″R″″, —CN, —NO2, —NR′SO2R″, —NR′C(O)R″, —NR′C(O)—OR″, —NR′OR″, in a number ranging from zero to (2m′+1), where m′ is the total number of carbon atoms in such radical. R, R′, R″, R′″, and R″″ each preferably independently refer to hydrogen, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl (e.g., aryl substituted with 1-3 halogens), substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, alkoxy, or thioalkoxy groups, or arylalkyl groups. When a compound described herein includes more than one R group, for example, each of the R groups is independently selected as are each R′, R″, R′″, and R″″ group when more than one of these groups is present. When R′ and R″ are attached to the same nitrogen atom, they can be combined with the nitrogen atom to form a 4-, 5-, 6-, or 7-membered ring. For example, —NR′R″ includes, but is not limited to, 1-pyrrolidinyl and 4-morpholinyl. From the above discussion of substituents, one of skill in the art will understand that the term “alkyl” is meant to include groups including carbon atoms bound to groups other than hydrogen groups, such as haloalkyl (e.g., —CF3and —CH2CF3) and acyl (e.g., —C(O)CH3, —C(O)CF3, —C(O)CH2OCH3, and the like). Similar to the substituents described for the alkyl radical, substituents for the aryl and heteroaryl groups are varied and are selected from, for example: —OR′, —NR′R″, —SR′, -halogen, —SiR′R″R′″, —OC(O)R′, —C(O)R′, —CO2R′, —CONR′R″, —OC(O)NR′R″, —NR″C(O)R′, —NR′—C(O)NR″R′″, —NR″C(O)2R′, —NR—C(NR′R″R′″)═NR″″, —NR—C(NR′R″)═NR′″, —S(O)R′, —S(O)2R′, —S(O)2NR′R″, —NRSO2R′, —NR′NR″R′″, —ONR′R″, —NR′C(O)NR″NR′″R″″, —CN, —NO2, —R′, —N3, —CH(Ph)2, fluoro(C1-C4)alkoxy, and fluoro(C1-C4)alkyl, —NR′SO2R″, —NR′C(O)R″, —NR′C(O)—OR″, —NR′OR″, in a number ranging from zero to the total number of open valences on the aromatic ring system; and where R′, R″, R′″, and R″″ are preferably independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl. When a compound described herein includes more than one R group, for example, each of the R groups is independently selected as are each R′, R″, R′″, and R″″ groups when more than one of these groups is present. Substituents for rings (e.g. cycloalkyl, heterocycloalkyl, aryl, heteroaryl, cycloalkylene, heterocycloalkylene, arylene, or heteroarylene) may be depicted as substituents on the ring rather than on a specific atom of a ring (commonly referred to as a floating substituent). In such a case, the substituent may be attached to any of the ring atoms (obeying the rules of chemical valency) and in the case of fused rings or spirocyclic rings, a substituent depicted as associated with one member of the fused rings or spirocyclic rings (a floating substituent on a single ring), may be a substituent on any of the fused rings or spirocyclic rings (a floating substituent on multiple rings). When a substituent is attached to a ring, but not a specific atom (a floating substituent), and a subscript for the substituent is an integer greater than one, the multiple substituents may be on the same atom, same ring, different atoms, different fused rings, different spirocyclic rings, and each substituent may optionally be different. Where a point of attachment of a ring to the remainder of a molecule is not limited to a single atom (a floating substituent), the attachment point may be any atom of the ring and in the case of a fused ring or spirocyclic ring, any atom of any of the fused rings or spirocyclic rings while obeying the rules of chemical valency. Where a ring, fused rings, or spirocyclic rings contain one or more ring heteroatoms and the ring, fused rings, or spirocyclic rings are shown with one more floating substituents (including, but not limited to, points of attachment to the remainder of the molecule), the floating substituents may be bonded to the heteroatoms. Where the ring heteroatoms are shown bound to one or more hydrogens (e.g. a ring nitrogen with two bonds to ring atoms and a third bond to a hydrogen) in the structure or formula with the floating substituent, when the heteroatom is bonded to the floating substituent, the substituent will be understood to replace the hydrogen, while obeying the rules of chemical valency. Two or more substituents may optionally be joined to form aryl, heteroaryl, cycloalkyl, or heterocycloalkyl groups. Such so-called ring-forming substituents are typically, though not necessarily, found attached to a cyclic base structure. In one embodiment, the ring-forming substituents are attached to adjacent members of the base structure. For example, two ring-forming substituents attached to adjacent members of a cyclic base structure create a fused ring structure. In another embodiment, the ring-forming substituents are attached to a single member of the base structure. For example, two ring-forming substituents attached to a single member of a cyclic base structure create a spirocyclic structure. In yet another embodiment, the ring-forming substituents are attached to non-adjacent members of the base structure. Two of the substituents on adjacent atoms of the aryl or heteroaryl ring may optionally form a ring of the formula -T-C(O)—(CRR′)q—U—, wherein T and U are independently —NR—, —O—, —CRR′—, or a single bond, and q is an integer of from 0 to 3. Alternatively, two of the substituents on adjacent atoms of the aryl or heteroaryl ring may optionally be replaced with a substituent of the formula -A-(CH2)r—B—, wherein A and B are independently —CRR′—, —O—, —NR—, —S—, —S(O)—, —S(O)2—, —S(O)2NR′—, or a single bond, and r is an integer of from 1 to 4. One of the single bonds of the new ring so formed may optionally be replaced with a double bond. Alternatively, two of the substituents on adjacent atoms of the aryl or heteroaryl ring may optionally be replaced with a substituent of the formula —(CRR′)s—X′— (C″R″R′″)d—, where s and d are independently integers of from 0 to 3, and X′ is —O—, —NR′—, —S—, —S(O)—, —S(O)2—, or —S(O)2NR′—. The substituents R, R′, R″, and R′″ are preferably independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl. As used herein, the terms “heteroatom” or “ring heteroatom” are meant to include oxygen (O), nitrogen (N), sulfur (S), phosphorus (P), and silicon (Si). A “substituent group,” as used herein, means a group selected from the following moieties:(A) oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8alkyl, C1-C6alkyl, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered heteroalkyl, 2 to 6 membered heteroalkyl, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8cycloalkyl, C3-C6cycloalkyl, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered heterocycloalkyl, 3 to 6 membered heterocycloalkyl, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10aryl, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered heteroaryl, 5 to 9 membered heteroaryl, or 5 to 6 membered heteroaryl), and(B) alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, substituted with at least one substituent selected from:(i) oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8alkyl, C1-C6alkyl, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered heteroalkyl, 2 to 6 membered heteroalkyl, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8cycloalkyl, C3-C6cycloalkyl, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered heterocycloalkyl, 3 to 6 membered heterocycloalkyl, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10aryl, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered heteroaryl, 5 to 9 membered heteroaryl, or 5 to 6 membered heteroaryl), and(ii) alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, substituted with at least one substituent selected from:(a) oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8alkyl, C1-C6alkyl, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered heteroalkyl, 2 to 6 membered heteroalkyl, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8cycloalkyl, C3-C6cycloalkyl, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered heterocycloalkyl, 3 to 6 membered heterocycloalkyl, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10aryl, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered heteroaryl, 5 to 9 membered heteroaryl, or 5 to 6 membered heteroaryl), and(b) alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, substituted with at least one substituent selected from: oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8alkyl, C1-C6alkyl, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered heteroalkyl, 2 to 6 membered heteroalkyl, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8cycloalkyl, C3-C6cycloalkyl, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered heterocycloalkyl, 3 to 6 membered heterocycloalkyl, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10aryl, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered heteroaryl, 5 to 9 membered heteroaryl, or 5 to 6 membered heteroaryl). A “size-limited substituent” or “size-limited substituent group,” as used herein, means a group selected from all of the substituents described above for a “substituent group,” wherein each substituted or unsubstituted alkyl is a substituted or unsubstituted C1-C20alkyl, each substituted or unsubstituted heteroalkyl is a substituted or unsubstituted 2 to 20 membered heteroalkyl, each substituted or unsubstituted cycloalkyl is a substituted or unsubstituted C3-C8cycloalkyl, each substituted or unsubstituted heterocycloalkyl is a substituted or unsubstituted 3 to 8 membered heterocycloalkyl, each substituted or unsubstituted aryl is a substituted or unsubstituted C6-C10aryl, and each substituted or unsubstituted heteroaryl is a substituted or unsubstituted 5 to 10 membered heteroaryl. A “lower substituent” or “lower substituent group,” as used herein, means a group selected from all of the substituents described above for a “substituent group,” wherein each substituted or unsubstituted alkyl is a substituted or unsubstituted C1-C8alkyl, each substituted or unsubstituted heteroalkyl is a substituted or unsubstituted 2 to 8 membered heteroalkyl, each substituted or unsubstituted cycloalkyl is a substituted or unsubstituted C3-C7cycloalkyl, each substituted or unsubstituted heterocycloalkyl is a substituted or unsubstituted 3 to 7 membered heterocycloalkyl, each substituted or unsubstituted aryl is a substituted or unsubstituted C6-C10aryl, and each substituted or unsubstituted heteroaryl is a substituted or unsubstituted 5 to 9 membered heteroaryl. In embodiments, a substituted or unsubstituted moiety (e.g., substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkylene, substituted or unsubstituted heteroalkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted heterocycloalkylene, substituted or unsubstituted arylene, and/or substituted or unsubstituted heteroarylene) is unsubstituted (e.g., is an unsubstituted alkyl, unsubstituted heteroalkyl, unsubstituted cycloalkyl, unsubstituted heterocycloalkyl, unsubstituted aryl, unsubstituted heteroaryl, unsubstituted alkylene, unsubstituted heteroalkylene, unsubstituted cycloalkylene, unsubstituted heterocycloalkylene, unsubstituted arylene, and/or unsubstituted heteroarylene, respectively). In embodiments, a substituted or unsubstituted moiety (e.g., substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkylene, substituted or unsubstituted heteroalkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted heterocycloalkylene, substituted or unsubstituted arylene, and/or substituted or unsubstituted heteroarylene) is substituted (e.g., is a substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene, and/or substituted heteroarylene, respectively). In embodiments, a substituted moiety (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene, and/or substituted heteroarylene) is substituted with at least one substituent group, wherein if the substituted moiety is substituted with a plurality of substituent groups, each substituent group may optionally be different. In embodiments, if the substituted moiety is substituted with a plurality of substituent groups, each substituent group is different. In embodiments, a substituted moiety (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene, and/or substituted heteroarylene) is substituted with at least one size-limited substituent group, wherein if the substituted moiety is substituted with a plurality of size-limited substituent groups, each size-limited substituent group may optionally be different. In embodiments, if the substituted moiety is substituted with a plurality of size-limited substituent groups, each size-limited substituent group is different. In embodiments, a substituted moiety (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene, and/or substituted heteroarylene) is substituted with at least one lower substituent group, wherein if the substituted moiety is substituted with a plurality of lower substituent groups, each lower substituent group may optionally be different. In embodiments, if the substituted moiety is substituted with a plurality of lower substituent groups, each lower substituent group is different. In embodiments, a substituted moiety (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene, and/or substituted heteroarylene) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted moiety is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different. In embodiments, if the substituted moiety is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group is different. In embodiments of the compounds herein, each substituted or unsubstituted alkyl may be a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted C1-C20alkyl, each substituted or unsubstituted heteroalkyl is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted 2 to 20 membered heteroalkyl, each substituted or unsubstituted cycloalkyl is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted C3-C8cycloalkyl, each substituted or unsubstituted heterocycloalkyl is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted 3 to 8 membered heterocycloalkyl, each or unsubstituted aryl is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted C6-C10aryl, and/or each substituted or unsubstituted heteroaryl is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted 5 to 10 membered heteroaryl. In embodiments herein, each substituted or unsubstituted alkylene is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted C1-C20alkylene, each substituted or unsubstituted heteroalkylene is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted 2 to 20 membered heteroalkylene, each substituted or unsubstituted cycloalkylene is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted C3-C8cycloalkylene, each substituted or unsubstituted heterocycloalkylene is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted 3 to 8 membered heterocycloalkylene, each substituted or unsubstituted arylene is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted C6-C10arylene, and/or each substituted or unsubstituted heteroarylene is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted 5 to 10 membered heteroarylene. In some embodiments, each substituted or unsubstituted alkyl is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted C1-C8alkyl, each substituted or unsubstituted heteroalkyl is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted 2 to 8 membered heteroalkyl, each substituted or unsubstituted cycloalkyl is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted C3-C7cycloalkyl, each substituted or unsubstituted heterocycloalkyl is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted 3 to 7 membered heterocycloalkyl, each substituted or unsubstituted aryl is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted C6-C10aryl, and/or each substituted or unsubstituted heteroaryl is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted 5 to 9 membered heteroaryl. In some embodiments, each substituted or unsubstituted alkylene is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted C1-C8alkylene, each substituted or unsubstituted heteroalkylene is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted 2 to 8 membered heteroalkylene, each substituted or unsubstituted cycloalkylene is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted C3-C7cycloalkylene, each substituted or unsubstituted heterocycloalkylene is a substituted or unsubstituted 3 to 7 membered heterocycloalkylene, each substituted or unsubstituted arylene is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted C6-C10arylene, and/or each substituted or unsubstituted heteroarylene is a substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted 5 to 9 membered heteroarylene. In some embodiments, the compound is a chemical species set forth in the Examples section, figures, or tables below. Certain compounds of the present invention possess asymmetric carbon atoms (optical or chiral centers) or double bonds; the enantiomers, racemates, diastereomers, tautomers, geometric isomers, stereoisometric forms that may be defined, in terms of absolute stereochemistry, as (R)- or (S)- or, as (D)- or (L)- for amino acids, and individual isomers are encompassed within the scope of the present invention. The compounds of the present invention do not include those that are known in art to be too unstable to synthesize and/or isolate. The present invention is meant to include compounds in racemic and optically pure forms. Optically active (R)- and (S)-, or (D)- and (L)-isomers may be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. When the compounds described herein contain olefinic bonds or other centers of geometric asymmetry, and unless specified otherwise, it is intended that the compounds include both E and Z geometric isomers. As used herein, the term “isomers” refers to compounds having the same number and kind of atoms, and hence the same molecular weight, but differing in respect to the structural arrangement or configuration of the atoms. The term “tautomer,” as used herein, refers to one of two or more structural isomers which exist in equilibrium and which are readily converted from one isomeric form to another. It will be apparent to one skilled in the art that certain compounds of this invention may exist in tautomeric forms, all such tautomeric forms of the compounds being within the scope of the invention. Unless otherwise stated, structures depicted herein are also meant to include all stereochemical forms of the structure; i.e., the (R) and (S) configurations for each asymmetric center. Therefore, single stereochemical isomers as well as enantiomeric and diastereomeric mixtures of the present compounds, generally recognized as stable by those skilled in the art, are within the scope of the invention. Unless otherwise stated, structures depicted herein are also meant to include compounds which differ only in the presence of one or more isotopically enriched atoms. For example, compounds having the present structures except for the replacement of a hydrogen by a deuterium or tritium, replacement of fluoride by18F, or the replacement of a carbon by13C- or14C-enriched carbon are within the scope of this invention. The compounds of the present invention may also contain unnatural proportions of atomic isotopes at one or more of the atoms that constitute such compounds. For example, the compounds may be radiolabeled with radioactive isotopes, such as for example tritium (3H), iodine-125 (125I), or carbon-14 (14C). All isotopic variations of the compounds of the present invention, whether radioactive or not, are encompassed within the scope of the present invention. It should be noted that throughout the application that alternatives are written in Markush groups, for example, each amino acid position that contains more than one possible amino acid. It is specifically contemplated that each member of the Markush group should be considered separately, thereby comprising another embodiment, and the Markush group is not to be read as a single unit. “Analog,” or “analogue” is used in accordance with its plain ordinary meaning within Chemistry and Biology and refers to a chemical compound that is structurally similar to another compound (i.e., a so-called “reference” compound) but differs in composition, e.g., in the replacement of one atom by an atom of a different element, or in the presence of a particular functional group, or the replacement of one functional group by another functional group, or the absolute stereochemistry of one or more chiral centers of the reference compound. Accordingly, an analog is a compound that is similar or comparable in function and appearance but not in structure or origin to a reference compound. The terms “a” or “an,” as used in herein means one or more. In addition, the phrase “substituted with a[n],” as used herein, means the specified group may be substituted with one or more of any or all of the named substituents. For example, where a group, such as an alkyl or heteroaryl group, is “substituted with an unsubstituted C1-C20alkyl, or unsubstituted 2 to 20 membered heteroalkyl,” the group may contain one or more unsubstituted C1-C20alkyls, and/or one or more unsubstituted 2 to 20 membered heteroalkyls. Where a moiety is substituted with an R substituent, the group may be referred to as “R-substituted.” Where a moiety is R-substituted, the moiety is substituted with at least one R substituent and each R substituent is optionally different. Where a particular R group is present in the description of a chemical genus (such as Formula (I)), a Roman decimal symbol may be used to distinguish each appearance of that particular R group. For example, where multiple R13substituents are present, each R13substituent may be distinguished as R13.1, R13.2, R13.3, R13.4, etc., wherein each of R13.1, R13.2, R13.3, R13.4, etc. is defined within the scope of the definition of R13and optionally differently. The terms “a” or “an,” as used in herein means one or more. In addition, the phrase “substituted with a[n],” as used herein, means the specified group may be substituted with one or more of any or all of the named substituents. For example, where a group, such as an alkyl or heteroaryl group, is “substituted with an unsubstituted C1-C20alkyl, or unsubstituted 2 to 20 membered heteroalkyl,” the group may contain one or more unsubstituted C1-C20alkyls, and/or one or more unsubstituted 2 to 20 membered heteroalkyls. Description of compounds of the present invention is limited by principles of chemical bonding known to those skilled in the art. Accordingly, where a group may be substituted by one or more of a number of substituents, such substitutions are selected so as to comply with principles of chemical bonding and to give compounds which are not inherently unstable and/or would be known to one of ordinary skill in the art as likely to be unstable under ambient conditions, such as aqueous, neutral, and several known physiological conditions. For example, a heterocycloalkyl or heteroaryl is attached to the remainder of the molecule via a ring heteroatom in compliance with principles of chemical bonding known to those skilled in the art thereby avoiding inherently unstable compounds. As defined herein, a term “poly (ADP-ribose) polymerase” or “PARP” refers to an enzyme that can be found in cell nucleus and is typically involved in various cellular functions, such as DNA repair, inflammatory response and the like, cvarious 16 isoforms, i.e. PARP1 (e.g., UniProtKB: P11103, P09874, and P18493); PARP2 (e.g., UniProtKB: Q9UGN5, O88554, and Q11207); PARP3 (e.g., UniProtKB: Q9Y6F1, Q3ULW8, and E1BD56); PARP4 (e.g, UniProtKB: Q9UKK3, E9PYK3, and E1BD73); PARP-5a (e.g, UniProtKB: Q95271); PARP-5b (e.g, UniProtKB: Q9H2K2); PARP6 (e.g, UniProtKB: Q2NL67, Q6P6P7, and F1N1A4); PARP7 (e.g, UniProtKB: Q7Z3E1); PARP8 (e.g, UniProtKB: Q8N3A8); PARP9 (e.g, UniProtKB: Q8IXQ6, Q8CAS9, and Q08DN9); PARP10 (e.g, UniProtKB: Q53GL7, Q8CIE4, and F6Z9X8), PARP11 (e.g, UniProtKB: Q9NR21, Q8CFF0, and A2VE05; PARP12 (e.g, UniProtKB: Q9H0J9, Q8BZ20, and D4A3V3); PARP14 (e.g, UniProtKB: Q460N5, Q2EMV9 and F1LZ05); PARP15 (e.g, UniProtKB: Q460N3, F1SQ35, and F6S617); and PARP16 (e.g, UniProtKB: Q8N5Y8, Q7TMM8, and Q5U2Q4). PARP can detect and initiate an immediate cellular response to single-strand DNA breaks (SSB), for example, by binding to the DNA, changing its structure, and synthesizing polymeric adenosine diphosphate ribose (poly (ADP-ribose) or PAR) chain, which acts as a signal for the other DNA-repairing enzymes. In addition, as defined herein, a term “poly ADP-ribosylation” or “PARylation” means a type of post-translational modification of protein, for example, by attaching or covalently bonding poly (ADP-ribose) to the protein, which is typically mediated by PARPs. During the damaged DNA repair, PARylation occurs at single-strand DNA breaks (SSB) or DNA lesions. As defined herein, a term “poly-(ADP-ribose) glycohydrolase” or “PARG” refers to an enzyme that can be found in cell nucleus and typically is involved in various cellular functions, such as DNA repair, inflammatory response and the like, particularly as a downstream process of PARylation. The family of PARP may include several isoforms, e.g., PARG1 (e.g., UniProtKB: Q86W56, Q867X0, and Q9SKB3), and PARG2 (e.g., UniProtKB: Q9N5L4, Q8VYA1, A0A178VXC5), which can hydrolyze glycosidic bond in the PARylated protein, thereby cleaving mono or poly (ADP-ribose) from the PARylated protein. In addition, as defined herein, a term “de-poly ADP-ribosylation” or “dePARylation” means a first step of hydrolysis of the poly (ADP-ribose) modified or PARylated protein, e.g. cleaving mono or poly (ADP-ribose) from the modified or PARylated protein. DePARylation is typically mediated by PARG during the damaged DNA repair. As defined herein, the term “inhibition”, “inhibit”, “inhibiting” and the like in reference to a protein-inhibitor interaction means negatively affecting (e.g. decreasing) the activity or function of the protein relative to the activity or function of the protein in the absence of the inhibitor. In embodiments inhibition means negatively affecting (e.g. decreasing) the concentration or levels of the protein relative to the concentration or level of the protein in the absence of the inhibitor. In embodiments inhibition refers to reduction of a disease or symptoms of disease. In embodiments, inhibition refers to a reduction in the activity of a particular protein target. Thus, inhibition includes, at least in part, partially or totally blocking stimulation, decreasing, preventing, or delaying activation, or inactivating, desensitizing, or down-regulating signal transduction or enzymatic activity or the amount of a protein. In embodiments, inhibition refers to a reduction of activity of a target protein resulting from a direct interaction (e.g. an inhibitor binds to the target protein). In embodiments, inhibition refers to a reduction of activity of a target protein from an indirect interaction (e.g. an inhibitor binds to a protein that activates the target protein, thereby preventing target protein activation). The term “inhibitor” may include synthetic or biological molecule (e.g. small molecule, nucleic acid, peptide or antibody) inhibiting or negatively affecting (e.g. decreasing) the activity or function of the protein relative to the activity or function of the protein in the absence of the inhibitor. In embodiments, the inhibitor is a small molecule. The term “small molecule” or the like as used herein refers, unless indicated otherwise, to a molecule having a molecular weight of less than about 700 Dalton, e.g., less than about 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 100, or even 50 Dalton. The term “pharmaceutically acceptable salts” is meant to include salts of the active compounds that are prepared with relatively nontoxic acids or bases, depending on the particular substituents found on the compounds described herein. When compounds of the present invention contain relatively acidic functionalities, base addition salts can be obtained by contacting the neutral form of such compounds with a sufficient amount of the desired base, either neat or in a suitable inert solvent. Examples of pharmaceutically acceptable base addition salts include sodium, potassium, calcium, ammonium, organic amino, or magnesium salt, or a similar salt. When compounds of the present invention contain relatively basic functionalities, acid addition salts can be obtained by contacting the neutral form of such compounds with a sufficient amount of the desired acid, either neat or in a suitable inert solvent. Examples of pharmaceutically acceptable acid addition salts include those derived from inorganic acids like hydrochloric, hydrobromic, nitric, carbonic, monohydrogencarbonic, phosphoric, monohydrogenphosphoric, dihydrogenphosphoric, sulfuric, monohydrogensulfuric, hydriodic, or phosphorous acids and the like, as well as the salts derived from relatively nontoxic organic acids like acetic, propionic, isobutyric, maleic, malonic, benzoic, succinic, suberic, fumaric, lactic, mandelic, phthalic, benzenesulfonic, p-tolylsulfonic, citric, tartaric, oxalic, methanesulfonic, and the like. Also included are salts of amino acids such as arginate and the like, and salts of organic acids like glucuronic or galactunoric acids and the like (see, for example, Berge et al., “Pharmaceutical Salts”,Journal of Pharmaceutical Science,1977, 66, 1-19). Certain specific compounds of the present invention contain both basic and acidic functionalities that allow the compounds to be converted into either base or acid addition salts. Thus, the compounds of the present invention may exist as salts, such as with pharmaceutically acceptable acids. The present invention includes such salts. Non-limiting examples of such salts include hydrochlorides, hydrobromides, phosphates, sulfates, methanesulfonates, nitrates, maleates, acetates, citrates, fumarates, proprionates, tartrates (e.g., (+)-tartrates, (−)-tartrates, or mixtures thereof including racemic mixtures), succinates, benzoates, and salts with amino acids such as glutamic acid, and quaternary ammonium salts (e.g. methyl iodide, ethyl iodide, and the like). These salts may be prepared by methods known to those skilled in the art. The neutral forms of the compounds are preferably regenerated by contacting the salt with a base or acid and isolating the parent compound in the conventional manner. The parent form of the compound may differ from the various salt forms in certain physical properties, such as solubility in polar solvents. In addition to salt forms, the present invention provides compounds, which are in a prodrug form. Prodrugs of the compounds described herein are those compounds that readily undergo chemical changes under physiological conditions to provide the compounds of the present invention. Prodrugs of the compounds described herein may be converted in vivo after administration. Additionally, prodrugs can be converted to the compounds of the present invention by chemical or biochemical methods in an ex vivo environment, such as, for example, when contacted with a suitable enzyme or chemical reagent. Certain compounds of the present invention can exist in unsolvated forms as well as solvated forms, including hydrated forms. In general, the solvated forms are equivalent to unsolvated forms and are encompassed within the scope of the present invention. Certain compounds of the present invention may exist in multiple crystalline or amorphous forms. In general, all physical forms are equivalent for the uses contemplated by the present invention and are intended to be within the scope of the present invention. “Pharmaceutically acceptable excipient” and “pharmaceutically acceptable carrier” refer to a substance that aids the administration of an active agent to and absorption by a subject and can be included in the compositions of the present invention without causing a significant adverse toxicological effect on the patient. Non-limiting examples of pharmaceutically acceptable excipients include water, NaCl, normal saline solutions, lactated Ringer's, normal sucrose, normal glucose, binders, fillers, disintegrants, lubricants, coatings, sweeteners, flavors, salt solutions (such as Ringer's solution), alcohols, oils, gelatins, carbohydrates such as lactose, amylose or starch, fatty acid esters, hydroxymethycellulose, polyvinyl pyrrolidine, and colors, and the like. Such preparations can be sterilized and, if desired, mixed with auxiliary agents such as lubricants, preservatives, stabilizers, wetting agents, emulsifiers, salts for influencing osmotic pressure, buffers, coloring, and/or aromatic substances and the like that do not deleteriously react with the compounds of the invention. One of skill in the art will recognize that other pharmaceutical excipients are useful in the present invention. As used herein, the term “salt” refers to acid or base salts of the compounds used in the methods of the present invention. Illustrative examples of acceptable salts are mineral acid (hydrochloric acid, hydrobromic acid, phosphoric acid, and the like) salts, organic acid (acetic acid, propionic acid, glutamic acid, citric acid and the like) salts, quaternary ammonium (methyl iodide, ethyl iodide, and the like) salts. “Treating” and “treatment” as used herein include prophylactic treatment. Treatment methods include administering to a subject a therapeutically effective amount of an active agent. The administering step may consist of a single administration or may include a series of administrations. The length of the treatment period depends on a variety of factors, such as the severity of the condition, the age of the patient, the concentration of active agent, the activity of the compositions used in the treatment, or a combination thereof. It will also be appreciated that the effective dosage of an agent used for the treatment or prophylaxis may increase or decrease over the course of a particular treatment or prophylaxis regime. Changes in dosage may result and become apparent by standard diagnostic assays known in the art. In some instances, chronic administration may be required. For example, the compositions are administered to the subject in an amount and for a duration sufficient to treat the patient. The term “treating” and conjugations thereof, may include prevention of an injury, pathology, condition, or disease. In embodiments, treating is preventing. In embodiments, treating does not include preventing. The term “prevent” refers to a decrease in the occurrence of disease (e.g., PARG associated disease) symptoms in a patient. As indicated above, the prevention may be complete (e.g., no detectable symptoms) or partial, such that fewer symptoms are observed than would likely occur absent treatment. “Patient,” “subject,” “patient in need thereof,” and “subject in need thereof” are herein used interchangeably and refer to a living organism suffering from or prone to a disease or condition that can be treated by administration of a pharmaceutical composition as provided herein. Non-limiting examples include humans, other mammals, bovines, rats, mice, dogs, monkeys, goat, sheep, cows, deer, and other non-mammalian animals. In some embodiments, a patient is human. An “effective amount” is an amount sufficient for a compound to accomplish a stated purpose relative to the absence of the compound (e.g. achieve the effect for which it is administered, treat a disease, reduce enzyme activity, increase enzyme activity, reduce a catabolic enzyme activity, or reduce one or more symptoms of a disease or condition). An example of an “effective amount” is an amount sufficient to contribute to the treatment, prevention, or reduction of a symptom or symptoms of a disease, which could also be referred to as a “therapeutically effective amount.” A “reduction” of a symptom or symptoms (and grammatical equivalents of this phrase) means decreasing of the severity or frequency of the symptom(s), or elimination of the symptom(s). A “prophylactically effective amount” of a drug is an amount of a drug that, when administered to a subject, will have the intended prophylactic effect, e.g., preventing or delaying the onset (or reoccurrence) of an injury, disease, pathology or condition, or reducing the likelihood of the onset (or reoccurrence) of an injury, disease, pathology, or condition, or their symptoms. The full prophylactic effect does not necessarily occur by administration of one dose, and may occur only after administration of a series of doses. Thus, a prophylactically effective amount may be administered in one or more administrations. An “activity decreasing amount,” as used herein, refers to an amount of antagonist required to decrease the activity of an enzyme relative to the absence of the antagonist. A “function disrupting amount,” as used herein, refers to the amount of antagonist required to disrupt the function of an enzyme or protein relative to the absence of the antagonist. The exact amounts will depend on the purpose of the treatment, and will be ascertainable by one skilled in the art using known techniques (see, e.g., Lieberman,Pharmaceutical Dosage Forms(vols. 1-3, 1992); Lloyd,The Art, Science and Technology of Pharmaceutical Compounding(1999); Pickar,Dosage Calculations(1999); andRemington: The Science and Practice of Pharmacy,20th Edition, 2003, Gennaro, Ed., Lippincott, Williams & Wilkins). For any compound described herein, the therapeutically effective amount can be initially determined from cell culture assays. Target concentrations will be those concentrations of active compound(s) that are capable of achieving the methods described herein, as measured using the methods described herein or known in the art. As is well known in the art, therapeutically effective amounts for use in humans can also be determined from animal models. For example, a dose for humans can be formulated to achieve a concentration that has been found to be effective in animals. The dosage in humans can be adjusted by monitoring compounds effectiveness and adjusting the dosage upwards or downwards, as described above. Adjusting the dose to achieve maximal efficacy in humans based on the methods described above and other methods is well within the capabilities of the ordinarily skilled artisan. The term “therapeutically effective amount,” as used herein, refers to that amount of the therapeutic agent sufficient to ameliorate the disorder, as described above. For example, for the given parameter, a therapeutically effective amount will show an increase or decrease of at least 5%, 10%, 15%, 20%, 25%, 40%, 50%, 60%, 75%, 80%, 90%, or at least 100%. Therapeutic efficacy can also be expressed as “-fold” increase or decrease. For example, a therapeutically effective amount can have at least a 1.2-fold, 1.5-fold, 2-fold, 5-fold, or more effect over a control. Dosages may be varied depending upon the requirements of the patient and the compound being employed. The dose administered to a patient, in the context of the present invention should be sufficient to effect a beneficial therapeutic response in the patient over time. The size of the dose also will be determined by the existence, nature, and extent of any adverse side-effects. Determination of the proper dosage for a particular situation is within the skill of the practitioner. Generally, treatment is initiated with smaller dosages which are less than the optimum dose of the compound. Thereafter, the dosage is increased by small increments until the optimum effect under circumstances is reached. Dosage amounts and intervals can be adjusted individually to provide levels of the administered compound effective for the particular clinical indication being treated. This will provide a therapeutic regimen that is commensurate with the severity of the individual's disease state. Utilizing the teachings provided herein, an effective prophylactic or therapeutic treatment regimen can be planned that does not cause substantial toxicity and yet is effective to treat the clinical symptoms demonstrated by the particular patient. This planning should involve the careful choice of active compound by considering factors such as compound potency, relative bioavailability, patient body weight, presence and severity of adverse side effects, preferred mode of administration and the toxicity profile of the selected agent. A “cell” as used herein, refers to a cell carrying out metabolic or other function sufficient to preserve or replicate its genomic DNA. A cell can be identified by well-known methods in the art including, for example, presence of an intact membrane, staining by a particular dye, ability to produce progeny or, in the case of a gamete, ability to combine with a second gamete to produce a viable offspring. Cells may include prokaryotic and eukaroytic cells. Prokaryotic cells include but are not limited to bacteria. Eukaryotic cells include but are not limited to yeast cells and cells derived from plants and animals, for example mammalian, insect (e.g.,spodoptera) and human cells. Cells may be useful when they are naturally nonadherent or have been treated not to adhere to surfaces, for example by trypsinization. “Control” or “control experiment” is used in accordance with its plain ordinary meaning and refers to an experiment in which the subjects or reagents of the experiment are treated as in a parallel experiment except for omission of a procedure, reagent, or variable of the experiment. In some instances, the control is used as a standard of comparison in evaluating experimental effects. In some embodiments, a control is the measurement of the activity of a protein in the absence of a compound as described herein (including embodiments and examples). “Contacting” is used in accordance with its plain ordinary meaning and refers to the process of allowing at least two distinct species (e.g. chemical compounds including biomolecules or cells) to become sufficiently proximal to react, interact or physically touch. It should be appreciated; however, the resulting reaction product can be produced directly from a reaction between the added reagents or from an intermediate from one or more of the added reagents which can be produced in the reaction mixture. The term “contacting” may also include allowing two species to react, interact, or physically touch, wherein the two species may be a compound as described herein and a protein or enzyme. Contacting may include allowing a compound described herein to interact with a protein or enzyme that is involved in a catabolism. As defined herein, the term “activation”, “activate”, “activating”, “activator” and the like in reference to a protein-inhibitor interaction means positively affecting (e.g. increasing) the activity or function of the protein relative to the activity or function of the protein in the absence of the activator. In embodiments activation means positively affecting (e.g. increasing) the concentration or levels of the protein relative to the concentration or level of the protein in the absence of the activator. The terms may reference activation, or activating, sensitizing, or up-regulating signal transduction or enzymatic activity or the amount of a protein decreased in a disease. Thus, activation may include, at least in part, partially or totally increasing stimulation, increasing or enabling activation, or activating, sensitizing, or up-regulating signal transduction or enzymatic activity or the amount of a protein associated with a disease (e.g., a protein which is decreased in a disease relative to a non-diseased control). Activation may include, at least in part, partially or totally increasing stimulation, increasing or enabling activation, or activating, sensitizing, or up-regulating signal transduction or enzymatic activity or the amount of a protein The term “modulate” is used in accordance with its plain ordinary meaning and refers to the act of changing or varying one or more properties. “Modulation” refers to the process of changing or varying one or more properties. For example, as applied to the effects of a modulator on a target protein (e.g., poly(ADP-ribose) glycohydrolase (PARG)), to modulate means to change by increasing or decreasing a property or function (e.g., activity or catabolic activity) of the target molecule or the amount of the target molecule. The term “modulate” is used in accordance with its plain ordinary meaning and refers to the act of changing or varying one or more properties. “Modulation” refers to the process of changing or varying one or more properties. For example, a modulator of a target protein changes by increasing or decreasing a property or function of the target molecule or the amount of the target molecule. A modulator of a disease decreases a symptom, cause, or characteristic of the targeted disease. “Selective” or “selectivity” or the like of a compound refers to the compound's ability to discriminate between molecular targets. “Specific”, “specifically”, “specificity”, or the like of a compound refers to the compound's ability to cause a particular action, such as inhibition, to a particular molecular target with minimal or no action to other proteins in the cell. “Pharmaceutically acceptable excipient” and “pharmaceutically acceptable carrier” refer to a substance that aids the administration of an active agent to and absorption by a subject and can be included in the compositions of the present invention without causing a significant adverse toxicological effect on the patient. Non-limiting examples of pharmaceutically acceptable excipients include water, NaCl, normal saline solutions, lactated Ringer's, normal sucrose, normal glucose, binders, fillers, disintegrants, lubricants, coatings, sweeteners, flavors, salt solutions (such as Ringer's solution), alcohols, oils, gelatins, carbohydrates such as lactose, amylose or starch, fatty acid esters, hydroxymethycellulose, polyvinyl pyrrolidine, and colors, and the like. Such preparations can be sterilized and, if desired, mixed with auxiliary agents such as lubricants, preservatives, stabilizers, wetting agents, emulsifiers, salts for influencing osmotic pressure, buffers, coloring, and/or aromatic substances and the like that do not deleteriously react with the compounds of the invention. One of skill in the art will recognize that other pharmaceutical excipients are useful in the present invention. The term “preparation” is intended to include the formulation of the active compound with encapsulating material as a carrier providing a capsule in which the active component with or without other carriers, is surrounded by a carrier, which is thus in association with it. Similarly, cachets and lozenges are included. Tablets, powders, capsules, pills, cachets, and lozenges can be used as solid dosage forms suitable for oral administration. As used herein, the term “administering” means oral administration, administration as a suppository, topical contact, intravenous, intraperitoneal, intramuscular, intralesional, intrathecal, intranasal or subcutaneous administration, or the implantation of a slow-release device, e.g., a mini-osmotic pump, to a subject. Administration is by any route, including parenteral and transmucosal (e.g., buccal, sublingual, palatal, gingival, nasal, vaginal, rectal, or transdermal) compatible with the preparation. Parenteral administration includes, e.g, intravenous, intramuscular, intra-arteriole, intradermal, subcutaneous, intraperitoneal, intraventricular, and intracranial. Other modes of delivery include, but are not limited to, the use of liposomal formulations, intravenous infusion, transdermal patches, etc. “Co-administer” it is meant that a composition described herein is administered at the same time, just prior to, or just after the administration of one or more additional therapies. The compounds of the invention can be administered alone or can be coadministered to the patient. Coadministration is meant to include simultaneous or sequential administration of the compounds individually or in combination (more than one compound). Thus, the preparations can also be combined, when desired, with other active substances (e.g. to reduce metabolic degradation). The compositions of the present invention can be delivered transdermally, by a topical route, or formulated as applicator sticks, solutions, suspensions, emulsions, gels, creams, ointments, pastes, jellies, paints, powders, and aerosols. The compositions disclosed herein can be delivered by transdermally, by a topical route, formulated as applicator sticks, solutions, suspensions, emulsions, gels, creams, ointments, pastes, jellies, paints, powders, and aerosols. Oral preparations include tablets, pills, powder, dragees, capsules, liquids, lozenges, cachets, gels, syrups, slurries, suspensions, etc., suitable for ingestion by the patient. Solid form preparations include powders, tablets, pills, capsules, cachets, suppositories, and dispersible granules. Liquid form preparations include solutions, suspensions, and emulsions, for example, water or water/propylene glycol solutions. The compositions of the present invention may additionally include components to provide sustained release and/or comfort. Such components include high molecular weight, anionic mucomimetic polymers, gelling polysaccharides and finely-divided drug carrier substrates. These components are discussed in greater detail in U.S. Pat. Nos. 4,911,920; 5,403,841; 5,212,162; and 4,861,760. The entire contents of these patents are incorporated herein by reference in their entirety for all purposes. The compositions disclosed herein can also be delivered as microspheres for slow release in the body. For example, microspheres can be administered via intradermal injection of drug-containing microspheres, which slowly release subcutaneously (see Rao,J. Biomater Sci. Polym. Ed. 7:623-645, 1995; as biodegradable and injectable gel formulations (see, e.g.,Gao Pharm. Res.12:857-863, 1995); or, as microspheres for oral administration (see, e.g., Eyles,J. Pharm. Pharmacol.49:669-674, 1997). In another embodiment, the formulations of the compositions of the present invention can be delivered by the use of liposomes which fuse with the cellular membrane or are endocytosed, i.e., by employing receptor ligands attached to the liposome, that bind to surface membrane protein receptors of the cell resulting in endocytosis. By using liposomes, particularly where the liposome surface carries receptor ligands specific for target cells, or are otherwise preferentially directed to a specific organ, one can focus the delivery of the compositions of the present invention into the target cells in vivo. (See, e.g., Al-Muhammed,J. Microencapsul.13:293-306, 1996; Chonn,Curr. Opin. Biotechnol.6:698-708, 1995; Ostro,Am. J. Hosp. Pharm.46:1576-1587, 1989). The compositions can also be delivered as nanoparticles. Pharmaceutical compositions may include compositions wherein the active ingredient (e.g. compounds described herein, including embodiments or examples) is contained in a therapeutically effective amount, i.e., in an amount effective to achieve its intended purpose. The actual amount effective for a particular application will depend, inter alia, on the condition being treated. When administered in methods to treat a disease, such compositions will contain an amount of active ingredient effective to achieve the desired result, e.g., modulating the activity of a target molecule, and/or reducing, eliminating, or slowing the progression of disease symptoms. The dosage and frequency (single or multiple doses) administered to a mammal can vary depending upon a variety of factors, for example, whether the mammal suffers from another disease, and its route of administration; size, age, sex, health, body weight, body mass index, and diet of the recipient; nature and extent of symptoms of the disease being treated, kind of concurrent treatment, complications from the disease being treated or other health-related problems. Other therapeutic regimens or agents can be used in conjunction with the methods and compounds of Applicants' invention. Adjustment and manipulation of established dosages (e.g., frequency and duration) are well within the ability of those skilled in the art. The compounds described herein can be used in combination with one another, with other active drugs known to be useful in treating a disease (e.g. cancer) or with adjunctive agents that may not be effective alone, but may contribute to the efficacy of the active agent. Thus, the compounds described herein may be co-administered with one another or with other active drugs known to be useful in treating a disease. By “co-administer” it is meant that a compound described herein is administered at the same time, just prior to, or just after the administration of one or more additional therapies, for example, an anticancer or antitumor agent as described herein. The compounds described herein can be administered alone or can be co-administered to the patient. Co-administration is meant to include simultaneous or sequential administration of the compound individually or in combination (more than one compound or agent). Thus, the preparations can also be combined, when desired, with other active substances (e.g. anticancer agents). Co-administration includes administering one active agent (e.g. a complex described herein) within 0.5, 1, 2, 4, 6, 8, 10, 12, 16, 20, or 24 hours of a second active agent (e.g. anticancer or antitumor agents). Also contemplated herein, are embodiments, where co-administration includes administering one active agent within 0.5, 1, 2, 4, 6, 8, 10, 12, 16, 20, or 24 hours of a second active agent. Co-administration includes administering two active agents simultaneously, approximately simultaneously (e.g., within about 1, 5, 10, 15, 20, or 30 minutes of each other), or sequentially in any order. Co-administration can be accomplished by co-formulation, i.e., preparing a single pharmaceutical composition including both active agents. In other embodiments, the active agents can be formulated separately. The active and/or adjunctive agents may be linked or conjugated to one another. The compounds described herein may be combined with treatments for cancer (e.g., breast cancer, ovarian cancer, lung cancer, pancreatic cancer, glioblastoma, uterine cancer, bladder cancer, esophagus cancer, gastric cancer, head and neck cancer, cholangiocarcinoma, mesothelioma, prostate cancer, colon carcinoma, fallopian tube cancer, lymphoma and leukemia). As used herein, the term “cancer” refers to all types of cancer, neoplasm, or malignant tumors found in mammals, including leukemia, lymphomas, carcinomas and sarcomas. Exemplary cancers include acute myeloid leukemia (“AML”), chronic myelogenous leukemia (“CML”), and cancer of the brain, breast, pancreas, colon, liver, kidney, lung, non-small cell lung, melanoma, ovary, sarcoma, and prostate. Additional examples include, cervix cancers, stomach cancers, head & neck cancers, uterus cancers, mesothelioma, metastatic bone cancer, Medulloblastoma, Hodgkin's Disease, Non-Hodgkin's Lymphoma, multiple myeloma, neuroblastoma, ovarian cancer, rhabdomyosarcoma, primary thrombocytosis, primary macroglobulinemia, primary brain tumors, cancer, malignant pancreatic insulanoma, malignant carcinoid, uterine cancer, urinary bladder cancer, bladder cancer, esophagus cancer, gastric cancer, head and neck cancer, cholangiocarcinoma, mesothelioma, premalignant skin lesions, testicular cancer, lymphomas, thyroid cancer, neuroblastoma, esophageal cancer, genitourinary tract cancer, malignant hypercalcemia, endometrial cancer, adrenal cortical cancer, fallopian tube cancer, neoplasms of the endocrine and exocrine pancreas cancer, prostate cancer, breast cancer including triple negative breast cancer, and cutaneous T-cell lymphoma. As used herein, the term “lymphoma” refers to a group of cancers affecting hematopoietic and lymphoid tissues. It begins in lymphocytes, the blood cells that are found primarily in lymph nodes, spleen, thymus, and bone marrow. Two main types of lymphoma are non-Hodgkin lymphoma and Hodgkin's disease. Hodgkin's disease represents approximately 15% of all diagnosed lymphomas. This is a cancer associated with Reed-Stemberg malignant B lymphocytes. Non-Hodgkin's lymphomas (NHL) can be classified based on the rate at which cancer grows and the type of cells involved. There are aggressive (high grade) and indolent (low grade) types of NHL. Based on the type of cells involved, there are B-cell and T-cell NHLs. Exemplary B-cell lymphomas that may be treated with a compound or method provided herein include, but are not limited to, small lymphocytic lymphoma, Mantle cell lymphoma, follicular lymphoma, marginal zone lymphoma, extranodal (MALT) lymphoma, nodal (monocytoid B-cell) lymphoma, splenic lymphoma, diffuse large cell B-lymphoma, Burkitt's lymphoma, lymphoblastic lymphoma, immunoblastic large cell lymphoma, or precursor B-lymphoblastic lymphoma. Exemplary T-cell lymphomas that may be treated with a compound or method provided herein include, but are not limited to, cutaneous T-cell lymphoma, peripheral T-cell lymphoma, anaplastic large cell lymphoma, mycosis fungoides, and precursor T-lymphoblastic lymphoma. In embodiments, “lymphoma” refers to a group of blood cell tumors that develop from cells of the immune system found in lymph, i.e. lymphocytes (e.g. natural killer cells (NK cells), T cells, and B cells). Lymphoma is typically classified into Hodgkin's lymphomas (HL) and the non-Hodgkin lymphomas (NHL) or based on whether it develops in B-lymphocytes (B-cells) or T-lymphocytes (T-cells). In embodiments, lymphoma is developed in B-cells. In embodiments, lymphoma is developed in T-cell. Cancer model organism, as used herein, is an organism exhibiting a phenotype indicative of cancer, or the activity of cancer causing elements, within the organism. The term cancer is defined above. A wide variety of organisms may serve as cancer model organisms, and include for example, cancer cells and mammalian organisms such as rodents (e.g. mouse or rat) and primates (such as humans). Cancer cell lines are widely understood by those skilled in the art as cells exhibiting phenotypes or genotypes similar to in vivo cancers. Cancer cell lines as used herein includes cell lines from animals (e.g. mice) and from humans. An “anticancer agent” as used herein refers to a molecule (e.g. compound, peptide, protein, nucleic acid, antibody) used to treat cancer through destruction or inhibition of cancer cells or tissues. Anticancer agents may be selective for certain cancers or certain tissues. In embodiments, anticancer agents herein may include epigenetic inhibitors and multi- or specific kinase inhibitors. The term “associated” or “associated with” in the context of a substance or substance activity or function associated with a disease (e.g. a protein associated disease, a cancer associated with PARG activity, PARG associated cancer, PARG associated disease (e.g., cancer, inflammatory disease, autoimmune disease, or infectious disease)) means that the disease (e.g. cancer, inflammatory disease, autoimmune disease, or infectious disease) is caused by (in whole or in part), or a symptom of the disease is caused by (in whole or in part) the substance or substance activity or function. For example, a cancer associated with PARG activity or function may be a cancer that results (entirely or partially) from aberrant PARG function (e.g. catabolic enzyme activity, protein-protein interaction, signaling pathway) or a cancer wherein a particular symptom of the disease is caused (entirely or partially) by aberrant PARG activity or function. As used herein, what is described as being associated with a disease, if a causative agent, could be a target for treatment of the disease. For example, a cancer associated with PARG activity or function or a PARG associated disease (e.g., cancer, inflammatory disease, autoimmune disease, or infectious disease), may be treated with a PARG modulator or PARG inhibitor, in the instance where increased PARG activity or function (e.g. catabolic enzyme activity) causes the disease (e.g., cancer, inflammatory disease, autoimmune disease, or infectious disease). For example, an inflammatory disease associated with PARG activity or function or a PARG associated inflammatory disease, may be treated with a PARG modulator or PARG inhibitor, in the instance where increased PARG activity or function (e.g. catabolic enzyme activity) causes the disease. “Disease” or “condition” refer to a state of being or health status of a patient or subject capable of being treated with the compounds or methods provided herein. In certain embodiments, disease as used herein may refer to cancer (e.g. breast cancer, ovarian cancer, lung cancer, pancreatic cancer, glioblastoma, uterine cancer, bladder cancer, esophagus cancer, gastric cancer, head and neck cancer, cholangiocarcinoma, mesothelioma, prostate cancer, colon carcinoma, fallopian tube cancer, lymphoma and leukemia). II. Compounds Provided herein are compounds having a structure of Formula (I): L1is a bond, —CR11R12—, —NR13—, —O—, —S—, —S(O)—, —S(O)2—, —NR13S(O)—, —NR13S(O)2—, —NR13C(O)—, —S(O)NR13—, —S(O)2NR13—, or —C(O)NR13—. R1is hydrogen, halogen, —CX13, —CHX12, —CH2X1, —OCX13, —OCH2X1, —OCHX12, —N3, —CN, —SOn1R1D, —SOv1NR1AR1B, —NHC(O)NR1AR1B, —N(O)m1, NR1AR1B, —C(O)R1C, —C(O)—OR1C, —C(O)NR1AR1B, —OR1D, —NR1ASO2R1D, —NR1AC(O) R1C, —NR1AC(O)OR1C, —NR1AOR1C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R2is hydrogen, halogen, —CX23, —CHX22, —CH2X2, —OCX23, —OCH2X2, —OCHX22, —N3, —CN, —SOn2R2D, —SOv2NR2AR2B, —NHC(O)NR2AR2B, —N(O)m2, —NR2AR2B, —C(O)R2C, —C(O)—OR2C, —C(O)NR2AR2B, —OR2D, —NR2ASO2R2D, —NR2AC(O)R2C, —NR2AC(O)OR2C, —NR2AOR2C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R3is hydrogen, halogen, —CX33, —CHX32, —CH2X3, —OCX33, —OCH2X3, —OCHX32, —N3, —CN, —SOn3R3D, —SOv3NR3AR3B, —NHC(O)NR3AR3B, —N(O)m3, —NR3AR3B, —C(O)R3C, C(O)—OR3C, —C(O)NR3AR3B, —OR3D, —NR3ASO2R3D, —NR3AC(O)R3C, —NR3AC(O)OR3C, —NR3AOR3C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R4is hydrogen, halogen, —CX43, —CHX42, —CH2X4, —OCX43, —OCH2X4, —OCHX42, —N3, —CN, —SOn4R4D, —SOv4NR4AR4B, —NHC(O)NR4AR4B, —N(O)m4, —NR4AR4B, —C(O)R4C, C(O)—OR4C, —C(O)NR4AR4B, —OR4D, —NR4ASO2R4D, —NR4AC(O)R4C, —NR4AC(O)OR4C, —NR4AOR4C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R5is hydrogen, halogen, —CX53, —CHX52, —CH2X5, —OCX53, —OCH2X5, —OCHX52, —N3, —CN, —SOn5R5D, —SOv5NR5AR5B, —NHC(O)NR5AR5B, —N(O)m5, —NR5AR5B, —C(O)R5C, —C(O)—OR5C, —C(O)NR5AR5B, —OR5D, —NR5ASO2R5D, —NR5AC(O)R5C, —NR5AC(O)OR5C, —NR5AOR5C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R6is hydrogen, halogen, —CX63, —CHX62, —CH2X6, —OCX63, —OCH2X6, —OCHX62, —N3, —CN, —SOn6R6D, —SOv6NR6AR6B, —NHC(O)NR6AR6B, —N(O)m6, —NR6AR6B, —C(O)R6C, C(O)—OR6C, —C(O)NR6AR6B, —OR6D, —NR6ASO2R6D, —NR6AC(O)R6C, —NR6AC(O)OR6C, —NR6AOR6C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R7is hydrogen, halogen, —CX73, —CHX72, —CH2X7, —OCX73, —OCH2X7, —OCHX72, —N3, —CN, —SOn7R7D, —SOv7NR7AR7B, —NHC(O)NR7AR7B, —N(O)m7, —NR7AR7B, —C(O)R7C, C(O)—OR7C, —C(O)NR7AR7B, —OR7D, —NR7ASO2R7D, —NR7AC(O)R7C, —NR7AC(O)OR7C, —NR7AOR7C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R8is hydrogen, halogen, —CX83, —CHX82, —CH2X8, —OCX83, —OCH2X8, —OCHX82, —N3, —CN, —SOn8R8D, —SOv8NR8AR8B, —NHC(O)NR8AR8B, —N(O)m8, —NR8AR8B, —C(O)R8C, C(O)—OR8C, —C(O)NR8AR8B, —OR8D, —NR8ASO2R8D, —NR8AC(O)R8C, —NR8AC(O)OR8C, —NR8AOR8C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R9is hydrogen, halogen, —CX93, —CHX92, —CH2X9, —OCX93, —OCH2X9, —OCHX92, —N3, —CN, —SOn9R9D, —SOv9NR9AR9B, —NHC(O)NR9AR9B, —N(O)m9, —NR9AR9B, —C(O)R9C, C(O)—OR9C, —C(O)NR9AR9B, —OR9D, —NR9ASO2R9D, —NR9AC(O)R9C, —NR9AC(O)OR9C, —NR9AOR9C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R10is hydrogen, halogen, —CX103, —CHX102, —CH2X10, —OCX103, —OCH2X10, —OCHX102, —N3, —CN, —SOn10R10C, —SOv10NR10AR10B, —NHC(O)NR10AR10B, —N(O)m10, —NR10AR10B, —C(O)R10C, —C(O)—OR10C, —C(O)NR10AR10B, —OR10D, —NR10ASO2R10D, —NR10AC(O) R10C, —NR10AC(O)OR10C, —NR10AOR10C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R11is hydrogen, halogen, —CX113, —CHX112, —CH2X11, —OCX113, —OCH2X11, —OCHX112, —N3, —CN, —SOn11R11D, —SOv11NR11AR11B, —NHC(O)NR11AR11B, —N(O)m11, —NR11AR11B, —C(O) R11C, —C(O)—OR11C, —C(O)NR11AR11B, —OR11D, —NR11ASO2R11D, —NR11AC(O)R11C, —NR11AC(O)OR11C, —NR11AOR11C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R12is hydrogen, halogen, —CX123, —CHX122, —CH2X12, —OCX123, —OCH2X12, —OCHX122, —N3, —CN, —SOnl2R12D, —SOv12NR12AR12B, —NHC(O)NR12AR12B, —N(O)m12, —NR12AR12B, —C(O)R12C, —C(O)—OR12C, —C(O)NR12AR12B, —OR12D, —NR12ASO2R12D, —NR12AC(O)R12C, —NR12AC(O)O R12C. —NR12AOR12C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R13is hydrogen, —CX133, —CHX132, —CH2X13, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. Each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12Cand R12Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R1is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R1is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R1is —OH or —OCH3, then at least one of R6, R7and R8are not —OCH3, or at least one of R8, R9and R10are not —OCH3. R1and R2together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R2and R3together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R3and R4together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R4and R5together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. The symbols n1, n2, n3, n4, n5, n6, n7, n8, n9, n10, n11 and n12 are independently an integer from 0 to 4 (e.g. 0). m1, m2, m3, m4, m5, m6, m7, m8, m9, m10, m11, m12, v1, v2, v3, v4, v5, v6, v7, v8, v9, v10, v11 and v12 are independently an integer from 1 to 2. X, X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, and X13are independently —F, —Cl, —Br, or —I. In embodiments, R1and R2together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R1and R2together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cyclopentyl. In embodiments, R1and R2together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cyclohexyl. In embodiments, R1and R2together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyridyl. In embodiments, R1and R2together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted piperidinyl. In embodiments, R1and R2together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted morpholinyl. In embodiments, R1and R2together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted phenyl. In embodiments, R1and R2together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyrrolyl. In embodiments, R1and R2together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyrimidinyl. In embodiments, R1and R2together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted thiophenyl. In embodiments, R2and R3together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R2and R3together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cyclopentyl. In embodiments, R2and R3together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cyclohexyl. In embodiments, R2and R3together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyridyl. In embodiments, R2and R3together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted piperidinyl. In embodiments, R2and R3together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted morpholinyl. In embodiments, R2and R3together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted phenyl. In embodiments, R2and R3together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyrrolyl. In embodiments, R2and R3together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyrimidinyl. In embodiments, R2and R3together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted thiophenyl. In embodiments, R3and R4together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R3and R4together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cyclopentyl. In embodiments, R3and R4together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cyclohexyl. In embodiments, R3and R4together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyridyl. In embodiments, R3and R4together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted piperidinyl. In embodiments, R3and R4together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted morpholinyl. In embodiments, R3and R4together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted phenyl. In embodiments, R3and R4together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyrrolyl. In embodiments, R3and R4together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyrimidinyl. In embodiments, R3and R4together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted thiophenyl. In embodiments, R4and R5together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R4and R5together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cyclopentyl. In embodiments, R4and R5together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cyclohexyl. In embodiments, R4and R5together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyridyl. In embodiments, R4and R5together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted piperidinyl. In embodiments, R4and R5together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted morpholinyl. In embodiments, R4and R5together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted phenyl. In embodiments, R4and R5together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyrrolyl. In embodiments, R4and R5together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyrimidinyl. In embodiments, R4and R5together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted thiophenyl. In embodiments, R6and R7together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R6and R7together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cyclopentyl. In embodiments, R6and R7together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cyclohexyl. In embodiments, R6and R7together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyridyl. In embodiments, R6and R7together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted piperidinyl. In embodiments, R6and R7together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted morpholinyl. In embodiments, R6and R7together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted phenyl. In embodiments, R6and R7together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyrrolyl. In embodiments, R6and R7together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyrimidinyl. In embodiments, R6and R7together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted thiophenyl. In embodiments, R7and R8together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R7and R8together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cyclopentyl. In embodiments, R7and R8together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cyclohexyl. In embodiments, R7and R8together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyridyl. In embodiments, R7and R8together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted piperidinyl. In embodiments, R7and R8together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted morpholinyl. In embodiments, R7and R8together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted phenyl. In embodiments, R7and R8together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyrrolyl. In embodiments, R7and R8together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyrimidinyl. In embodiments, R7and R8together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted thiophenyl. In embodiments, R8and R9together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R8and R9together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cyclopentyl. In embodiments, R8and R9together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cyclohexyl. In embodiments, R8and R9together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyridyl. In embodiments, R8and R9together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted piperidinyl. In embodiments, R8and R9together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted morpholinyl. In embodiments, R8and R9together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted phenyl. In embodiments, R8and R9together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyrrolyl. In embodiments, R8and R9together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyrimidinyl. In embodiments, R8and R9together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted thiophenyl. In embodiments, R9and R10together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R9and R10together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cyclopentyl. In embodiments, R9and R10together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cyclohexyl. In embodiments, R9and R10together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyridyl. In embodiments, R9and R10together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted piperidinyl. In embodiments, R9and R10together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted morpholinyl. In embodiments, R9and R10together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted phenyl. In embodiments, R9and R10together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyrrolyl. In embodiments, R9and R10together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted pyrimidinyl. In embodiments, R9and R10together with atoms attached thereto are joined to form substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted thiophenyl. In embodiments, the compound has a formula (IIA): In formula (IIA), L1, R1, R2, R3, R6, R7, R8, R9, and R10are as described herein. In embodiments, the compound has a formula (IIB): In formula (IIB), L1, R1, R2, R3, R6, R7, R8, R9, and R10are as described herein. R14is hydrogen, halogen, —CX143, —CHX142, —CH2X14, —OCX143, —OCH2X14, —OCHX142, —N3, —CN, —SOn14R14D, —SOv14NR14AR14B, —NHC(O)NR14AR14B, —N(O)m14, —NR14AR14B, —C(O)R14C, —C(O)—OR14C, —C(O)NR14AR14B, —OR14D, —NR14ASO2R14D, —NR14AC(O)R14C, —NR14AC(O)OR14C, —NR14AOR14C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R15is hydrogen, halogen, —CX153, —CHX152, —CH2X15, —OCX153, —OCH2X15, —OCHX152, —N3, —CN, —SOnl5R15D, —SOv15NR15AR15B, —NHC(O)NR15AR15B, —N(O)m15, —NR15AR15B, —C(O)R15C, —C(O)—OR15C, —C(O)NR15AR15B, —OR15D, —NR15ASO2R15D, —NR15AC(O)R15C, —NR15AC(O)OR15C, —NR15AOR15C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R16is hydrogen, halogen, —CX163, —CHX162, —CH2X16, —OCX163, —OCH2X16, —OCHX162, —N3, —CN, —SOn16R16D, —SOv16NR16AR16B, —NHC(O)NR16AR16B, —N(O)m16, —NR16AR16B, —C(O)R16C, —C(O)—OR16C, —C(O)NR16AR16B, —OR16D, —NR16ASO2R16D, —NR16AC(O)R16C, —NR16AC(O)OR16C, —NR16AOR16C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. R17is hydrogen, halogen, —CX173, —CHX172, —CH2X17, —OCX173, —OCH2X17, —OCHX172, —N3, —CN, —SOn17R17D, —SOv17NR17AR17B, —NHC(O)NR17AR17B, —N(O)m17, —NR17AR17B, —C(O)R17C, —C(O)—OR17C, —C(O)NR17AR17B, —OR17D, —NR17ASO2R17D, —NR17AC(O)R17C, —NR17AC(O)OR17C, —NR17AOR17C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. Each R14A, R14B, R14C, R14D, R15A, R15B, R15C, R15D, R16A, R16B, R16C, R16D, R17A, R17B, R17C, and R17Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. The symbols n14, n15, n16, and n17 are independently an integer from 0 to 4 (e.g. 0). The symbols m14, m15, m16, m17, v14, v15, v16, and v17 are independently an integer from 1 to 2. The symbols X14, X15, X16, and X17are independently —F, —Cl, —Br, or —I. In embodiments, L1is —CR11R12—, —NR13—, —O—, or —S—. In embodiments, L1is —NR13—, —O—, or —S—. In embodiments, L1is —CR11R12—, —O—, or —S—. In embodiments, L1is —O—, or —S—. In embodiments, L1is —O—. In embodiments, L1is —S—. In embodiments, L1is —NR13—. In embodiments, L1is —NH—. In embodiments, L1is a bond. In embodiments, L1is —S(O)—. In embodiments, L1is —S(O)2—. In embodiments, L1is —NR13S(O)2—. In embodiments, L1is —NR13C(O)—. In embodiments, L1is —NHS(O)2—. In embodiments, L1is —NHC(O)—. In embodiments, L1is —NCH3S(O)2—. In embodiments, L1is —NCH3C(O)—. In embodiments, L1is —CH2—. In embodiments, L1is —S(O)NR13—. In embodiments, L1is —S(O)2NR13—. In embodiments, L1is —C(O)NR13—. In embodiments, L1is not a bond. In embodiments, R11is hydrogen, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —N3, —CN, —SH, —SCH3, —SO2H, —NO2, —NH2, —OH, —OCH3, substituted or unsubstituted C1-C6alkyl, or substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R11is hydrogen. In embodiments, R11is —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, or —CH2I. In embodiments, R11is —N3. In embodiments, R11is —CN. In embodiments, R11is —SH. In embodiments, R11is —SCH3. In embodiments, R11is —SO2H. In embodiments, R11is —NO2. In embodiments, R11is —NH2. In embodiments, R11is —OH. In embodiments, R11is —OCH3. In embodiments, R11is substituted or unsubstituted C1-C6alkyl. In embodiments, R11is substituted or unsubstituted C1-C4alkyl. In embodiments, R11is substituted or unsubstituted C1-C2alkyl. In embodiments, R11is substituted methyl. In embodiments, R11is unsubstituted methyl. In embodiments, R11is substituted ethyl. In embodiments, R11is unsubstituted ethyl. In embodiments, R11is substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R11is substituted or unsubstituted 2 to 4 membered heteroalkyl. In embodiments, R11is substituted or unsubstituted 2 to 3 membered heteroalkyl. In embodiments, R11is substituted 2 membered heteroalkyl. In embodiments, R11is unsubstituted 2 membered heteroalkyl. In embodiments, R11is substituted 3 membered heteroalkyl. In embodiments, R11is unsubstituted 3 membered heteroalkyl. In embodiments, R12is hydrogen, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —N3, —CN, —SH, —SCH3, —SO2H, —NO2. —NH2, —OH, —OCH3, substituted or unsubstituted C1-C6alkyl, or substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R12is hydrogen. In embodiments, R12is —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, or —CH2I. In embodiments, R12is —N3. In embodiments, R12is —CN. In embodiments, R12is —SH. In embodiments, R12is —SCH3. In embodiments, R12is —SO2H. In embodiments, R12is —NO2. In embodiments, R12is —NH2. In embodiments, R12is —OH. In embodiments, R12is —OCH3. In embodiments, R12is substituted or unsubstituted C1-C6alkyl. In embodiments, R12is substituted or unsubstituted C1-C4alkyl. In embodiments, R12is substituted or unsubstituted C1-C2alkyl. In embodiments, R12is substituted methyl. In embodiments, R12is unsubstituted methyl. In embodiments, R12is substituted ethyl. In embodiments, R12is unsubstituted ethyl. In embodiments, R12is substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R12is substituted or unsubstituted 2 to 4 membered heteroalkyl. In embodiments, R12is substituted or unsubstituted 2 to 3 membered heteroalkyl. In embodiments, R12is substituted 2 membered heteroalkyl. In embodiments, R12is unsubstituted 2 membered heteroalkyl. In embodiments, R12is substituted 3 membered heteroalkyl. In embodiments, R12is unsubstituted 3 membered heteroalkyl. In embodiments, R13is hydrogen, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —COOH, —CONH2, substituted or unsubstituted C1-C6, alkyl, or substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R13is hydrogen. In embodiments, R13is —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, or —CHI2. In embodiments, R13is —COOH. In embodiments, R13is —CONH2. In embodiments, R13is substituted or unsubstituted C1-C6, alkyl. In embodiments, R13is substituted or unsubstituted C1-C4alkyl. In embodiments, R13is substituted or unsubstituted C1-C2alkyl. In embodiments, R13is substituted methyl. In embodiments, R13is unsubstituted methyl. In embodiments, R13is substituted ethyl. In embodiments, R13is unsubstituted ethyl. In embodiments, R13is substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R13is substituted or unsubstituted 2 to 4 membered heteroalkyl. In embodiments, R13is substituted or unsubstituted 2 to 3 membered heteroalkyl. In embodiments, R13is substituted 2 membered heteroalkyl. In embodiments, R13is unsubstituted 2 membered heteroalkyl. In embodiments, R13is substituted 3 membered heteroalkyl. In embodiments, R13is unsubstituted 3 membered heteroalkyl. In embodiments, R1is hydrogen, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —SH, —NO2, —NH2, —C(O)H, —C(O)OH, —C(O)OCH3, —OH, —OCH3, substituted or unsubstituted C1-C4alkyl, or substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R1is hydrogen. In embodiments, R1is —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, or —OCH2I. In embodiments, R1is —SH. In embodiments, R1is —NO2. In embodiments, R1is —NH2. In embodiments, R1is —C(O)H. In embodiments, R1is —C(O)OH. In embodiments, R1is —C(O)OCH3. In embodiments, R1is —OH. In embodiments, R1is —OCH3. In embodiments, R1is substituted or unsubstituted C1-C4alkyl. In embodiments, R1is substituted or unsubstituted C1-C4alkyl. In embodiments, R1is substituted methyl. In embodiments, R1is unsubstituted methyl. In embodiments, R1is substituted ethyl. In embodiments, R1is unsubstituted ethyl. In embodiments, R1is substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R1is substituted or unsubstituted 2 to 4 membered heteroalkyl. In embodiments, R1is substituted or unsubstituted 2 to 3 membered heteroalkyl. In embodiments, R1is substituted 2 membered heteroalkyl. In embodiments, R1is unsubstituted 2 membered heteroalkyl. In embodiments, R1is substituted 3 membered heteroalkyl. In embodiments, R1is unsubstituted 3 membered heteroalkyl. In embodiments, R2is hydrogen, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —SH, —NO2, —NH2, —C(O)H, —C(O)OH, —C(O)OCH3, —OH, —OCH3, substituted or unsubstituted C1-C4alkyl, or substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R2is hydrogen. In embodiments, R2is —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, or —OCH2I. In embodiments, R2is —SH. In embodiments, R2is —NO2. In embodiments, R2is —NH2. In embodiments, R2is —C(O)H. In embodiments, R2is —C(O)OH. In embodiments, R2is —C(O)OCH3. In embodiments, R2is —OH. In embodiments, R2is —OCH3. In embodiments, R2is substituted or unsubstituted C1-C4alkyl. In embodiments, R2is substituted or unsubstituted C1-C2alkyl. In embodiments, R2is substituted methyl. In embodiments, R2is unsubstituted methyl. In embodiments, R2is substituted ethyl. In embodiments, R2is unsubstituted ethyl. In embodiments, R2is substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R2is substituted or unsubstituted 2 to 4 membered heteroalkyl. In embodiments, R2is substituted or unsubstituted 2 to 3 membered heteroalkyl. In embodiments, R2is substituted 2 membered heteroalkyl. In embodiments, R2is unsubstituted 2 membered heteroalkyl. In embodiments, R2is substituted 3 membered heteroalkyl. In embodiments, R2is unsubstituted 3 membered heteroalkyl. In embodiments, R3is hydrogen, —OCF3, —OCCl3, —OCBr2, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —SH, —NO2, —NH2, —C(O)H, —C(O)OH, —C(O)OCH3, —OH, —OCH3, substituted or unsubstituted C1-C4alkyl, or substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R3is hydrogen. In embodiments, R3is —OCF3, —OCCl3, —OCBr2, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, or —OCH2I. In embodiments, R3is —SH. In embodiments, R3is —NO2. In embodiments, R3is —NH2. In embodiments, R3is —C(O)H. In embodiments, R3is —C(O)OH. In embodiments, R3is —C(O)OCH3. In embodiments, R3is —OH. In embodiments, R3is —OCH3. In embodiments, R3is substituted or unsubstituted C1-C4alkyl. In embodiments, R3is substituted or unsubstituted C1-C2alkyl. In embodiments, R3is substituted methyl. In embodiments, R3is unsubstituted methyl. In embodiments, R3is substituted ethyl. In embodiments, R3is unsubstituted ethyl. In embodiments, R3is substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R3is substituted or unsubstituted 2 to 4 membered heteroalkyl. In embodiments, R3is substituted or unsubstituted 2 to 3 membered heteroalkyl. In embodiments, R3is substituted 2 membered heteroalkyl. In embodiments, R3is unsubstituted 2 membered heteroalkyl. In embodiments, R3is substituted 3 membered heteroalkyl. In embodiments, R3is unsubstituted 3 membered heteroalkyl. In embodiments, at least one of R1, R2and R3are —OH. In embodiments, R1is —OH. In embodiments, R2is —OH. In embodiments, R3is —OH. In embodiments, at least two of R1, R2and R3are —OH. In embodiments, R1and R2are —OH. In embodiments, R2and R3are —OH. In embodiments, R1and R3are —OH. In embodiments, R1, R2and R3are —OH. In embodiments, at least one of R1, R2and R3are —OCH3. In embodiments, R1is —OCH3. In embodiments, R2is —OCH3. In embodiments, R3is —OCH3. In embodiments, at least two of R1, R2and R3are —OCH3. In embodiments, R1and R2are —OCH3. In embodiments, R2and R3are —OCH3. In embodiments, R1and R3are —OCH3. In embodiments, R1, R2and R3are —OCH3. In embodiments, L1is —S—, and R1is —OH. In embodiments, L1is —O—, and R1is —OH. In embodiments, L1is —S—, and R2is —OH. In embodiments, L1is —O—, and R2is —OH. In embodiments, L1is —S—, and R3is —OH. In embodiments, L1is —O—, and R3is —OH. In embodiments, L1is —NH—, and R1is —OH. In embodiments, L1is —S(O)—, and R1is —OH. In embodiments, L1is —S(O)2—, and R1is —OH. In embodiments, L1is —NHC(O)—, and R1is —OH. In embodiments, L1is —NHS(O)—, and R1is —OH. In embodiments, L1is —NHS(O)2—, and R1is —OH. In embodiments, L1is a bond, and R1is —OH. In embodiments, L1is —S—, and R1is —OCH3. In embodiments, L1is —O—, and R1is —OCH3. In embodiments, L1is —NH—, and R1is —OCH3. In embodiments, L1is —S(O)—, and R1is —OCH3. In embodiments, L1is —S(O)2—, and R1is —OCH3. In embodiments, L1is —NHC(O)—, and R1is —OCH3. In embodiments, L1is —NHS(O)—, and R1is —OCH3. In embodiments, L1is —NHS(O)2—, and R1is —OCH3. In embodiments, L1is a bond, and R1is —OCH3. In embodiments, R7is hydrogen, —OCF3, —OCCl3, —OCBr2, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —SH, —NO2, —NH2, —C(O)H, —C(O)OH, —C(O)OCH3, —OH, —OCH3, substituted or unsubstituted C1-C4alkyl, or substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R7is hydrogen. In embodiments, R7is —OCF3, —OCCl3, —OCBr2, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, or —OCH2I. In embodiments, R7is —SH. In embodiments, R7is —NO2. In embodiments, R7is —NH2. In embodiments, R7is —C(O)H. In embodiments, R7is —C(O)OH. In embodiments, R7is —C(O)OCH3. In embodiments, R7is —OH. In embodiments, R7is —OCH3. In embodiments, R7is substituted or unsubstituted C1-C4alkyl. In embodiments, R7is substituted or unsubstituted C1-C2alkyl. In embodiments, R7is substituted methyl. In embodiments, R7is unsubstituted methyl. In embodiments, R7is substituted ethyl. In embodiments, R7is unsubstituted ethyl. In embodiments, R7is substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R7is substituted or unsubstituted 2 to 4 membered heteroalkyl. In embodiments, R7is substituted or unsubstituted 2 to 3 membered heteroalkyl. In embodiments, R7is substituted 2 membered heteroalkyl. In embodiments, R7is unsubstituted 2 membered heteroalkyl. In embodiments, R7is substituted 3 membered heteroalkyl. In embodiments, R7is unsubstituted 3 membered heteroalkyl. In embodiments, R9is hydrogen, —OCF3, —OCCl3, —OCBr2, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —SH, —NO2, —NH2, —C(O)H, —C(O)OH, —C(O)OCH3, —OH, —OCH3, substituted or unsubstituted C1-C4alkyl, or substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R9is hydrogen. In embodiments, R9is —OCF3, —OCCl3, —OCBr2, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, or —OCH2I. In embodiments, R9is —SH. In embodiments, R9is —NO2. In embodiments, R9is —NH2. In embodiments, R9is —C(O)H. In embodiments, R9is —C(O)OH. In embodiments, R9is —C(O)OCH3. In embodiments, R9is —OH. In embodiments, R9is —OCH3. In embodiments, R9is substituted or unsubstituted C1-C4alkyl. In embodiments, R9is substituted or unsubstituted C1-C2alkyl. In embodiments, R9is substituted methyl. In embodiments, R9is unsubstituted methyl. In embodiments, R9is substituted ethyl. In embodiments, R9is unsubstituted ethyl. In embodiments, R9is substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R9is substituted or unsubstituted 2 to 4 membered heteroalkyl. In embodiments, R9is substituted or unsubstituted 2 to 3 membered heteroalkyl. In embodiments, R9is substituted 2 membered heteroalkyl. In embodiments, R9is unsubstituted 2 membered heteroalkyl. In embodiments, R9is substituted 3 membered heteroalkyl. In embodiments, R9is unsubstituted 3 membered heteroalkyl. In embodiments, at least one of R7and R9are hydrogen. In embodiments, R7is hydrogen. In embodiments, R9is hydrogen. In embodiments, R7and R9are hydrogen. In embodiments, R7is not hydrogen. In embodiments, R9is not hydrogen. In embodiments, R6is hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, substituted or unsubstituted C1-C4alkyl, or substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R6is hydrogen. In embodiments, R6is —F, —Cl, —Br, or —I. In embodiments, R6is —N3. In embodiments, R6is —CN. In embodiments, R6is —NO2. In embodiments, R6is —NH2, —C(O)H, —C(O)CH3. In embodiments, R6is —C(O)OH, —C(O)OCH3. In embodiments, R6is —C(O)NH2. In embodiments, R6is —OH. In embodiments, R6is —OCH3. In embodiments, R6is substituted or unsubstituted C1-C4alkyl. In embodiments, R6is substituted or unsubstituted C1-C2alkyl. In embodiments, R6is substituted methyl. In embodiments, R6is unsubstituted methyl. In embodiments, R6is substituted ethyl. In embodiments, R6is unsubstituted ethyl. In embodiments, R6is substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R6is substituted or unsubstituted 2 to 4 membered heteroalkyl. In embodiments, R6is substituted or unsubstituted 2 to 3 membered heteroalkyl. In embodiments, R6is substituted 2 membered heteroalkyl. In embodiments, R6is unsubstituted 2 membered heteroalkyl. In embodiments, R6is substituted 3 membered heteroalkyl. In embodiments, R6is unsubstituted 3 membered heteroalkyl. In embodiments, R8is hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, substituted or unsubstituted C1-C4alkyl, or substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R8is hydrogen. In embodiments, R8is halogen. In embodiments, R8is —F, —Cl, —Br, or —I. In embodiments, R8is —N3. In embodiments, R8is —CN. In embodiments, R8is —NO2. In embodiments, R8is —NH2, —C(O)H, —C(O)CH3. In embodiments, R8is —C(O)OH, —C(O)OCH3. In embodiments, R8is —C(O)NH2. In embodiments, R8is —OH. In embodiments, R8is —OCH3. In embodiments, R8is substituted or unsubstituted C1-C4alkyl. In embodiments, R8is substituted or unsubstituted C1-C2alkyl. In embodiments, R8is substituted methyl. In embodiments, R8is unsubstituted methyl. In embodiments, R8is substituted ethyl. In embodiments, R8is unsubstituted ethyl. In embodiments, R8is substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R8is substituted or unsubstituted 2 to 4 membered heteroalkyl. In embodiments, R8is substituted or unsubstituted 2 to 3 membered heteroalkyl. In embodiments, R8is substituted 2 membered heteroalkyl. In embodiments, R8is unsubstituted 2 membered heteroalkyl. In embodiments, R8is substituted 3 membered heteroalkyl. In embodiments, R8is unsubstituted 3 membered heteroalkyl. In embodiments, R10is hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3Jsubstituted or unsubstituted C1-C4alkyl, or substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R10is hydrogen. In embodiments, R10is halogen. In embodiments, R10is —F, —Cl, —Br, or —I. In embodiments, R10is —N3. In embodiments, R10is —CN. In embodiments, R10is —NO2. In embodiments, R10is —NH2, —C(O)H, —C(O)CH3. In embodiments, R10is —C(O)OH, —C(O)OCH3. In embodiments, R10is —C(O)NH2. In embodiments, R10is —OH. In embodiments, R10is —OCH3. In embodiments, R10is substituted or unsubstituted C1-C4alkyl. In embodiments, R10is substituted or unsubstituted C1-C2alkyl. In embodiments, R10is substituted methyl. In embodiments, R10is unsubstituted methyl. In embodiments, R10is substituted ethyl. In embodiments, R10is unsubstituted ethyl. In embodiments, R10is substituted or unsubstituted 2 to 6 membered heteroalkyl. In embodiments, R10is substituted or unsubstituted 2 to 4 membered heteroalkyl. In embodiments, R10is substituted or unsubstituted 2 to 3 membered heteroalkyl. In embodiments, R10is substituted 2 membered heteroalkyl. In embodiments, R10is unsubstituted 2 membered heteroalkyl. In embodiments, R10is substituted 3 membered heteroalkyl. In embodiments, R10is unsubstituted 3 membered heteroalkyl. In embodiments, each R6, R8, and R10is independently hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, or substituted or unsubstituted C1-C3alkyl. In embodiments, each R6and R10is independently hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, or substituted or unsubstituted C1-C3alkyl. In embodiments, each R6and R8is independently hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, or substituted or unsubstituted C1-C3alkyl. In embodiments, each R8, and R10is independently hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, or substituted or unsubstituted C1-C3alkyl. In embodiments, at least one of R6, R8, and R10are hydrogen. In embodiments, R6is hydrogen. In embodiments, R8is hydrogen. In embodiments, R10is hydrogen. In embodiments, at least two of R6, R8, and R10are hydrogen. In embodiments, R6and R10are hydrogen. In embodiments, R8and R10are hydrogen. In embodiments, R6and R8are hydrogen. In embodiments, R6, R8, and R10are hydrogen. In embodiments, the compound has a formula: wherein R1, R2, R3, R6, R7, R8, R9, R10, R15, R16, and R17are as described herein. In embodiments, the compound has a formula: wherein R1, R2, R3, R6, R7, R8, R9, R10, R15, R16, and R17are as described herein. In embodiments, the compound has a formula: wherein R1, R2, R3, R6, R7, R8, R9, R10, R15, R16, and R17are as described herein. In embodiments, the compound has a formula: wherein R1, R2, R3, R6, R7, R8, R9, R10, R15, R16, and R17are as described herein. In embodiments, the compound has a formula: wherein R1, R2, R3, R6, R7, R8, R9, R10, R15, R16, and R17are as described herein. In embodiments, the compound has a formula: wherein R1, R2, R3, R6, R7, R8, R9, and R10are as described herein. In embodiments, the compound has a formula: wherein R1, R2, R3, R6, R7, R8, R9, and R10are as described herein. In embodiments, the compound has a formula: wherein R1, R2, R3, R6, R7, R8, R9, and R10are as described herein. In embodiments, the compound has a formula: wherein R1, R2, R3, R6, R7, R8, R9, and R10are as described herein. In embodiments, the compound has a formula: wherein R1, R2, R3, R6, R7, R8, R9, and R10are as described herein. In embodiments, the compound has a formula (III), In formula (III), R2, R3, R8, R14, R15, R16, and R17are as described herein. In embodiments, the compound has a formula (IV), In formula (IV), R2, R3, R6, R8, and R10are as described herein. In embodiments, the compound has a formula (V), In formula (V), R1and R8are as described herein. In embodiments, the compound has a formula (VI), In formula (VI), R1and R6are as described herein. In embodiments, the compound has a formula (VII), In formula (VII), R1and R6are as described herein. In embodiments, the compound has a formula (VIII), In formula (VIII), R1D, R6, R7and R8are as described herein. In embodiments, R1Dis hydrogen or unsubstituted C1-C4alkyl and R6is hydrogen or —C(O)—OR6C. In embodiments, R1Dis hydrogen or unsubstituted C1-C4alkyl and R7is hydrogen or halogen. In embodiments, R1Dis hydrogen or unsubstituted C1-C4alkyl and R8is halogen, —OR8D, —C(O)—OR8C, or unsubstituted C2-C4alkyl. In embodiments, R1Dis hydrogen or unsubstituted C1-C4alkyl; R6is hydrogen or —C(O)—OR6C; and R7is hydrogen or halogen. In embodiments, R1Dis hydrogen or unsubstituted C1-C4alkyl; R6is hydrogen or —C(O)—OR6C; and R8is halogen, —OR8D, —C(O)—OR8C, or unsubstituted C2-C4alkyl. In embodiments, R1Dis hydrogen or unsubstituted C1-C4alkyl; R7is hydrogen or halogen; and R8is halogen, —OR8D, —C(O)—OR8C, or unsubstituted C2-C4alkyl. In embodiments, R1Dis hydrogen or unsubstituted C1-C4alkyl; R6is hydrogen or —C(O)—OR6C; R7is hydrogen or halogen; and R8is halogen, —OR8D, —C(O)—OR8C, or unsubstituted C2-C4alkyl. In embodiments, R1Dis hydrogen or unsubstituted C1-C4alkyl. In embodiments, R1Dis hydrogen. In embodiments, R1Dis unsubstituted C1-C4alkyl. In embodiments, R1Dis unsubstituted methyl. In embodiments, R1Dis unsubstituted ethyl. In embodiments, R1Dis unsubstituted propyl. In embodiments, R1Dis unsubstituted isopropyl. In embodiments, R1Dis unsubstituted butyl. In embodiments, R1Dis unsubstituted t-butyl. In embodiments, R6is hydrogen or —C(O)—OR6C. In embodiments, R6is hydrogen. In embodiments, R6is —C(O)—OR6C. In embodiments, R6is —C(O)—OH. In embodiments, R6is —C(O)—OCH3. In embodiments, R6is —C(O)—OCH2CH3. In embodiments, R7is hydrogen or halogen. In embodiments, R7is hydrogen. In embodiments, R7halogen. In embodiments, R7is —F. In embodiments, R7is —Cl. In embodiments, R7is —Br. In embodiments, R7is —I. In embodiments, R8is halogen, —OR8D, —C(O)—OR8C, or unsubstituted C2-C4alkyl. In embodiments, R8is halogen. In embodiments, R8is —F. In embodiments, R8is —Cl. In embodiments, R8is —Br. In embodiments, R8is —I. In embodiments, R8is —OR8D. In embodiments, R8is —OH. In embodiments, R8is —OCH3. In embodiments, R8is —OCH2CH3. In embodiments, R8is —C(O)—OR8C. In embodiments, R8is —C(O)—OH. In embodiments, R8is —C(O)—OCH3. In embodiments, R8is —C(O)—OCH2CH3. In embodiments, R8is —C(O)—OC(CH3)3. In embodiments, R8is unsubstituted C2-C4alkyl. In embodiments, R8is unsubstituted ethyl. In embodiments, R8is unsubstituted propyl. In embodiments, R8is unsubstituted propyl. In embodiments, R8is unsubstituted butyl. In embodiments, R8is unsubstituted t-butyl. In embodiments, R1D, R6C, R8C, and R8Dare independently hydrogen or unsubstituted C1-C3alkyl. In embodiments, R1Dis hydrogen or unsubstituted C1-C3alkyl. In embodiments, R1Dis hydrogen. In embodiments, R1Dis unsubstituted C1-C3alkyl. In embodiments, R1Dis —CH3. In embodiments, R1Dis —CH3. In embodiments, R1Dis —CH2CH3. In embodiments, R1Dis —C(CH3)3. In embodiments, R1Dis —CH2CH2CH3. In embodiments, R1Dis —CH(CH3)2. In embodiments, R6Cis hydrogen or unsubstituted C1-C3alkyl. In embodiments, R6Cis hydrogen. In embodiments, R6Cis unsubstituted C1-C3alkyl. In embodiments, R6Cis —CH3. In embodiments, R6Cis —CH3. In embodiments, R6Cis —CH2CH3. In embodiments, R6Cis —C(CH3)3. In embodiments, R6Cis —CH2CH2CH3. In embodiments, R6Cis —CH(CH3)2. In embodiments, R8Cis hydrogen or unsubstituted C1-C3alkyl. In embodiments, R8Cis hydrogen. In embodiments, R8Cis unsubstituted C1-C3alkyl. In embodiments, R8Cis —CH3. In embodiments, R8Cis —CH3. In embodiments, R8Cis —CH2CH3. In embodiments, R8Cis —C(CH3)3. In embodiments, R8Cis —CH2CH2CH3. In embodiments, R8Cis —CH(CH3)2. In embodiments, R8Dis hydrogen or unsubstituted C1-C3alkyl. In embodiments, R8Dis hydrogen. In embodiments, R8Dis unsubstituted C1-C3alkyl. In embodiments, R8Dis —CH3. In embodiments, R8Dis —CH3. In embodiments, R8Dis —CH2CH3. In embodiments, R8Dis —C(CH3)3. In embodiments, R8Dis —CH2CH2CH3. In embodiments, R8Dis —CH(CH3)2. In embodiments, R1Dis hydrogen; R6and R7are hydrogen; and R8is —OH, —OCH3, —COOH, —Br, or —C(CH3)3. In embodiments, R1Dis hydrogen; R6is hydrogen; and R8is —OH, —OCH3, —COOH, —Br, or —C(CH3)3. In embodiments, R1Dis hydrogen; R7is hydrogen; and R8is —OH, —OCH3, —COOH, —Br, or —C(CH3)3. In embodiments, R1Dis hydrogen; and R8is —OH, —OCH3, —COOH, —Br, or —C(CH3)3. In embodiments, R1Dis hydrogen and R6and R7are hydrogen. In embodiments, R6and R7are hydrogen; and R8is —OH, —OCH3, —COOH, —Br, or —C(CH3)3. In embodiments, R6is hydrogen; and R8is —OH, —OCH3, —COOH, —Br, or —C(CH3)3. In embodiments, R7is hydrogen; and R8is —OH, —OCH3, —COOH, —Br, or —C(CH3)3. In embodiments, R1Dis hydrogen; R6and R7are hydrogen; and R8is —OR8D, —COOR8C, halogen, or unsubstituted C2-C4alkyl. In embodiments, R1Dis hydrogen. In embodiments, R6and R7are hydrogen. In embodiments, R6is hydrogen. In embodiments, R7is hydrogen. In embodiments, R8is —OR8D. In embodiments, R8is —OH. In embodiments, R8is —OCH3. In embodiments, R8is —OCH2CH3. In embodiments, R8is —COOH. In embodiments, R8is —COOCH3. In embodiments, R8is —COOCH2CH3. In embodiments, R8is —COOC(CH3)3. In embodiments, R8is halogen. In embodiments, R8is —F. In embodiments, R8is —Cl. In embodiments, R8is —Br. In embodiments, R8is —I. In embodiments, R8is unsubstituted C1-C4alkyl. In embodiments, R8is unsubstituted C2-C4alkyl. In embodiments, R8is —CH3. In embodiments, R8is —CH3. In embodiments, R8is —CH2CH3. In embodiments, R8is —C(CH3)3. In embodiments, R8is —CH2CH2CH3. In embodiments, R8is —CH(CH3)2. In embodiments, R1Dis —CH3; R6and R7are hydrogen; and R8is —OH, —OCH3, —COOH, —COOCH3, —Cl, —Br, or —C(CH3)3. In embodiments, R1Dis —CH3; R6is hydrogen; and R7and R8are halogen. In embodiments, R1Dis —CH3; and R7and R8are halogen. In embodiments, R1Dis —CH3; R6is hydrogen; and R8is halogen. In embodiments, R1Dis —CH3; R6is hydrogen; and R7is halogen. In embodiments, R1Dis —CH3. In embodiments, R1Dis —CH2CH3. In embodiments, R6is hydrogen. In embodiments, R7and R8are halogen. In embodiments, R7is —F. In embodiments, R7is —Cl. In embodiments, R7is —Br. In embodiments, R7is —I. In embodiments, R8is —F. In embodiments, R8is —Cl. In embodiments, R8is —Br. In embodiments, R8is —I. In embodiments, R1Dis hydrogen or —CH3; R6is —C(O)—OR6C; and R7and R8are hydrogen. In embodiments, R1Dis hydrogen; R6is —C(O)—OR6C; and R7and R8are hydrogen. In embodiments, R1Dis-CH3; R6is —C(O)—OR6C; and R7and R8are hydrogen. In embodiments, R1Dis hydrogen or —CH3; and R7and R8are hydrogen. In embodiments, R1Dis hydrogen or —CH3and R6is —C(O)—OR6C. In embodiments, R1Dis hydrogen or —CH3; R6is —C(O)—OH; and R7and R8are hydrogen. In embodiments, R1Dis hydrogen or —CH3; R6is —C(O)—OCH3; and R7and R8are hydrogen. In embodiments, R1Dis hydrogen or —CH3; R6is —C(O)—OR6C; and R7is hydrogen. In embodiments, R1Dis hydrogen or —CH3; R6is —C(O)—OR6C; and R8is hydrogen. In embodiments, R1Dis hydrogen. In embodiments, R1Dis —CH3. In embodiments, R6is —C(O)OH. In embodiments, R6is —C(O)OCH3. In embodiments, R7and R8are hydrogen. In embodiments, R7is hydrogen. In embodiments, R8is hydrogen. In embodiments, the compound has a formula (IX), In formula (IX), R1D, R2D, R3D, and R6are as described herein. In embodiments, R1D, R2D, and R3Dare independently hydrogen or unsubstituted C1-C4alkyl; and R6is hydrogen, halogen, —C(O)—OR6C, —OR6D, or unsubstituted C1-C4alkyl. In embodiments, R1D, R2D, and R3Dare independently hydrogen or unsubstituted C1-C4alkyl. In embodiments, R1Dis hydrogen or unsubstituted C1-C4alkyl. In embodiments, R1Dis hydrogen. In embodiments, R1Dis unsubstituted C1-C4alkyl. In embodiments, R1Dis unsubstituted methyl. In embodiments, R1Dis unsubstituted ethyl. In embodiments, R1Dis unsubstituted propyl. In embodiments, R1Dis unsubstituted propyl. In embodiments, R1Dis unsubstituted butyl. In embodiments, R1Dis unsubstituted t-butyl. In embodiments, R2Dis hydrogen or unsubstituted C1-C4alkyl. In embodiments, R2Dis hydrogen. In embodiments, R2Dis unsubstituted C1-C4alkyl. In embodiments, R2Dis unsubstituted methyl. In embodiments, R2Dis unsubstituted ethyl. In embodiments, R2Dis unsubstituted propyl. In embodiments, R2Dis unsubstituted propyl. In embodiments, R2Dis unsubstituted butyl. In embodiments, R2Dis unsubstituted t-butyl. In embodiments, R3Dis hydrogen or unsubstituted C1-C4alkyl. In embodiments, R3Dis hydrogen. In embodiments, R3Dis unsubstituted C1-C4alkyl. In embodiments, R3Dis unsubstituted methyl. In embodiments, R3Dis unsubstituted ethyl. In embodiments, R3Dis unsubstituted propyl. In embodiments, R3Dis unsubstituted propyl. In embodiments, R3Dis unsubstituted butyl. In embodiments, R3Dis unsubstituted t-butyl. In embodiments, R6is hydrogen, halogen, —C(O)—OR6C, —OR6D, or unsubstituted C1-C4alkyl. In embodiments, R6is hydrogen. In embodiments, R6is halogen. In embodiments, R6is —F. In embodiments, R6is —Cl. In embodiments, R6is —Br. In embodiments, R6is —I. In embodiments, R6is —C(O)—OR6C. In embodiments, R6is —C(O)—OH. In embodiments, R6is —C(O)—OCH3. In embodiments, R6is —C(O)—OCH2CH3. In embodiments, R6is —OR6D. In embodiments, R6is —OH. In embodiments, R6is —OCH3. In embodiments, R6is —OCH2CH3. In embodiments, R6is —OC(CH3)3. In embodiments, R6is unsubstituted C1-C4alkyl. In embodiments, R6is unsubstituted methyl. In embodiments, R6is unsubstituted ethyl. In embodiments, R6is unsubstituted propyl. In embodiments, R6is unsubstituted propyl. In embodiments, R6is unsubstituted butyl. In embodiments, R6is unsubstituted t-butyl. In embodiments, R1D, R2D, and R3Dare independently hydrogen or —CH3; and R6Cand R6Dare independently hydrogen or —CH3. In embodiments, R1D, and R3Dare independently hydrogen or —CH3; and R6Cand R6Dare independently hydrogen or —CH3. In embodiments, R1D, and R2Dare independently hydrogen or —CH3; and R6Cand R6Dare independently hydrogen or —CH3. In embodiments, R1Dis hydrogen or —CH3; and R6Cand R6Dare independently hydrogen or —CH3. In embodiments, R2Dis hydrogen or —CH3; and R6Cand R6Dare independently hydrogen or —CH3. In embodiments, R3Dis hydrogen or —CH3; and R6Cand R6Dare independently hydrogen or —CH3. In embodiments, R1D, R2D, and R3Dare independently hydrogen or —CH3. In embodiments, R1Dis hydrogen or —CH3. In embodiments, R1Dis hydrogen. In embodiments, R1Dis —CH3. In embodiments, R2Dis hydrogen or —CH3. In embodiments, R2Dis hydrogen. In embodiments, R2Dis —CH3. In embodiments, R3Dis hydrogen or —CH3. In embodiments, R3Dis hydrogen. In embodiments, R3Dis —CH3. In embodiments, R1D, and R3Dare hydrogen. In embodiments, R2D, and R3Dare hydrogen. In embodiments, R1D, and R2Dare hydrogen. In embodiments, R1D, R2D, and R3Dare hydrogen. In embodiments, R1D, and R3Dare —CH3. In embodiments, R2D, and R3Dare —CH3. In embodiments, R1D, and R2Dare —CH3. In embodiments, R1D, R2D, and R3Dare —CH3. In embodiments, R6Cand R6Dare independently hydrogen or —CH3. In embodiments, R6Cis hydrogen or —CH3. In embodiments, R6Cis hydrogen. In embodiments, R6Cis —CH3. In embodiments, R6Dis hydrogen or —CH3. In embodiments, R6Dis hydrogen. In embodiments, R6Dis —CH3. In embodiments, R6Cand R6Dare hydrogen. In embodiments, R6Cand R6Dare —CH3. In embodiments, the compound is: In embodiments, the compound is: In embodiments, the compound is not In embodiments, the compound is not In embodiments, the compound is not In embodiments, the compound is not In embodiments, the compound is not In embodiments, the compound is In embodiments, the compound is not embodiments, the compound is not In embodiments, the compound is not In embodiments, the compound is not In an aspect is provided a compound, the compound has a formula (X), Formula (X). In formula (X), R1is as described herein. In embodiments, R20is -L1-Ring A. Ring A is substituted or unsubstituted aryl. L1is a bond, —CR11R12—, —NR13—, —O—, —S—, —S(O)—, —S(O)2—, —NR13S(O)—, —NR13S(O)2—, or —NR13C(O)—. In embodiments, L1is a bond. In embodiments, L1is —CR11R12—. In embodiments, L1is —CH2—. In embodiments, L1is —NR13—. In embodiments, L1is —NH—. In embodiments, L1is —NCH3—. In embodiments, L1is —O—. In embodiments, L1is —S—. In embodiments, L1is —S(O)2—. In embodiments, L1is —NR13S(O)2—. In embodiments, L1is —NHS(O)2—. In embodiments, L1is —NR13C(O)—. In embodiments, L1is —NHC(O)—. Ring A is substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl). In embodiments, Ring A is substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl). In embodiments, Ring A is substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) aryl (e.g., C6-C12, C6-C10, or phenyl). In embodiments, Ring A is an unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl). Ring A is R19-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl). In embodiments, Ring A is R19-substituted aryl (e.g., C6-C12, C6-C10, or phenyl). Ring A is R19-unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl). In embodiments, Ring A is R19-substituted or unsubstituted phenyl. In embodiments, Ring A is R19-substituted phenyl. In embodiments, Ring A is unsubstituted phenyl. In embodiments, Ring A is R19-substituted or unsubstituted naphthyl. In embodiments, Ring A is R19-substituted naphthyl. In embodiments, Ring A is unsubstituted naphthyl. In embodiments, Ring A is R19-substituted or unsubstituted anthracenyl. In embodiments, Ring A is R19-substituted anthracenyl. In embodiments, Ring A is unsubstituted anthracenyl. In embodiments, Ring A is R19-substituted or unsubstituted phenanthenyl. In embodiments, Ring A is R19-substituted phenanthenyl. In embodiments, Ring A is unsubstituted phenanthenyl. In embodiments, Ring A is R19-substituted or unsubstituted chrysenyl. In embodiments, Ring A is R19-substituted chrysenyl. In embodiments, Ring A is unsubstituted chrysenyl. In embodiments, Ring A is R19-substituted or unsubstituted pyrenyl. In embodiments, Ring A is R19-substituted pyrenyl. In embodiments, Ring A is unsubstituted pyrenyl. R19is independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R19F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R19F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R19F-substituted or unsubstituted cycloalkyl(e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R19F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R19F-substituted or unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R19F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). R19is independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —COMB, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R19F-substituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R19F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R19F-substituted cycloalkyl(e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R19F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R19F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R19F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). R19is independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl(e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, in the formula (X), R1is —OCH3. In embodiments, R20is: In embodiments, in the formula (X), R1is —OH. In embodiments, R20is: In embodiments, R1is hydrogen, halogen (e.g., —F, —Cl, Br, —I), —CX13, —CHX12, —CH2X1, —OCX13, —OCH2X1, —OCHX12, —N3, —CN, —SOn1R1D, —SOv1NR1AR1B, —NHC(O)NR1AR1B, —N(O)m1, —NR1AR1B, —C(O)R1C, —C(O)—OR1C, —C(O)NR1AR1B, —OR1D, —NR1ASO2R1D, —NR1AC(O) R1C, —NR1AC(O)OR1C, —NR1AOR1C, substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). n1 is an integer from 0 to 4 (e.g. 0). m1 and v1 are independently an integer from 1 to 2. X1is independently —F, —Cl, —Br, or —I. In embodiments, R1is —CF3, —CHF2, —CH2F, —CCl3, —CH2Cl, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, or —NCH3OCH3. In embodiments R1is hydrogen, —F, —Cl, Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R1E-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R1E-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R1E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R1E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R1E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R1E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R1is hydrogen, —F, —Cl, Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R1E-substituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R1E-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R1E-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R1E-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R1E-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R1E-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R1is hydrogen, —F, —Cl, Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, unsubstituted alkyl (e.g, C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). R1Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R1F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R1F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R1F-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R1F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R1F-substituted or unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R1F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R1Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R1F-substituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R1F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R1F-substituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R1F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R1F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R1F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R1Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R2is hydrogen, halogen (e.g., —F, —Cl, —Br, —I), —CX23, —CHX22, —CH2X2, —OCX23, —OCH2X2, —OCHX22, —N3, —CN, —SOn2R2D, —SOv2NR2AR2B, —NHC(O)NR2AR2B, —N(O)m2, —NR2AR2B, —C(O)R2C, —C(O)—OR2C, —C(O)NR2AR2B, —OR2D, —NR2ASO2R2D, —NR2AC(O) R2C, —NR2AC(O)OR2C, —NR2AOR2C, substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C12. C1-C8. C1-C6, C1-C4, or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). n2 is an integer from 0 to 4 (e.g. 0). m2 and v2 are independently an integer from 1 to 2. X2is independently —F, —Cl, —Br, or —I. In embodiments, R2is e.g., —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, or —NCH3OCH3. In embodiments, R2is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl3, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R2E-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R2E-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R2E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R2E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R2E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R2E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R2is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R2E-substituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R2E-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R2E-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R2E-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R2E-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R2E-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R2is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, unsubstituted alkyl (e.g, C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). R2Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R2F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R2F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R2F-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R2F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R2F-substituted or unsubstituted aryl (e.g., C6-C10, C in aryl, or phenyl), or R2F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R2Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R2F-substituted alkyl (e.g, C1-C8, C1-C6, or C1-C4alkyl), R2F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R2F-substituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R2F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R2F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R2F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R2Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —COMB, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R1and R2together with atoms attached thereto are joined to form R1E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R1E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R1E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R1E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R1and R2together with atoms attached thereto are joined to form R1E-substituted or unsubstituted cyclopentyl. In embodiments, R1and R2together with atoms attached thereto are joined to form R1E-substituted or unsubstituted cyclohexyl. In embodiments, R1and R2together with atoms attached thereto are joined to form R1E-substituted or unsubstituted pyridyl. In embodiments, R1and R2together with atoms attached thereto are joined to form R1E-substituted or unsubstituted piperidinyl. In embodiments, R1and R2together with atoms attached thereto are joined to form R1E-substituted or unsubstituted morpholinyl. In embodiments, R1and R2together with atoms attached thereto are joined to form R1E-substituted or unsubstituted phenyl. In embodiments, R1and R2together with atoms attached thereto are joined to form R1E-substituted or unsubstituted pyrrolyl. In embodiments, R1and R2together with atoms attached thereto are joined to form R1E-substituted or unsubstituted pyrimidinyl. In embodiments, R1and R2together with atoms attached thereto are joined to form R1E-substituted or unsubstituted thiophenyl. In embodiments, R3is hydrogen, halogen (e.g., —F, —Cl, —Br, —I), —CX33, —CHX32, —CH2X3, —OCX33, —OCH2X3, —OCHX32, —N3, —CN, —SOn3R3D, —SOv3NR3AR3B, —NHC(O)NR3AR3B, —N(O)m3, —NR3AR3B, —C(O)R3C, —C(O)—OR3C, —C(O)NR3AR3B, —OR3D, —NR3ASO2R3D, —NR3AC(O)R3C, —NR3AC(O) OR3C, —NR3AOR3C, substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). n3 is an integer from 0 to 4 (e.g. 0). m3 and v3 are independently an integer from 1 to 2. X3is independently —F, —Cl, —Br, or —I. In embodiments, R3is —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, or —NCH3OCH3. In embodiments, R3is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R3E-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R3E-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R3E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R3E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R3E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R3E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R3is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R3E-substituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R3E-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R3E-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R3E-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R3E-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R3E-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R3is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). R3Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CH2Cl, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCH2Cl, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R3F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R3F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R3F-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R3F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R3F-substituted or unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R3F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R3Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CH2Cl, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCH2Cl, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R3F-substituted alkyl (e.g, C1-C8, C1-C6, or C1-C4alkyl), R3F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R3F-substituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R3F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R3F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R3F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R3Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R2and R3together with atoms attached thereto are joined to form R2E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R2E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R2E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R2E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R2and R3together with atoms attached thereto are joined to form R2E-substituted or unsubstituted cyclopentyl. In embodiments, R2and R3together with atoms attached thereto are joined to form R2E-substituted or unsubstituted cyclohexyl. In embodiments, R2and R3together with atoms attached thereto are joined to form R2E-substituted or unsubstituted pyridyl. In embodiments, R2and R3together with atoms attached thereto are joined to form R2E-substituted or unsubstituted piperidinyl. In embodiments, R2and R3together with atoms attached thereto are joined to form R2E-substituted or unsubstituted morpholinyl. In embodiments, R2and R3together with atoms attached thereto are joined to form R2E-substituted or unsubstituted phenyl. In embodiments, R2and R3together with atoms attached thereto are joined to form R2E-substituted or unsubstituted pyrrolyl. In embodiments, R2and R3together with atoms attached thereto are joined to form R2E-substituted or unsubstituted pyrimidinyl. In embodiments, R2and R3together with atoms attached thereto are joined to form R2E-substituted or unsubstituted thiophenyl. In embodiments, R4is hydrogen, halogen (e.g., —F, —Cl, —Br, —I), —CX43, —CHX42, —CH2X4, —OCX43, —OCH2X4, —OCHX42, —N3, —CN, —SOn4R4D, —SOv4NR4AR4B, —NHC(O)NR4AR4B, —N(O)m4, —NR4AR4B, —C(O)R4C, —C(O)—OR4C, —C(O)NR4AR4B, —OR4D, —NR4ASO2R4D, —NR4AC(O) R4C, —NR4AC(O)OR4C, —NR4AOR4C, substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C12. C1-C6, C1-C6, C1-C4, or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). n4 is an integer from 0 to 4 (e.g. 0). m4 and v4 are independently an integer from 1 to 2. X4is independently —F, —Cl, —Br, or —I. In embodiments, R4is (e.g., —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, or —NCH3OCH3). In embodiments, R4is hydrogen. In embodiments, R4is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R4E-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R4E-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R4E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R4E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R4E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R4E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R4is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R4E-substituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R4E-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R4E-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R4E-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R4E-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R4E-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R4is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, unsubstituted alkyl (e.g, C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). R4Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R4F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R4F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R4F-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R4F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R4F-substituted or unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R4F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R4Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R4F-substituted alkyl (e.g, C1-C8, C1-C6, or C1-C4alkyl), R4F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R4F-substituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R4F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R4F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R4F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R4Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R3and R4together with atoms attached thereto are joined to form R3E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R3E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R3E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R3E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R3and R4together with atoms attached thereto are joined to form R3E-substituted or unsubstituted cyclopentyl. In embodiments, R3and R4together with atoms attached thereto are joined to form R3E-substituted or unsubstituted cyclohexyl. In embodiments, R3and R4together with atoms attached thereto are joined to form R3E-substituted or unsubstituted pyridyl. In embodiments, R3and R4together with atoms attached thereto are joined to form R3E-substituted or unsubstituted piperidinyl. In embodiments, R3and R4together with atoms attached thereto are joined to form R3E-substituted or unsubstituted morpholinyl. In embodiments, R3and R4together with atoms attached thereto are joined to form R3E-substituted or unsubstituted phenyl. In embodiments, R3and R4together with atoms attached thereto are joined to form R3E-substituted or unsubstituted pyrrolyl. In embodiments, R3and R4together with atoms attached thereto are joined to form R3E-substituted or unsubstituted pyrimidinyl. In embodiments, R3and R4together with atoms attached thereto are joined to form R3E-substituted or unsubstituted thiophenyl. In embodiments, R5is hydrogen, halogen (e.g., —F, —Cl, —Br, —I), —CX53, —CHX52, —CH2X5, —OCX53, —OCH2X5, —OCHX52, —N3, —CN, —SOn5R5D, —SOv5NR5AR5B, —NHC(O)NR5AR5B, —N(O)m5, —NR5AR5B, —C(O)R5C, —C(O)—OR5C, —C(O)NR5AR5B, —OR5D, —NR5ASO2R5D, —NR5AC(O)R5C, —NR5AC(O) OR5C, —NR5AOR5C(e.g., —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, or —NCH3OCH3), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). n5 is an integer from 0 to 4 (e.g. 0). m5 and v5 are independently an integer from 1 to 2. X5is independently —F, —Cl, —Br, or —I. In embodiments, R5is hydrogen. In embodiments, R5is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R5E-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R5E-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R5E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R5E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R5E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R5E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R5is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R5E-substituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R5E-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R5E-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R5E-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R5E-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R5E-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R5is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl3, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, unsubstituted alkyl (e.g, C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). R5Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl3, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R5F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R5F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R5F-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R5F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R5F-substituted or unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R5F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R5Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R5F-substituted alkyl (e.g, C1-C8, C1-C6, or C1-C4alkyl), R5F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R5F-substituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R5F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R5F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R5F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R5Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2—CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R4and R5together with atoms attached thereto are joined to form R4E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C5, or C5-C6), R4E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R4E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R4E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R4and R5together with atoms attached thereto are joined to form R4E-substituted or unsubstituted cyclopentyl. In embodiments, R4and R5together with atoms attached thereto are joined to form R4E-substituted or unsubstituted cyclohexyl. In embodiments, R4and R5together with atoms attached thereto are joined to form R4E-substituted or unsubstituted pyridyl. In embodiments, R4and R5together with atoms attached thereto are joined to form R4E-substituted or unsubstituted piperidinyl. In embodiments, R4and R5together with atoms attached thereto are joined to form R4E-substituted or unsubstituted morpholinyl. In embodiments, R4and R5together with atoms attached thereto are joined to form R4E-substituted or unsubstituted phenyl. In embodiments, R4and R5together with atoms attached thereto are joined to form R4E-substituted or unsubstituted pyrrolyl. In embodiments, R4and R5together with atoms attached thereto are joined to form R4E-substituted or unsubstituted pyrimidinyl. In embodiments, R4and R5together with atoms attached thereto are joined to form R4E-substituted or unsubstituted thiophenyl. In embodiments, R6is hydrogen, halogen (e.g., —F, —Cl, —Br, —I), —CX63, —CHX62, —CH2X6, —OCX63, —OCH2X6, —OCHX62, —N3, —CN, —SOn6R6D, —SOv6NR6AR6B, —NHC(O)NR6AR6B, —N(O)m6, —NR6AR6B, —C(O)R6C, —C(O)—OR6C, —C(O)NR6AR6B, —OR6D, —NR6ASO2R6D, —NR6AC(O) R6C, —NR6AC(O)OR6C, —NR6AOR6C(e.g, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, or —NCH3OCH3), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). n6 is an integer from 0 to 4 (e.g. 0). m6 and v6 are independently an integer from 1 to 2. X6is independently —F, —Cl, —Br, or —I. In embodiments, R6is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R6E-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R6E-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R6E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R6E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R6E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R6E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R6is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R6E-substituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R6E-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R6E-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R6E-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R6E-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R6E-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R6is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCH2Cl, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, unsubstituted alkyl (e.g, C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). R6Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —N3, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R6F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R6F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R6F-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R6F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R6F-substituted or unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R6F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R6Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl3, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R6F-substituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R6F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R6F-substituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R6F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R6F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R6F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R6Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl3, —CHBr2—CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C5, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R7is hydrogen, halogen (e.g., —F, —Cl, —Br, —I), —CX73, —CHX72, —CH2X7, —OCX73, —OCH2X7, —OCHX72, —N3, —CN, —SOn7R7D, —SOv7NR7AR7B, —NHC(O)NR7AR7B, —N(O)m7, —NR7AR7B, —C(O)R7C, —C(O)—OR7C, —C(O)NR7AR7B, —OR7D, —NR7ASO2R7D, —NR7AC(O) R7C, —NR7AC(O)OR7C, —NR7AOR7C(e.g., —CF3, —CHF2, —CH2F, —CCl3, —CHCl3, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, or —NCH3OCH3), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or tot lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). n7 is an integer from 0 to 4 (e.g. 0). m7 and v7 are independently an integer from 1 to 2. X7is independently —F, —Cl, —Br, or —I. In embodiments, R7is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R7E-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R7E-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R7E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R7E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R7E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R7E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R7is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R7E-substituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R7E-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R7E-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R7E-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R7E-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R7E-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R7is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, unsubstituted alkyl (e.g, C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). R7Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R7F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R7F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R7F-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R7F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R7F-substituted or unsubstituted aryl (e.g., C6-C10, C in aryl, or phenyl), or R7F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R7Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R7F-substituted alkyl (e.g, C1-C8, C1-C6, or C1-C4alkyl), R7F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R7F-substituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R7F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R7F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R7F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R7Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R6and R7together with atoms attached thereto are joined to form R6E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R6E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R6E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R6E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R6and R7together with atoms attached thereto are joined to form R6E-substituted or unsubstituted cyclopentyl. In embodiments, R6and R7together with atoms attached thereto are joined to form R6E-substituted or unsubstituted cyclohexyl. In embodiments, R6and R7together with atoms attached thereto are joined to form R6E-substituted or unsubstituted pyridyl. In embodiments, R6and R7together with atoms attached thereto are joined to form R6E-substituted or unsubstituted piperidinyl. In embodiments, R6and R7together with atoms attached thereto are joined to form R6E-substituted or unsubstituted morpholinyl. In embodiments, R6and R7together with atoms attached thereto are joined to form R6E-substituted or unsubstituted phenyl. In embodiments, R6and R7together with atoms attached thereto are joined to form R6E-substituted or unsubstituted pyrrolyl. In embodiments, R6and R7together with atoms attached thereto are joined to form R6E-substituted or unsubstituted pyrimidinyl. In embodiments, R6and R7together with atoms attached thereto are joined to form R6E-substituted or unsubstituted thiophenyl. In embodiments, R8is hydrogen, halogen (e.g., —F, —Cl, —Br, —I), —CX83, —CHX82, —CH2X8, —OCX83, —OCH2X8, —OCHX82, —N3, —CN, —SOn8R8D, —SOv8NR8AR8B, —NHC(O)NR8AR8B, —N(O)m8, —NR8AR8B, —C(O)R8C, —C(O)—OR8C, —C(O)NR8AR8B, —OR8D, —NR8ASO2R8D, —NR8AC(O) R8C, —NR8AC(O)OR8C, —NR8AOR8C(e.g., —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, or —NCH3OCH3substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). n8 is an integer from 0 to 4 (e.g. 0). m8 and v8 are independently an integer from 1 to 2. X8is independently —F, —Cl, —Br, or —I. In embodiments, R8is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R8E-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R8E-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R8E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R8E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R8E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R8E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R8is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R8E-substituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R8E-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R8E-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R8E-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R8E-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R8E-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R8is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCH2Cl, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). R8Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CH2Cl, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCH2Cl, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R8F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R8F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R8F-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R8F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R8F-substituted or unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R8F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R8Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CH2Cl, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCH2Cl, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R8F-substituted alkyl (e.g, C1-C8, C1-C6, or C1-C4alkyl), R8F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R8F-substituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R8F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R8F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R8F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R8Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R7and R8together with atoms attached thereto are joined to form R7E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R7E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R7E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R7E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R7and R8together with atoms attached thereto are joined to form R7E-substituted or unsubstituted cyclopentyl. In embodiments, R7and R8together with atoms attached thereto are joined to form R7E-substituted or unsubstituted cyclohexyl. In embodiments, R7and R8together with atoms attached thereto are joined to form R7E-substituted or unsubstituted pyridyl. In embodiments, R7and R8together with atoms attached thereto are joined to form R7E-substituted or unsubstituted piperidinyl. In embodiments, R7and R8together with atoms attached thereto are joined to form R7E-substituted or unsubstituted morpholinyl. In embodiments, R7and R8together with atoms attached thereto are joined to form R7E-substituted or unsubstituted phenyl. In embodiments, R7and R8together with atoms attached thereto are joined to form R7E-substituted or unsubstituted pyrrolyl. In embodiments, R7and R8together with atoms attached thereto are joined to form R7E-substituted or unsubstituted pyrimidinyl. In embodiments, R7and R8together with atoms attached thereto are joined to form R7E-substituted or unsubstituted thiophenyl. In embodiments, R9is hydrogen, halogen (e.g., —F, —Cl, —Br, —I), —CX93, —CHX92, —CH2X9, —OCX93, —OCH2X9, —OCHX92, —N3, —CN, —SOn9R9D, —SOv9NR9AR9B, —NHC(O)NR9AR9B, —N(O)m9, —NR9AR9B, —C(O)R9C, —C(O)—OR9C, —C(O)NR9AR9B, —OR9D, —NR9ASO2R9D, —NR9AC(O) R9C, —NR9AC(O)OR9C, —NR9AOR9C(e.g, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, or —NCH3OCH3), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). n9 is an integer from 0 to 4 (e.g. 0). m9 and v9 are independently an integer from 1 to 2. X9is independently —F, —Cl, —Br, or —I. In embodiments, R9is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R9E-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R9E-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R9E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R9E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R9E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R9E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R9is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl3, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R9E-substituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R9E-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R9E-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R9E-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R9E-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R9E-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R9is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, unsubstituted alkyl (e.g, C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). R9Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl3, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R9F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R9F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R9F-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R9F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R9F-substituted or unsubstituted aryl (e.g., C6-C10, C in aryl, or phenyl), or R9F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R9Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl3, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R9F-substituted alkyl (e.g, C1-C8, C1-C6, or C1-C4alkyl), R9F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R9F-substituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R9F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R9F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R9F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R9Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl3, —CHBr2—CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R8and R9together with atoms attached thereto are joined to form R8E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R8E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R8E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R8E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R8and R9together with atoms attached thereto are joined to form R8E-substituted or unsubstituted cyclopentyl. In embodiments, R8and R9together with atoms attached thereto are joined to form R8E-substituted or unsubstituted cyclohexyl. In embodiments, R8and R9together with atoms attached thereto are joined to form R8E-substituted or unsubstituted pyridyl. In embodiments, R8and R9together with atoms attached thereto are joined to form R8E-substituted or unsubstituted piperidinyl. In embodiments, R8and R9together with atoms attached thereto are joined to form R8E-substituted or unsubstituted morpholinyl. In embodiments, R8and R9together with atoms attached thereto are joined to form R8E-substituted or unsubstituted phenyl. In embodiments, R8and R9together with atoms attached thereto are joined to form R8E-substituted or unsubstituted pyrrolyl. In embodiments, R8and R9together with atoms attached thereto are joined to form R8E-substituted or unsubstituted pyrimidinyl. In embodiments, R8and R9together with atoms attached thereto are joined to form R8E-substituted or unsubstituted thiophenyl. In embodiments, R10is hydrogen, halogen (e.g., —F, —Cl, —Br, —I), —CX103, —CHX102, —CH2X10, —OCX103, —OCH2X10, —OCHX102, —N3, —CN, —SOn10R10D, —SOv10NR10AR10B, —NHC(O)NR10AR10B, —N(O)m10, —NR10AR10B, —C(O)R10C, —C(O)—OR10C, —C(O)NR10AR10B, —OR10D, —NR10ASO2R10D, —NR10AC(O)R10C, —NR10AC(O)OR10C, —NR10AOR10C(e.g., —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, or —NCH3OCH3), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). n10 is an integer from 0 to 4 (e.g. 0). m10 and v10 are independently an integer from 1 to 2. X10is independently —F, —Cl, —Br, or —I. In embodiments, R10is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R10E-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R10E-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R10E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R10E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R10E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R10E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R10is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R10E-substituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R10E-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R10E-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R10E-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R10E-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R10E-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R10is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). R10Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R10F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R10F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R10F-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R10F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R10F-substituted or unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R10F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R10Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R10F-substituted alkyl (e.g, C1-C8, C1-C6, or C1-C4alkyl), R10F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R10F-substituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R10F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R10F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R10F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R10Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R9and R10together with atoms attached thereto are joined to form R9E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R9E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R9E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R9E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R9and R10together with atoms attached thereto are joined to form R9E-substituted or unsubstituted cyclopentyl. In embodiments, R9and R10together with atoms attached thereto are joined to form R9E-substituted or unsubstituted cyclohexyl. In embodiments, R9and R10together with atoms attached thereto are joined to form R9E-substituted or unsubstituted pyridyl. In embodiments, R9and R10together with atoms attached thereto are joined to form R9E-substituted or unsubstituted piperidinyl. In embodiments, R9and R10together with atoms attached thereto are joined to form R9E-substituted or unsubstituted morpholinyl. In embodiments, R9and R10together with atoms attached thereto are joined to form R9E-substituted or unsubstituted phenyl. In embodiments, R9and R10together with atoms attached thereto are joined to form R9E-substituted or unsubstituted pyrrolyl. In embodiments, R9and R10together with atoms attached thereto are joined to form R9E-substituted or unsubstituted pyrimidinyl. In embodiments, R9and R10together with atoms attached thereto are joined to form R9E-substituted or unsubstituted thiophenyl. In embodiments, R11is hydrogen, halogen (e.g., —F, —Cl, Br, —I), —CX113, —CHX112, —CH2X11, —OCX113, —OCH2X11, —OCHX112, —N3, —CN, —SOn11R11D, —SOv11NR11AR11B, —NHC(O)NR11AR11B, —N(O)m11, —NR11AR11B, —C(O)R11C, —C(O)—OR11C, —C(O)NR11AR11B, —OR11D, —NR11ASO2R11D, —NR11AC(O)R11C, —NR11AC(O)OR11C, —NR11AOR11C(e.g, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, or —NCH3OCH3), substituted (e.g, substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), substituted (e.g, substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g, 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g, substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). n11 is an integer from 0 to 4 (e.g. 0). m11 and v11 are independently an integer from 1 to 2. X11is independently —F, —Cl, —Br, or —I. In embodiments, R11is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R11E-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R11E-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R11E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R11E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R11E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R11E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R11is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R11E-substituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R11E-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R11E-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R11E-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R11E-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R11E-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R11is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl3, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). R11Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl3, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R11F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R11F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R11F-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R11F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R11F-substituted or unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R11F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R11Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R11F-substituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R11F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R11F-substituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R11F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R11F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R11F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R11Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R12is hydrogen, halogen (e.g., —F, —Cl, —Br, —I), —CX123, —CHX122, —CH2X12, —OCX123, —OCH2X12, —OCHX122, —N3, —CN, —SOnl2R12D, —SOv12NR12AR12B, —NHC(O)NR12AR12B, —N(O)m12, —NR12AR12B, —C(O)R12C, —C(O)—OR12C, —C(O)NR12AR12B, —OR12D, —NR12ASO2R12D, —NR12AC(O)R12C, —NR12AC(O)OR12C, —NR12AOR12C(e.g., —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, or —NCH3OCH3), substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). n12 is an integer from 0 to 4 (e.g. 0). m12 and v12 are independently an integer from 1 to 2. X12is independently —F, —Cl, —Br, or —I. In embodiments, R12is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R12E-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R12E-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R12E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C5, C3-C6, C4-C6, or C5-C6), R12E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R12E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R12E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R12is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R12E-substituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R12E-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R12E-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R12E-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R12E-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R12E-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R12is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). R12Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R12F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R12F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R12F-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R12F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R12F-substituted or unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R12F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R12Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —COMB, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R12F-substituted alkyl (e.g, C1-C8, C1-C6, or C1-C4alkyl), R12F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R12F-substituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R12F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R12F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R12F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R12Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R13is hydrogen, halogen (e.g., —F, —Cl, —Br, —I), —CX133, —CHX132, (e.g., —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, or —CH2I), —C(O)OH, —C(O)NH2, substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). X13is independently —F, —Cl, —Br, or —I. In embodiments, R13is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —C(O)OH, —C(O)NH2, R13E—R13E-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R13E-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R13E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R13E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R13E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R13E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R13is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —C(O)OH, —C(O)NH2, R13E-substituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R13E-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R13E-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R13E-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R13E-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R13E-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R13is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —C(O)OH, —C(O)NH2, unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). R13Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl3, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R13F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R13F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R13F-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R13F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R13F-substituted or unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R13F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R13Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl3, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —COMB, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R13F-substituted alkyl (e.g, C1-C8, C1-C6, or C1-C4alkyl), R13F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R13F-substituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R13F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R13F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R13F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R13Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl3, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R14is hydrogen, halogen (e.g., —F, —Cl, —Br, —I), —CX143, —CHX142, —CH2X14, —OCX143, —OCH2X14, —OCHX142, —N3, —CN, —SOn14R14D, —SOv14NR14AR14B, —NHC(O)NR14AR14B, —N(O)m14, —NR14AR14B, —C(O)R14C, —C(O)—OR14C, —C(O)NR14AR14B, —OR14D, —NR14ASO2R14D, —NR14AC(O)R14C, —NR14AC(O)OR14C, —NR14AOR14C(e.g., —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, or —NCH3OCH3), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). n14 is an integer from 0 to 4 (e.g. 0). m14 and v14 are independently an integer from 1 to 2. X14is independently —F, —Cl, —Br, or —I. In embodiments, R14is hydrogen. In embodiments, R14is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R14E-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R14E-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R14E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R14E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R14E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R14E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R14is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl3, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R14E-substituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R14E-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R14E-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R14E-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R14E-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R14E-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R14is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl3, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). R14Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R14F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R14F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R14F-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R14F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R14F-substituted or unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R14F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R14Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R14F-substituted alkyl (e.g, C1-C8, C1-C6, or C1-C4alkyl), R14F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R14F-substituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R14F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R14F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R14F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R14Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R15is hydrogen, halogen (e.g., —F, —Cl, —Br, —I), —CX153, —CHX152, —CH2X15, —OCX153, —OCH2X15, —OCHX152, —N3, —CN, —SOnl5R15D, —SOv15NR15AR15B, —NHC(O)NR15AR15B, —N(O)m15, —NR15AR15B, —C(O)R15C, —C(O)—OR15C, —C(O)NR15AR15B, —OR15D, —NR15ASO2R15D, —NR15AC(O)R15C, —NR15AC(O)OR15C, —NR15AOR15C(e.g, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, or —NCH3OCH3), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). n15 is an integer from 0 to 4 (e.g. 0). m15 and v15 are independently an integer from 1 to 2. X15is independently —F, —Cl, —Br, or —I. In embodiments, R15is hydrogen. In embodiments, R15is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R15E-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R15E-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R15E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R15E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R15E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R15E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R15is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R15E-substituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R15E-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R15E-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R15E-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R15E-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R15E-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R15is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). R15Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R15F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R15F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R15F-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R15F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R15F-substituted or unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R15F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R15Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R15F-substituted alkyl (e.g, C1-C8, C1-C6, or C1-C4alkyl), R15F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R15F-substituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R15F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R15F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R15F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R15Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R16is hydrogen, halogen (e.g., —F, —Cl, —Br, —I), —CX163, —CHX162, —CH2X16, —OCX163, —OCH2X16, —OCHX162, —N3, —CN, —SOn16R16D, —SOv16NR16AR16B, —NHC(O)NR16AR16B, —N(O)m16, —NR16AR16B, —C(O)R16C, —C(O)—OR16C, —C(O)NR16AR16B, —OR16D, —NR16ASO2R16D, —NR16AC(O)R16C, —NR16AC(O)OR16C, —NR16AOR16C(e.g., —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, or —NCH3OCH3), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). n16 is an integer from 0 to 4 (e.g. 0). m16 and v16 are independently an integer from 1 to 2. X16is independently —F, —Cl, —Br, or —I. In embodiments, R16is hydrogen. In embodiments, R16is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R16E-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R16E-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R16E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R16E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R16E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R16E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R16is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl3, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R16E-substituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R16E-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R16E-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R16E-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R16E-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R16E-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R16is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl3, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). R16Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl3, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R16F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R16F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R16F-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R16F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R16F-substituted or unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R16F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R16Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R16F-substituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R16F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R16F-substituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R16F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R16F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R16F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R16Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R17is hydrogen, halogen (e.g., —F, —Cl, —Br, —I), —CX173, —CHX172, —CH2X17, —OCX173, —OCH2X17, —OCHX172, —N3, —CN, —SOn17R17D, —SOv17NR17AR17B, —NHC(O)NR17AR17B, —N(O)m17, —NR17AR17B, —C(O)R17C, —C(O)—OR17C, —C(O)NR17AR17B, —OR17D, —NR17ASO2R17D, —NR17AC(O)R17C, —NR17AC(O)OR17C, —NR17AOR17C(e.g., —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, or —NCH3OCH3), substituted (e.g, substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). n17 is an integer from 0 to 4 (e.g. 0). m17 and v17 are independently an integer from 1 to 2. X17is independently —F, —Cl, —Br, or —I. In embodiments, R17is hydrogen. In embodiments, R17is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CH2Cl, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R17E-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R17E-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R17E-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R17E-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R17E-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R17E-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R17is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, R17E-substituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R17E-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R17E-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R17E-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R17E-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R17E-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, R17is hydrogen, —F, —Cl, —Br, —I, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, —N3, —CN, —SH, —SCH3, —SO2H, —SO2CH3, —SO2NH2, —SO2NHCH3, —NHC(O)NH2, —NHC(O)NHCH3, —NO2, —NH2, —NHCH3, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —C(O)NHCH3, —OH, —OCH3, —NHSO2H, —NHSO2CH3, —NHC(O)H, —NCH3C(O)H, —NHC(O)OH, —NCH3C(O)OH, —NHOH, —NCH3OH, —NCH3OCH3, unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). R17Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R17F-substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), R17F-substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R17F-substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R17F-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R17F-substituted or unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R17F-substituted or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R17Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —COMB, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, R17F-substituted alkyl (e.g, C1-C8, C1-C6, or C1-C4alkyl), R17F-substituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), R17F-substituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), R17F-substituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), R17F-substituted aryl (e.g., C6-C10, C10aryl, or phenyl), or R17F-substituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). In embodiments, R17Eis independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10, C10aryl, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). Each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12C, R12D, R14A, R14B, R14C, R14D, R15A, R15B, R15C, R15D, R16A, R16B, R16C, R16D, R17A, R17B, R17C, and R17Dare independently hydrogen, —CX3, —CHX2, —CH2X (e.g., —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I), —COOH, —CONH2, substituted (e.g, substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted alkyl (e.g., C1-C20, C1-C20, C1-C8, C1-C6, C1-C4, or C1-C2), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or substituted (e.g., substituted with a substituent group, a size-limited substituent group, or lower substituent group) or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). X is independently —F, —Cl, —Br, or —I. In embodiments, each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12C, R12D, R14A, R14B, R14C, R14D, R15A, R15B, R15C, R15D, R16A, R16B, R16C, R16D, R17A, R17B, R17C, and R17Dare independently hydrogen, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —COOH, —CONH2, R18-substituted or unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R18-substituted or unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R18-substituted or unsubstituted cycloalkyl (e.g., C3-C10, C3-C85, C3-C6, C4-C6, or C5-C6), R18-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R18-substituted or unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R18-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12C, R12D, R14A, R14B, R14C, R14D, R15A, R15B, R15C, R15D, R16A, R16B, R16C, R16D, R17A, R17B, R17C, and R17Dare independently hydrogen, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —COOH, —CONH2, R18-substituted alkyl (e.g, C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), R18-substituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), R18-substituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), R18-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), R18-substituted aryl (e.g., C6-C12, C6-C10, or phenyl), or R18-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12C, R12D, R14A, R14B, R14C, R14D, R15A, R15B, R15C, R15D, R16A, R16B, R16C, R16D, R17A, R17B, R17C, and R17Dare independently hydrogen, —CF3, —CHF2, —CH2F, —CCl3, —CHCl2, —CH2Cl, —CBr3, —CHBr2, —CH2Br, —CI3, —CHI2, —CH2I, —COOH, —CONH2, unsubstituted alkyl (e.g., C1-C20, C1-C12, C1-C8, C1-C6, C1-C4, or C1-C2), unsubstituted heteroalkyl (e.g., 2 to 20 membered, 2 to 12 membered, 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4 to 5 membered), unsubstituted cycloalkyl (e.g., C3-C10, C3-C8, C3-C6, C4-C6, or C5-C6), unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), unsubstituted aryl (e.g., C6-C12, C6-C10, or phenyl), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12C, R12D, R14A, R14B, R14C, R14D, R15A, R15B, R15C, R15D, R16A, R16B, R16C, R16D, R17A, R17B, R17C, and R17Dare independently hydrogen. Each R1Aand R1B, R2Aand R2B, R3Aand R3B, R4Aand R4B, R5Aand R5B, R6Aand R6B, R7Aand R7B, R8Aand R8B, R9Aand R9B, R10Aand R10B, R11Aand R11B, R12Aand R12B, R14Aand R14B, R15Aand R15B, R16Aand R16B, and R17Aand R17Btogether with nitrogen attached thereto may be joined to form R18-substituted or unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), or R18-substituted or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). Each R1Aand R1B, R2Aand R2B, R3Aand R3B, R4Aand R4B, R5Aand R5B, R6Aand R6B, R7Aand R7B, R8Aand R8B, R9Aand R9B, R10Aand R10B, R11Aand R11B, R12Aand R12B, R14Aand R14B, R15Aand R15B, R16Aand R16B, and R17Aand R17Btogether with nitrogen attached thereto may be joined to form R18-substituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), or R18-substituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). Each R1Aand R1B, R2Aand R2B, R3Aand R3B, R4Aand R4B, R5Aand R5B, R6Aand R6B, R7Aand R7B, R8Aand R8B, R9Aand R9B, R10Aand R10B, R11Aand R11B, R12Aand R12B, R14Aand R14B, R15Aand R15B, R16Aand R16B, and R17Aand R17Btogether with nitrogen attached thereto may be joined to form unsubstituted heterocycloalkyl (e.g., 3 to 10 membered, 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), or unsubstituted heteroaryl (e.g., 5 to 12 membered, 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered). In embodiments, each R1Aand R1B, R2Aand R2B, R3Aand R3B, R4Aand R4B, R5Aand R5B, R6Aand R6B, R7Aand R7B, R8Aand R8B, R9Aand R9B, R10Aand R10B, R11Aand R11B, R12Aand R12B, R14Aand R14B, R15Aand R15B, R16Aand R16B, and R17Aand R17Btogether with nitrogen attached thereto may be joined to form R18-substituted or unsubstituted pyridyl. In embodiments, each R1Aand R1B, R2Aand R2B, R3Aand R3B, R4Aand R4B, R5Aand R5B, R6Aand R6B, R7Aand R7B, R8Aand R8B, R9Aand R9B, R10Aand R10B, R11Aand R11B, R12Aand R12B, R14Aand R14B, R15Aand R15B, R16Aand R16B, and R17Aand R17Btogether with nitrogen attached thereto may be joined to form R18-substituted or unsubstituted piperidinyl. In embodiments, each R1Aand R1B, R2Aand R2B, R3Aand R3B, R4Aand R4B, R5Aand R5B, R6Aand R6B, R7Aand R7B, R8Aand R8B, R9Aand R9B, R10Aand R10B, R11Aand R11B, R12Aand R12B, R14Aand R14B, R15Aand R15B, R16Aand R16B, and R17Aand R17Btogether with nitrogen attached thereto may be joined to form R18-substituted or unsubstituted morpholinyl. In embodiments, each R1Aand R1B, R2Aand R2B, R3Aand R3B, R4Aand R4B, R5Aand R5B, R6Aand R6B, R7Aand R7B, R8Aand R8B, R9Aand R9B, R10Aand R10B, R11Aand R11B, R12Aand R12B, R14Aand R14B, R15Aand R15B, R16Aand R16B, and R17Aand R17Bjoined to form R18-substituted or unsubstituted pyrrolyl. In embodiments, each R1Aand R1B, R2Aand R2B, R3Aand R3B, R4Aand R4B, R5Aand R5B, R6Aand R6B, R7Aand R7B, R8Aand R8B, R9Aand R9B, R10Aand R10B, R11Aand R11B, R12Aand R12B, R14Aand R14B, R15Aand R15B, R16Aand R16B, and R17Aand R17Btogether with nitrogen attached thereto may be joined to form R18-substituted or unsubstituted pyrimidinyl. R1F, R2F, R3F, R4F, R5F, R6F, R7F, R8F, R9F, R10F, R11F, R12F, R13F, R14F, R15F, R16F, R17F, R18and R19Fare independently oxo, halogen, —CF3, —CCl3, —CBr3, —CI3, —CHF2, —CHCl2, —CHBr2, —CHI2, —CH2F, —CH2Cl, —CH2Br, —CH2I, —CN, —N3, —OH, —NH2, —COOH, —CONH2, —NO2, —SH, —SCH3, —SO3H, —SO4H, —SO2NH2, —NHNH2, —ONH2, —NHC(O)NHNH2, —NHC(O)NH2, —NHSO2H, —NHC(O)H, —NHC(O)OH, —NHOH, —OCF3, —OCCl3, —OCBr3, —OCI3, —OCHF2, —OCHCl2, —OCHBr2, —OCHI2, —OCH2F, —OCH2Cl, —OCH2Br, —OCH2I, unsubstituted alkyl (e.g., C1-C8, C1-C6, or C1-C4alkyl), unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, or 2 to 4 membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, or C5-C6cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, or 5 to 6 membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C10aryl, C10aryl or phenyl), or unsubstituted heteroaryl (e.g., 5 to 10 membered, 5 to 9 membered, or 5 to 6 membered heteroaryl). X, X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, X13, X14, X15, X16, and X17are independently —F, —Cl, —Br, or —I. In embodiments, X is —F. In embodiments, X is —Cl. In embodiments, X is —Br. In embodiments, X is —I. In embodiments, X1is —F. In embodiments, X1is —Cl. In embodiments, X1is —Br. In embodiments, X1is —I. In embodiments, X1is —F. In embodiments, X1is —Cl. In embodiments, X1is —Br. In embodiments, X1is —I. In embodiments, X2is —F. In embodiments, X2is —Cl. In embodiments, X2is —Br. In embodiments, X2is —I. In embodiments, X3is —F. In embodiments, X3is —Cl. In embodiments, X3is —Br. In embodiments, X3is —I. In embodiments, X4is —F. In embodiments, X4is —Cl. In embodiments, X4is —Br. In embodiments, X4is —I. In embodiments, X5is —F. In embodiments, X5is —Cl. In embodiments, X5is —Br. In embodiments, X5is —I. In embodiments, X6is —F. In embodiments, X6is —Cl. In embodiments, X6is —Br. In embodiments, X6is —I. In embodiments, X7is —F. In embodiments, X7is —Cl. In embodiments, X7is —Br. In embodiments, X7is —I. In embodiments, X8is —F. In embodiments, X8is —Cl. In embodiments, X8is —Br. In embodiments, X8is —I. In embodiments, X9is —F. In embodiments, X9is —Cl. In embodiments, X9is —Br. In embodiments, X9is —I. In embodiments, X10is —F. In embodiments, X10is —Cl. In embodiments, X10is —Br. In embodiments, X10is —I. In embodiments, X11is —F. In embodiments, X11is —Cl. In embodiments, X11is —Br. In embodiments, X11is —I. In embodiments, X12is —F. In embodiments, X12is —Cl. In embodiments, X12is —Br. In embodiments, X12is —I. In embodiments, X13is —F. In embodiments, X13is —Cl. In embodiments, X13is —Br. In embodiments, X13is —I. In embodiments, X14is —F. In embodiments, X14is —Cl. In embodiments, X14is —Br. In embodiments, X14is —I. In embodiments, X15is —F. In embodiments, X15is —Cl. In embodiments, X15is —Br. In embodiments, X15is —I. In embodiments, X16is —F. In embodiments, X16is —Cl. In embodiments, X16is —Br. In embodiments, X16is —I. In embodiments, X17is —F. In embodiments, X17is —Cl. In embodiments, X17is —Br. In embodiments, X17is —I. n1, n2, n3, n4, n5, n6, n7, n8, n9, n10, n12, n14, n15, n16 and n17 are independently an integer from 0 to 4 (e.g. 0). In embodiments, n1 is 0. In embodiments, n1 is 1. In embodiment, n1 is 2. In embodiments, n1 is 3. In embodiment, n1 is 4. In embodiments, n2 is 0. In embodiments, n2 is 1. In embodiment, n2 is 2. In embodiments, n2 is 3. In embodiment, n2 is 4. In embodiments, n3 is 0. In embodiments, n3 is 1. In embodiment, n3 is 2. In embodiments, n3 is 3. In embodiment, n3 is 4. In embodiments, n4 is 0. In embodiments, n4 is 1. In embodiment, n4 is 2. In embodiments, n4 is 3. In embodiment, n4 is 4. In embodiments, n5 is 0. In embodiments, n5 is 1. In embodiment, n5 is 2. In embodiments, n5 is 3. In embodiment, n5 is 4. In embodiments, n6 is 0. In embodiments, n6 is 1. In embodiment, n6 is 2. In embodiments, n6 is 3. In embodiment, n6 is 4. In embodiments, n7 is 0. In embodiments, n7 is 1. In embodiment, n7 is 2. In embodiments, n7 is 3. In embodiment, n7 is 4. In embodiments, n8 is 0. In embodiments, n8 is 1. In embodiment, n8 is 2. In embodiments, n8 is 3. In embodiment, n8 is 4. In embodiments, n9 is 0. In embodiments, n9 is 1. In embodiment, n9 is 2. In embodiments, n9 is 3. In embodiment, n9 is 4. In embodiments, n10 is 0. In embodiments, n10 is 1. In embodiment, n10 is 2. In embodiments, n10 is 3. In embodiment, n10 is 4. In embodiments, n11 is 0. In embodiments, n11 is 1. In embodiment, n11 is 2. In embodiments, n11 is 3. In embodiment, n11 is 4. In embodiments, n12 is 0. In embodiments, n12 is 1. In embodiment, n12 is 2. In embodiments, n12 is 3. In embodiment, n12 is 4. In embodiments, n14 is 0. In embodiments, n14 is 1. In embodiment, n14 is 2. In embodiments, n14 is 3. In embodiment, n14 is 4. In embodiments, n15 is 0. In embodiments, n15 is 1. In embodiment, n15 is 2. In embodiments, n15 is 3. In embodiment, n15 is 4. In embodiments, n16 is 0. In embodiments, n16 is 1. In embodiment, n16 is 2. In embodiments, n16 is 3. In embodiment, n16 is 4. In embodiments, n17 is 0. In embodiments, n17 is 1. In embodiment, n17 is 2. In embodiments, n17 is 3. In embodiment, n17 is 4. m1, m2, m3, m4, m5, m6, m7, m8, m9, m10, m11, m12, m14, m15, m16, and m17 are independently an integer from 1 to 2. In embodiments, m1 is 1. In embodiment, m1 is 2. In embodiments, m2 is 1. In embodiment, m2 is 2. In embodiments, m3 is 1. In embodiment, m3 is 2. In embodiments, m4 is 1. In embodiment, m4 is 2. In embodiments, m5 is 1. In embodiment, m5 is 2. In embodiments, m6 is 1. In embodiment, m6 is 2. In embodiments, m7 is 1. In embodiment, m7 is 2. In embodiments, m8 is 1. In embodiment, m8 is 2. In embodiments, m9 is 1. In embodiment, m9 is 2. In embodiments, m10 is 1. In embodiment, m10 is 2. In embodiments, m11 is 1. In embodiment, m11 is 2. In embodiments, m12 is 1. In embodiment, m12 is 2. In embodiments, m14 is 1. In embodiment, m14 is 2. In embodiments, m15 is 1. In embodiment, m15 is 2. In embodiments, m16 is 1. In embodiment, m16 is 2. In embodiments, m17 is 1. In embodiment, m17 is 2. v1, v2, v3, v4, v5, v6, v7, v8, v9, v10, v11, v12, v14, v15, v16 and v17 are independently an integer from 1 to 2. In embodiments, v1 is 1. In embodiment, v1 is 2. In embodiments, v2 is 1. In embodiment, v2 is 2. In embodiments, v3 is 1. In embodiment, v3 is 2. In embodiments, v4 is 1. In embodiment, v4 is 2. In embodiments, v5 is 1. In embodiment, v5 is 2. In embodiments, v6 is 1. In embodiment, v6 is 2. In embodiments, v7 is 1. In embodiment, v7 is 2. In embodiments, v8 is 1. In embodiment, v8 is 2. In embodiments, v9 is 1. In embodiment, v9 is 2. In embodiments, v10 is 1. In embodiment, v10 is 2. In embodiments, v11 is 1. In embodiment, v11 is 2. In embodiments, v12 is 1. In embodiment, v12 is 2. In embodiments, v14 is 1. In embodiment, v14 is 2. In embodiments, v15 is 1. In embodiment, v15 is 2. In embodiments, v16 is 1. In embodiment, v16 is 2. In embodiments, v17 is 1. In embodiment, v17 is 2. In embodiment, v17 is 2. In embodiments, when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH3. In embodiments, when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH2CH3. In embodiments, when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH3. In embodiments, when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH2CH3. In embodiments, when L1is —S— and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH3. In embodiments, when L1is —S—, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH2CH3. In embodiments, when L1is —S— and R1is —OH, then R6is not —CH3. In embodiments, when L1is —S— and R1is —OH, then R6is not —CH2CH3. In embodiments, when L1is —S— or —O—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH3. In embodiments, when L1is —S— or —O, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH2CH3. In embodiments, R6is not —CH3. In embodiments, R6is not —CH2CH3. In embodiments, R6is not —CH3. In embodiments, R6is not substituted or unsubstituted C1-C3alkyl. In embodiments, R6is not unsubstituted C1-C3alkyl. In embodiments, when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R8is not —CH3. In embodiments, when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R8is not —CH2CH3. In embodiments, when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R8is not —CH3. In embodiments, when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R8is not —CH2CH3. In embodiments, when L1is —S— and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R8is not —CH3. In embodiments, when L1is —S—, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R8is not —CH2CH3. In embodiments, when L1is —S— and R1is —OH, then R8is not —CH3. In embodiments, when L1is —S— and R1is —OH, then R8is not —CH2CH3. In embodiments, when L1is —S— or —O—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R8is not —CH3. In embodiments, when L1is —S— or —O, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R8is not —CH2CH3. In embodiments, R8is not —CH3. In embodiments, R8is not —CH2CH3. In embodiments, R8is not —CH3. In embodiments, R8is not substituted or unsubstituted C1-C3alkyl. In embodiments, R8is not unsubstituted C1-C3alkyl. In embodiments, when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH3. In embodiments, when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH2CH3. In embodiments, when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH3. In embodiments, when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH2CH3. In embodiments, when L1is —S— and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH3. In embodiments, when L1is —S— and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH2CH3. In embodiments, when L1is —S— and R1is —OH, then R10is not —CH3. In embodiments, when L1is —S— and R1is —OH, then R10is not —CH2CH3. In embodiments, when L1is —S— or —O—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH3. In embodiments, when L1is —S— or —O, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH2CH3. In embodiments, R10is not —CH3. In embodiments, R10is not —CH2CH3. In embodiments, R10is not —CH3. In embodiments, R10is not substituted or unsubstituted C1-C3alkyl. In embodiments, R10is not unsubstituted C1-C3alkyl. In embodiments, when L1is —S—, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH3. In embodiments, when L1is —S—, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH2CH3. In embodiments, when L1is —S—, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH3. In embodiments, when L1is —S—, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH2CH3. In embodiments, when L1is —S—, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH3. In embodiments, when L1is —S— and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH2CH3. In embodiments, when L1is —S— and R5is —OH, then R6is not —CH3. In embodiments, when L1is —S— and R5is —OH, then R6is not —CH2CH3. In embodiments, when L1is —S— or —O—, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH3. In embodiments, when L1is —S— or —O, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH2CH3. In embodiments, R6is not —CH3. In embodiments, R6is not —CH2CH3. In embodiments, R6is not —CH3. In embodiments, R6is not substituted or unsubstituted C1-C3alkyl. In embodiments, R6is not unsubstituted C1-C3alkyl. In embodiments, when L1is —S—, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R8is not —CH3. In embodiments, when L1is —S—, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R8is not —CH2CH3. In embodiments, when L1is —S—, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R8is not —CH3. In embodiments, when L1is —S—, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R8is not —CH2CH3. In embodiments, when L1is —S—, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R8is not —CH3. In embodiments, when L1is —S— and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R8is not —CH2CH3. In embodiments, when L1is —S— and R5is —OH, then R8is not —CH3. In embodiments, when L1is —S— and R5is —OH, then R8is not —CH2CH3. In embodiments, when L1is —S— or —O—, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R8is not —CH3. In embodiments, when L1is —S— or —O, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R8is not —CH2CH3. In embodiments, R8is not —CH3. In embodiments, R8is not —CH2CH3. In embodiments, R8is not —CH3. In embodiments, R8is not substituted or unsubstituted C1-C3alkyl. In embodiments, R8is not unsubstituted C1-C3alkyl. In embodiments, when L1is —S—, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH3. In embodiments, when L1is —S—, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH2CH3. In embodiments, when L1is —S—, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH3. In embodiments, when L1is —S—, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH2CH3. In embodiments, when L1is —S— and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH3. In embodiments, when L1is —S—, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH2CH3. In embodiments, when L1is —S— and R5is —OH, then R10is not —CH3. In embodiments, when L1is —S— and R5is —OH, then R10is not —CH2CH3. In embodiments, when L1is —S— or —O—, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH3. In embodiments, when L1is —S— or —O—, R5is —OH, and R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH2CH3. In embodiments, R10is not —CH3. In embodiments, R10is not —CH2CH3. In embodiments, R10is not —CH3. In embodiments, R10is not substituted or unsubstituted C1-C3alkyl. In embodiments, R10is not unsubstituted C1-C3alkyl. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R7, R8and R9are hydrogen, then R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R1is —OH, and R7, R8and R9are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R1is —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R7and R9are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R7and R8are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R8and R9are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R7is hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R8is hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R9is hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R7and R9are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R7and R8are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R8and R9are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R7is hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R8is hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R9is hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R5is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is a bond, R5is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R5is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R5is —OH or —OCH3, and R7, R8and R9are hydrogen, then R10is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R5is —OH, and R7, R8and R9are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R5is —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R5is —OH or —OCH3, and R7and R9are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R5is —OH or —OCH3, and R7and R8are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R5is —OH or —OCH3, and R8and R9are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R5is —OH or —OCH3, and R7is hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R5is —OH or —OCH3, and R8is hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R5is —OH or —OCH3, and R9is hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is a bond, R5is —OH or —OCH3, and R7and R9are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is a bond, R5is —OH or —OCH3, and R7and R8are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is a bond, R5is —OH or —OCH3, and R8and R9are hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is a bond, R5is —OH or —OCH3, and R7is hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is a bond, R5is —OH or —OCH3, and R8is hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R1and R2together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is a bond, R5is —OH or —OCH3, and R9is hydrogen, then R6or R10is not —C(O)NH2. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R1is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is —S— or —S(O)2—, R1is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R1is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R1is —OH, and R6, R7, R9and R10are hydrogen, then R8is not —Cl. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R1is —OH, and R6, R7, R9and R10are hydrogen, then R8is not-CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S—, R1is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S—, R1is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R1is —OH, and R6and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R1is —OH, and R7and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R1is —OH, and R6and R7are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R1is —OH, and R7and R9are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R1is —OH, and R6, R7and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R1is —OH, and R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R1is —OH, and R6, R7and R9are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R5is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is —S— or —S(O)2—, R5is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R5is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R5is —OH, and R6, R7, R9and R10are hydrogen, then R8is not —Cl. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R5is —OH, and R6, R7, R9and R10are hydrogen, then R8is not-CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S—, R5is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S—, R5is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R5is —OH, and R6and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R5is —OH, and R7and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R5is —OH, and R6and R7are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R5is —OH, and R7and R9are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R5is —OH, and R6, R7and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R5is —OH, and R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R5is —OH, and R6, R7and R9are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R1is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is —S(O)2—, R1is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R1is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R1is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R1is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not unsubstituted C1-C3alkyl. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R1is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not substituted or unsubstituted C1-C3alkyl. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R1is —OCH3, and R6and R10are hydrogen, then R8is not hydrogen or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R1is —OCH3, and R6, and R7are hydrogen, then R8is not hydrogen or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R1is —OCH3, and R6and R9are hydrogen, then R8is not hydrogen or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R1is —OCH3, and R7and R9are hydrogen, then R8is not hydrogen or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R1is —OCH3, and R9and R10are hydrogen, then R8is not hydrogen or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R5is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is —S(O)2—, R5is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R5is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R5is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R5is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not unsubstituted C1-C3alkyl. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R5is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not substituted or unsubstituted C1-C3alkyl. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R5is —OCH3, and R6and R10are hydrogen, then R8is not hydrogen or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R5is —OCH3, and R6, and R7are hydrogen, then R8is not hydrogen or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R5is —OCH3, and R6and R9are hydrogen, then R8is not hydrogen or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R5is —OCH3, and R7and R9are hydrogen, then R8is not hydrogen or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R5is —OCH3, and R9and R10are hydrogen, then R8is not hydrogen or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not —Cl. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not halogen. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not unsubstituted C1-C3alkyl. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not substituted or unsubstituted C1-C3alkyl. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NH—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R6and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R6and R7are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R6and R9are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R7and R9are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R7and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R6, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R6, R7, and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R6, R7, and R9are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not —Cl. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not halogen. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not unsubstituted C1-C3alkyl. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not substituted or unsubstituted C1-C3alkyl. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NH—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R6and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R6and R7are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R6and R9are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R7and R9are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R7and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R6, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R6, R7, and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R5is —OH or —OCH3, and R6, R7, and R9are hydrogen, then R8is not hydrogen, —Cl or —CH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6and R7are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6and R9are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7and R9are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not halogen. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not unsubstituted C1-C4alkyl. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not substituted or unsubstituted C1-C4alkyl. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7and R9are hydrogen, then R8is not —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R7and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6and R7are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6and R9are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R7and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R7and R9are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not halogen. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not unsubstituted C1-C4alkyl. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not substituted or unsubstituted C1-C4alkyl. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R7and R9are hydrogen, then R8is not —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6and R7are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7and R9are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not halogen. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not unsubstituted C1-C4alkyl. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not substituted or unsubstituted C1-C4alkyl. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R7and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6and R7are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R7and R9are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R7and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not halogen. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not unsubstituted C1-C4alkyl. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not substituted or unsubstituted C1-C4alkyl. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH, and R6, R8and R10are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R8and R10are hydrogen, then R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not halogen. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not unsubstituted C1-C4alkyl. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not substituted or unsubstituted C1-C4alkyl. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R8and R10are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6and R10are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6and R8are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH, and R6, R8and R10are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R8and R10are hydrogen, then R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not halogen. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not unsubstituted C1-C4alkyl. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not substituted or unsubstituted C1-C4alkyl. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R8and R10are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6and R10are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6and R8are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH, and R7, R8and R9are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7, R8and R9are hydrogen, then R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R8and R9are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7and R9are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7and R8are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not halogen. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —OH, or —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not unsubstituted C1-C4alkyl. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not substituted or unsubstituted C1-C4alkyl. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH, and R7, R8and R9are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R7, R8and R9are hydrogen, then R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R8and R9are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R7and R9are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R7and R8are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not halogen. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —OH, or —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not unsubstituted C1-C4alkyl. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R5is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not substituted or unsubstituted C1-C4alkyl. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R1is —OH or —OCH3, then at least one of R6, R7and R8are not —OCH3, or at least one of R8, R9and R10are not —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is —NHC(O)—, and R1is —OH or —OCH3, then at least one of R6, R7and R8are not —OCH3, or at least one of R8, R9and R10are not —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R1is —OCH3, then at least one of R6, R7and R8are not —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R1is —OH, then at least one of R7and R8are not —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R1is —OH or —OCH3, then at least one of R6and R8are not —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R1is —OH or —OCH3, then at least one of R6and R7are not —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R1is —OH or —OCH3, then at least one of R9and R10are not —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R1is —OH or —OCH3, then at least one of R8and R10are not —OCH3. In embodiments, when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R1is —OH or —OCH3, then at least one of R8and R9are not —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R5is —OH or —OCH3, then at least one of R6, R7and R8are not —OCH3, or at least one of R8, R9and R10are not —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form substituted or unsubstituted phenyl, L1is —NHC(O)—, and R5is —OH or —OCH3, then at least one of R6, R7and R8are not —OCH3, or at least one of R8, R9and R10are not —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R5is —OCH3, then at least one of R6, R7and R8are not —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R5is —OH, then at least one of R7and R8are not —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R5is —OH or —OCH3, then at least one of R6and R8are not —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R5is —OH or —OCH3, then at least one of R6and R7are not —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R5is —OH or —OCH3, then at least one of R9and R10are not —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R5is —OH or —OCH3, then at least one of R8and R10are not —OCH3. In embodiments, when R1and R2together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R5is —OH or —OCH3, then at least one of R8and R9are not —OCH3. In embodiments, the compound is: In embodiments, the compound is a compound described herein (e.g., in an aspect, embodiment, example, table, figure, scheme, appendix, or claim). III. Pharmaceutical Compositions Also provided herein are pharmaceutical formulations. In embodiments, the pharmaceutical formulation includes a compound (e.g. formula (I), (IIA), (IIB), (III), (IV), (V), (VI), (VII), or (VIII)) described above (including all embodiments thereof) and a pharmaceutically acceptable excipient. In embodiments, the pharmaceutical composition includes a compound (e.g. formula (I), (IIA), (IIB), (III), (IV), (V), (VI), (VII), or (VIII))) described above that inhibits poly(ADP-ribose) Glycohydrolase (PARG) in a cancer cell. In embodiments, the compound has a half maximal inhibitory concentration (IC50) against PARG less than about 100 μM. In embodiments, the compound has IC50against PARG less than about 10 μM. In embodiments, the compound has IC50against PARG less than about 1 μM. In embodiments, the compound has IC50against PARG less than about 500 nM. In embodiments, the compound has IC50against PARG less than about 400 nM. In embodiments, the compound has IC50against PARG less than about 300 nM. In embodiments, the compound has IC50against PARG less than about 200 nM. In embodiments, the compound has IC50against PARG less than about 100 nM. In embodiments, the compound has IC50against PARG less than about 90 nM. In embodiments, the compound has IC50against PARG less than about 80 nM. In embodiments, the compound has IC50against PARG less than about 70 nM. In embodiments, the compound has IC50against PARG less than about 60 nM. In embodiments, the compound has IC50against PARG less than about 50 nM. In embodiments, the compound has IC50against PARG less than about 40 nM. In embodiments, the compound has IC50against PARG less than about 30 nM. In embodiments, the compound has IC50against PARG less than about 20 nM. In embodiments, the compound has an inhibitory concentration against PARG less than about 10 nM. In embodiments, the pharmaceutical composition includes a compound of: The pharmaceutical compositions described herein, including embodiments thereof may be used in the treatment of cancers. In embodiments, the pharmaceutical compositions described herein, including embodiments thereof may be used in the treatment of solid and blood tumors, including ovarian cancer, breast cancer (e.g. triple-negative breast cancer), lung cancer (e.g. small cell or non-small cell lung cancer), leukemia (e.g. AML or CML), lymphoma, pancreatic cancer, kidney cancer, uterine cancer, colon cancer (e.g. colon carcinoma), fallopian tube cancer, melanoma, liver cancer, sarcoma, multiple myeloma, brain cancer (e.g. glioblastoma), bladder cancer, esophagus cancer, gastric cancer, head and neck cancer, cholangiocarcinoma, mesothelioma and prostate cancer. In embodiments, the pharmaceutical compositions described herein, including embodiments thereof may be used in the treatment of breast cancer, e.g. triple-negative breast cancer. In embodiments, the pharmaceutical compositions described herein, including embodiments thereof may be used in the treatment of ovarian cancer. In embodiments, the pharmaceutical compositions described herein, including embodiments thereof may be used in the treatment of non-small cell lung cancer. In embodiments, the pharmaceutical compositions described herein, including embodiments thereof may be used in the treatment of pancreatic cancer. In embodiments, the pharmaceutical compositions described herein, including embodiments thereof may be used in the treatment of glioblastoma. In embodiments, the pharmaceutical compositions described herein, including embodiments thereof may be used in the treatment of uterine cancer. In embodiments, the pharmaceutical compositions described herein, including embodiments thereof may be used in the treatment of prostate cancer. In embodiments, the pharmaceutical compositions described herein, including embodiments thereof may be used in the treatment of colon carcinoma. In embodiments, the pharmaceutical compositions described herein, including embodiments thereof may be used in the treatment of fallopian tube cancer. In embodiments, the pharmaceutical compositions described herein, including embodiments thereof may be used in the treatment of acute leukemia. In embodiments, the pharmaceutical composition includes a compound described herein (e.g., in an aspect, embodiment, example, table, figure, scheme, appendix, or claim) and a pharmaceutically acceptable excipient. 1. Formulations The pharmaceutical composition may be prepared and administered in a wide variety of dosage formulations. Compounds described may be administered orally, rectally, or by injection (e.g. intravenously, intramuscularly, intracutaneously, subcutaneously, intraduodenally, or intraperitoneally). For preparing pharmaceutical compositions from compounds described herein, pharmaceutically acceptable carriers can be either solid or liquid. Solid form preparations include powders, tablets, pills, capsules, cachets, suppositories, and dispersible granules. A solid carrier may be one or more substance that may also act as diluents, flavoring agents, binders, preservatives, tablet disintegrating agents, or an encapsulating material. In powders, the carrier may be a finely divided solid in a mixture with the finely divided active component. In tablets, the active component may be mixed with the carrier having the necessary binding properties in suitable proportions and compacted in the shape and size desired. The powders and tablets preferably contain from 5% to 70% of the active compound. Suitable carriers are magnesium carbonate, magnesium stearate, talc, sugar, lactose, pectin, dextrin, starch, gelatin, tragacanth, methylcellulose, sodium carboxymethylcellulose, a low melting wax, cocoa butter, and the like. The term “preparation” is intended to include the formulation of the active compound with encapsulating material as a carrier providing a capsule in which the active component with or without other carriers, is surrounded by a carrier, which is thus in association with it. Similarly, cachets and lozenges are included. Tablets, powders, capsules, pills, cachets, and lozenges can be used as solid dosage forms suitable for oral administration. For preparing suppositories, a low melting wax, such as a mixture of fatty acid glycerides or cocoa butter, is first melted and the active component is dispersed homogeneously therein, as by stirring. The molten homogeneous mixture is then poured into convenient sized molds, allowed to cool, and thereby to solidify. Liquid form preparations include solutions, suspensions, and emulsions, for example, water or water/propylene glycol solutions. For parenteral injection, liquid preparations can be formulated in solution in aqueous polyethylene glycol solution. Aqueous solutions suitable for oral use can be prepared by dissolving the active component in water and adding suitable colorants, flavors, stabilizers, and thickening agents as desired. Aqueous suspensions suitable for oral use can be made by dispersing the finely divided active component in water with viscous material, such as natural or synthetic gums, resins, methylcellulose, sodium carboxymethylcellulose, and other well-known suspending agents. Also included are solid form preparations that are intended to be converted, shortly before use, to liquid form preparations for oral administration. Such liquid forms include solutions, suspensions, and emulsions. These preparations may contain, in addition to the active component, colorants, flavors, stabilizers, buffers, artificial and natural sweeteners, dispersants, thickeners, solubilizing agents, and the like. The pharmaceutical preparation is preferably in unit dosage form. In such form the preparation is subdivided into unit doses containing appropriate quantities of the active component. The unit dosage form can be a packaged preparation, the package containing discrete quantities of preparation, such as packeted tablets, capsules, and powders in vials or ampoules. Also, the unit dosage form can be a capsule, tablet, cachet, or lozenge itself, or it can be the appropriate number of any of these in packaged form. The quantity of active component in a unit dose preparation may be varied or adjusted from 0.1 mg to 10000 mg according to the particular application and the potency of the active component. The composition can, if desired, also contain other compatible therapeutic agents. Some compounds may have limited solubility in water and therefore may require a surfactant or other appropriate co-solvent in the composition. Such co-solvents include: Polysorbate 20, 60, and 80; Pluronic F-68, F-84, and P-103; cyclodextrin; and polyoxyl 35 castor oil. Such co-solvents are typically employed at a level between about 0.01% and about 2% by weight. Viscosity greater than that of simple aqueous solutions may be desirable to decrease variability in dispensing the formulations, to decrease physical separation of components of a suspension or emulsion of formulation, and/or otherwise to improve the formulation. Such viscosity building agents include, for example, polyvinyl alcohol, polyvinyl pyrrolidone, methyl cellulose, hydroxy propyl methylcellulose, hydroxyethyl cellulose, carboxymethyl cellulose, hydroxy propyl cellulose, chondroitin sulfate and salts thereof, hyaluronic acid and salts thereof, and combinations of the foregoing. Such agents are typically employed at a level between about 0.01% and about 2% by weight. The pharmaceutical compositions may additionally include components to provide sustained release and/or comfort. Such components include high molecular weight, anionic mucomimetic polymers, gelling polysaccharides, and finely-divided drug carrier substrates. These components are discussed in greater detail in U.S. Pat. Nos. 4,911,920; 5,403,841; 5,212,162; and 4,861,760. The entire contents of these patents are incorporated herein by reference in their entirety for all purposes. The pharmaceutical composition may be intended for intravenous use. The pharmaceutically acceptable excipient can include buffers to adjust the pH to a desirable range for intravenous use. Many buffers including salts of inorganic acids such as phosphate, borate, and sulfate are known. 2. Effective Dosages The pharmaceutical composition may include compositions wherein the active ingredient is contained in a therapeutically effective amount, i.e., in an amount effective to achieve its intended purpose. The actual amount effective for a particular application will depend, inter alia, on the condition being treated. The dosage and frequency (single or multiple doses) of compounds administered can vary depending upon a variety of factors, including route of administration; size, age, sex, health, body weight, body mass index, and diet of the recipient; nature and extent of symptoms of the disease being treated; presence of other diseases or other health-related problems; kind of concurrent treatment; and complications from any disease or treatment regimen. Other therapeutic regimens or agents can be used in conjunction with the methods and compounds disclosed herein. As is well known in the art, therapeutically effective amounts for use in humans can also be determined from animal models. For example, a dose for humans can be formulated to achieve a concentration that has been found to be effective in animals. The dosage in humans can be adjusted by monitoring compounds effectiveness and adjusting the dosage upwards or downwards, as described above. Adjusting the dose to achieve maximal efficacy in humans based on the methods described above and other methods is well within the capabilities of the ordinarily skilled artisan. Dosages may be varied depending upon the requirements of the subject and the compound being employed. The dose administered to a subject, in the context of the pharmaceutical compositions presented herein, should be sufficient to effect a beneficial therapeutic response in the subject over time. The size of the dose also will be determined by the existence, nature, and extent of any adverse side effects. Generally, treatment is initiated with smaller dosages, which are less than the optimum dose of the compound. Thereafter, the dosage is increased by small increments until the optimum effect under circumstances is reached. Dosage amounts and intervals can be adjusted individually to provide levels of the administered compounds effective for the particular clinical indication being treated. This will provide a therapeutic regimen that is commensurate with the severity of the individual's disease state. Utilizing the teachings provided herein, an effective prophylactic or therapeutic treatment regimen can be planned that does not cause substantial toxicity and yet is entirely effective to treat the clinical symptoms demonstrated by the particular patient. This planning should involve the careful choice of active compound by considering factors such as compound potency, relative bioavailability, patient body weight, presence and severity of adverse side effects, preferred mode of administration, and the toxicity profile of the selected agent. 3. Toxicity The ratio between toxicity and therapeutic effect for a particular compound is its therapeutic index and can be expressed as the ratio between LD50(the amount of compound lethal in 50% of the population) and ED50(the amount of compound effective in 50% of the population). Compounds that exhibit high therapeutic indices are preferred. Therapeutic index data obtained from cell culture assays and/or animal studies can be used in formulating a range of dosages for use in humans. The dosage of such compounds preferably lies within a range of plasma concentrations that include the ED50with little or no toxicity. The dosage may vary within this range depending upon the dosage form employed and the route of administration utilized. See, e.g. Fingl et al. In: THE PHARMACOLOGICAL BASIS OF THERAPEUTICS, Ch. 1, p. 1, 1975. The exact formulation, route of administration, and dosage can be chosen by the individual physician in view of the patient's condition and the particular method in which the compound is used. When parenteral application is needed or desired, particularly suitable admixtures for the compounds included in the pharmaceutical composition may be injectable, sterile solutions, oily or aqueous solutions, as well as suspensions, emulsions, or implants, including suppositories. In particular, carriers for parenteral administration include aqueous solutions of dextrose, saline, pure water, ethanol, glycerol, propylene glycol, peanut oil, sesame oil, polyoxyethylene-block polymers, and the like. Ampoules are convenient unit dosages. Pharmaceutical admixtures suitable for use in the pharmaceutical compositions presented herein may include those described, for example, in Pharmaceutical Sciences (17th Ed., Mack Pub. Co., Easton, PA) and WO 96/05309, the teachings of both of which are hereby incorporated by reference. IV. Methods of Treatments Provided herein are methods of treating a cancer in a subject in need thereof, the method comprising administering an effective amount a compound (e.g. formula (I), (IIA), (IIB), (III), (IV), (V), (VI), (VII), or (VIII)) described herein. In embodiments, the cancer is ovarian cancer, breast cancer (e.g. triple-negative breast cancer), lung cancer (e.g. small cell or non-small cell lung cancer), leukemia (e.g. AML or CML), lymphoma, pancreatic cancer, kidney cancer, uterine cancer, colon cancer (e.g. colon carcinoma), fallopian tube cancer, melanoma, liver cancer, sarcoma, multiple myeloma, brain cancer (e.g. glioblastoma), bladder cancer, esophagus cancer, gastric cancer, head and neck cancer, cholangiocarcinoma, mesothelioma or prostate cancer. In embodiments, the cancer is breast cancer, e.g. triple-negative breast cancer. In embodiments, the cancer is ovarian cancer. In embodiments, the cancer is non-small cell lung cancer. In embodiments, the cancer is pancreatic cancer. In embodiments, the cancer is glioblastoma. In embodiments, the cancer is uterine cancer. In embodiments, the cancer is prostate cancer. In embodiments, the cancer is colon carcinoma. In embodiments, the cancer is fallopian tube cancer. In embodiments, the cancer is acute leukemia. In embodiments, the cancer is bladder cancer. In embodiments, the cancer is esophagus cancer. In embodiments, the cancer is gastric cancer. In embodiments, the cancer is head and neck cancer. In embodiments, the cancer is cholangiocarcinoma. In embodiments, the cancer is mesothelioma. In embodiments, the cancer is prostate cancer. In embodiments, the cancer is BRCA1-mutant TNBC. In embodiments, the cancer is BRCA2-mutant TNBC. In embodiments, the cancer is BRCA1-deficient TNBC. In embodiments, the cancer is BRCA2-deficient TNBC. In embodiments, the cancer is PARPi-resistance ovarian cancer (e.g., UWB1.289). In embodiments, the cancer is osteosarcoma. In embodiments, the method of treating cancer includes suppression or inhibition of PARylation and/or dePARylation in the tumor cells with defective DNA repair system. In embodiments, the method of treating cancer includes suppression or inhibition of dePARylation in the tumor cells by inhibiting dePARylation enzyme (PARG). In embodiments, the method of treating cancer includes inhibiting dePARylation enzyme (PARG) by using an effective amount of the PARG inhibitor (e.g., a compound described herein). In embodiments, the method of treating cancer includes suppression or reduction of dePARylation in the tumor cells by contacting the cancer or tumor cell with an effective amount of the PARG inhibitor. In embodiments, the method of treating cancer includes inhibiting dePARylation enzyme (PARG) by using effective amount of a compound (e.g. formula (I), (IIA), (IIB), (III), (IV), (V), (VI), (VII), or (VIII)) described herein (including all embodiments thereof). In embodiments, the method of treating cancer includes inhibiting dePARylation enzyme (PARG) in a cancer or tumor cell by contacting the cancer or tumor cell with the effective amount of a compound (e.g. formula (I), (IIA), (IIB), (III), (IV), (V), (VI), (VII), or (VIII)) described above (including all embodiments thereof). In embodiments, the tumor cell is a breast cancer cell, e.g., triple-negative breast cancer cell. In embodiments, the compound is: In embodiments, the methods of treating cancer described herein yield a suppression of tumor growth. The suppressed tumor growth may indicate the absence of toxicity symptoms (e.g. body weight loss). Those skilled in the art understand that body weight loss observed during cancer treatments is a result of toxicity associated with the treatment (e.g. killing of healthy tissue). Accordingly, the compounds described herein may provide effective therapeutic value without toxicity issues normally associated with cancer treatments. V. Other Aspects Embodiments P Embodiment P1. A method of treating cancer in a subject in need thereof, the method comprising administering to the subject an effective amount of a compound having a formula (I), wherein:L1is —CR11R12—, —NR13—, —O—, or —S—;R1is hydrogen, halogen, —CX13, —CHX12, —CH2X1, —OCX1C, —OCH2X1, —OCHX12, —N3, —CN, —SOn1R1D, —SOv1NR1AR1B, —NHC(O)NR1AR1B, —N(O)m1, —NR1AR1B, —C(O)R1C, C(O)—OR1C, —C(O)NR1AR1B, —OR1D, —NR1ASO2R1D, —NR1AC(O)R1C, —NR1AC(O)OR1C, —NR1AOR1C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R2is hydrogen, halogen, —CX23, —CHX22, —CH2X2, —OCX23, —OCH2X2, —OCHX22, —N3, —CN, —SOn2R2D, —SOv2NR2AR2B, —NHC(O)NR2AR2B, —N(O)m2, —NR2AR2B, —C(O)R2C, C(O)—OR2C, —C(O)NR2AR2B, —OR2D, —NR2ASO2R2D, —NR2AC(O)R2C, —NR2AC(O)OR2C, —NR2AOR2C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R3is hydrogen, halogen, —CX33, —CHX32, —CH2X3, —OCX33, —OCH2X3, —OCHX32, —N3, —CN, —SOn3R3D, —SOv3NR3AR3B, —NHC(O)NR3AR3B, —N(O)m3, —NR3AR3B, —C(O)R3C, C(O)—OR3C, —C(O)NR3AR3B, —OR3D, —NR3ASO2R3D, —NR3AC(O)R3C, —NR3AC(O)OR3C, —NR3AOR3C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4is hydrogen, halogen, —CX43, —CHX42, —CH2X4, —OCX43, —OCH2X4, —OCHX42, —N3, —CN, —SOn4R4D, —SOv4NR4AR4B, —NHC(O)NR4AR4B, —N(O)m4, —NR4AR4B, —C(O)R4C, C(O)—OR4C, —C(O)NR4AR4B, —OR4D, —NR4ASO2R4D, —NR4AC(O)R4C, —NR4AC(O)OR4C, —NR4AOR4C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R5is hydrogen, halogen, —CX53, —CHX52, —CH2X5, —OCX53, —OCH2X5, —OCHX52, —N3, —CN, —SOn5R5D, —SOv5NR5AR5B, —NHC(O)NR5AR5B, —N(O)m5, —NR5AR5B, —C(O)R5C, C(O)—OR5C, —C(O)NR5AR5B, —OR5D, —NR5ASO2R5D, —NR5AC(O)R5C, —NR5AC(O)OR5C, —NR5AOR5C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R6is hydrogen, halogen, —CX63, —CHX62, —CH2X6, —OCX63, —OCH2X6, —OCHX62, —N3, —CN, —SOn6R6D, —SOv6NR6AR6B, —NHC(O)NR6AR6B, —N(O)m6, —NR6AR6B, —C(O)R6C, C(O)—OR6C, —C(O)NR6AR6B, —OR6D, —NR6ASO2R6D, —NR6AC(O)R6C, —NR6AC(O)OR6C, —NR6AOR6C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R7is hydrogen, halogen, —CX73, —CHX72, —CH2X7, —OCX73, —OCH2X7, —OCHX72, —N3, —CN, —SOn7R7D, —SOv7NR7AR7B, —NHC(O)NR7AR7B, —N(O)m7, —NR7AR7B, —C(O)R7C, C(O)—OR7C, —C(O)NR7AR7B, —OR7D, —NR7ASO2R7D, —NR7AC(O)R7C, —NR7AC(O)OR7C, —NR7AOR7C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R8is hydrogen, halogen, —CX83, —CHX82, —CH2X8, —OCX83, —OCH2X8, —OCHX82, —N3, —CN, —SOn8R8D, —SOv8NR8AR8B, —NHC(O)NR8AR8B, —N(O)m8, —NR8AR8B, —C(O)R8C, C(O)—OR8C, —C(O)NR8AR8B, —OR8D, —NR8ASO2R8D, —NR8AC(O)R8C, —NR8AC(O)OR8C, —NR8AOR8C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R9is hydrogen, halogen, —CX93, —CHX92, —CH2X9, —OCX93, —OCH2X9, —OCHX92, —N3, —CN, —SOn9R9D, —SOv9NR9AR9B, —NHC(O)NR9AR9B, —N(O)m9, —NR9AR9B, —C(O)R9C, C(O)—OR9C, —C(O)NR9AR9B, —OR9D, —NR9ASO2R9D, —NR9AC(O)R9C, —NR9AC(O)OR9C, —NR9AOR9C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R10is hydrogen, halogen, —CX103, —CHX102, —CH2X10, —OCX103, —OCH2X10, —OCHX102, —N3, —CN, —SOn10R10D, —SOv10NR10AR10B, —NHC(O)NR10AR10B, —N(O)m10, —NR10AR10B, —C(O)R10C, —C(O)—OR10C, —C(O)NR10AR10B, —OR10D, —NR10ASO2R10D, —NR10AC(O)R10C, —NR10AC(O)OR10C, —NR10AOR10C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R11is hydrogen, halogen, —CX113, —CHX112, —CH2X11, —OCX113, —OCH2X11, —OCHX112, —N3, —CN, —SOn11R11D, —SOv11NR11AR11B, —NHC(O)NR11AR11B, —N(O)m11, —NR11AR11B, —C(O)R11C, —C(O)—OR11C, —C(O)NR11AR11B, —OR11D, —NR11ASO2R11D, —NR11AC(O)R11C, —NR11AC(O)OR11C, —NR11AOR11C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R12is hydrogen, halogen, —CX123, —CHX122, —CH2X12, —OCX123, —OCH2X12, —OCHX122, —N3, —CN, —SOnl2R12D, —SOv12NR12AR12B, —NHC(O)NR12AR12B, —N(O)m12, —NR12AR12B, —C(O)R12C, —C(O)—OR12C, —C(O)NR12AR12B, —OR12D, —NR12ASO2R12D, —NR12AC(O) R12C, —NR12AC(O)OR12C, —NR12AOR12C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R13is hydrogen, —CX133, —CHX132, —CH2X13, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12Cand R12Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R1and R2together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4and R5together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n1, n2, n3, n4, n5, n6, n7, n8, n9, n10, n11 and n12 are independently an integer from 0 to 4;m1, m2, m3, m4, m5, m6, m7, m8, m9, m10, m11, m12, v1, v2, v3, v4, v5, v6, v7, v8, v9, v10, v11 and v12 are independently an integer from 1 to 2; andX, X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, and X13are independently —F, —Cl, —Br, or —I,or a salt thereof. Embodiment P2. The method of Embodiment P1, wherein the compound has a formula (II): wherein:R14is hydrogen, halogen, —CX143, —CHX142, —CH2X14, —OCX143, —OCH2X14, —OCHX142, —N3, —CN, —SOn14R14D, —SOv14NR14AR14B, —NHC(O)NR14AR14B, —N(O)m14, —NR14AR14B, —C(O)R14C, —C(O)—OR14C, —C(O)NR14AR14B, —OR14D, —NR14ASO2R14D, —NR14AC(O) R14C, —NR14AC(O)OR14C, —NR14AOR14C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R15is hydrogen, halogen, —CX153, —CHX152, —CH2X15, —OCX153, —OCH2X15, —OCHX152, —N3, —CN, —SOnl5R15D, —SOv15NR15AR15B, —NHC(O)NR15AR15B, —N(O)m15, —NR15AR15B, —C(O)R15C, —C(O)—OR15C, —C(O)NR15AR15B, —OR15D, —NR15ASO2R15D, —NR15AC(O) R15C, —NR15AC(O)OR15C, —NR15AOR15C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R16is hydrogen, halogen, —CX163, —CHX162, —CH2X16, —OCX163, —OCH2X16, —OCHX162, —N3, —CN, —SOn16R16D, —SOv16NR16AR16B, —NHC(O)NR16AR16B, —N(O)m16, —NR16AR16B, —C(O)R16C, —C(O)—OR16C, —C(O)NR16AR16B, —OR16D, —NR16ASO2R16D, —NR16AC(O)R16C, —NR16AC(O)OR16C, —NR16AOR16C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R17is hydrogen, halogen, —CX173, —CHX172, —CH2X17, —OCX173, —OCH2X17, —OCHX172, —N3, —CN, —SOnl7R17D, —SOv17NR17AR17B, —NHC(O)NR17AR17B, —N(O)m17, —NR17AR17B, —C(O)R17C, —C(O)—OR17C, —C(O)NR17AR17B, —OR17D, —NR17ASO2R17D, —NR17AC(O) R17C, —NR17AC(O)OR17C, —NR17AOR17C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R14A, R14B, R14C, R14D, R15A, R15BR15C, R15D, R16A, R16B, R16C, R16D, R17A, R17B, R17C, and R17Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n14, n15, n16, and n17 are independently an integer from 0 to 4;m14, m15, m16, m17, v14, v15, v16, and v17 are independently an integer from 1 to 2; andX14, X15, X16, and X17are independently —F, —Cl, —Br, or —I. Embodiment P3. The method of any one of Embodiments P1-P2, wherein L1is —O— or —S—. Embodiment P4. The method of any one of Embodiments P1-P3, wherein at least one of R1, R2and R3are —OH. Embodiment P5. The method of any one of Embodiments P1-P4, wherein R7and R9are hydrogen. Embodiment P6. The method of any one of Embodiments P1-P5, wherein each R6, R8, and R10is independently hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, or substituted or unsubstituted C1-C3alkyl. Embodiment P7. The method of any one of Embodiments P1-P6, wherein the compound has a formula (III), Embodiment P8. The method of any one of Embodiments P1-P6, wherein the compound has a formula (III), Embodiment P9. The method of any one of Embodiments P1-P8, wherein the compound is Embodiment P10. The method of any one of Embodiments P1-P9, wherein the compound inhibits poly(ADP-ribose) glycohydrolase (PARG) in a cancer cell. Embodiment P11. The method of any one of Embodiments P1-P10, wherein the cancer is selected from: breast cancer, ovarian cancer, lung cancer, pancreatic cancer, glioblastoma, uterine cancer, bladder cancer, esophagus cancer, gastric cancer, head and neck cancer, cholangiocarcinoma, mesothelioma, prostate cancer, colon carcinoma, fallopian tube cancer, lymphoma and leukemia. Embodiment P12. The method of Embodiment P11, wherein the cancer is lymphoma. Embodiment P13. A method of inhibiting a poly(ADP-ribose) glycohydrolase (PARG), the method comprising contacting the PARG with a compound having a formula (I), wherein:L1is-CR11R12—, —NR13—, —O—, or —S—;R1is hydrogen, halogen, —CX13, —CHX12, —CH2X1, —OCX13, —OCH2X1, —OCHX12, —N3, —CN, —SOn1R1D, —SOv1NR1AR1B, —NHC(O)NR1AR1B, —N(O)m1, —NR1AR1B, —C(O)R1C, —C(O)—OR1C, —C(O)NR1AR1B, —OR1D, —NR1ASO2R1D, —NR1AC(O)R1C, —NR1AC(O)OR1C, —NR1AOR1C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R2is hydrogen, halogen, —CX23, —CHX22, —CH2X2, —OCX23, —OCH2X2, —OCHX22, —N3, —CN, —SOn2R2D. —SOv2NR2AR2B, —NHC(O)NR2AR2B, —N(O)m2, —NR2AR2B, —C(O)R2C, —C(O)—OR2C, —C(O)NR2AR2B, —OR2D, —NR2ASO2R2D, —NR2AC(O)R2C, —NR2AC(O)OR2C, —NR2AOR2C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R3is hydrogen, halogen, —CX33, —CHX32, —CH2X3, —OCX33, —OCH2X3, —OCHX32, —N3, —CN, —SOn3R3D. —SOv3NR3AR3B, —NHC(O)NR3AR3B, —N(O)m3, —NR3AR3B, —C(O)R3C, —C(O)—OR3C, —C(O)NR3AR3B, —OR3D, —NR3ASO2R3D, —NR3AC(O)R3C, —NR3AC(O)OR3C, —NR3AOR3C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4is hydrogen, halogen, —CX43, —CHX42, —CH2X4, —OCX43, —OCH2X4, —OCHX42, —N3, —CN, —SOn4R4D, —SOv4NR4AR4B, —NHC(O)NR4AR4B, —N(O)m4, —NR4AR4B, —C(O)R4C, —C(O)—OR4C, —C(O)NR4AR4B, —OR4D, —NR4ASO2R4D, —NR4AC(O)R4C, —NR4AC(O)OR4C, —NR4AOR4C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R5is hydrogen, halogen, —CX53, —CHX52, —CH2X5, —OCX53, —OCH2X5, —OCHX52, —N3, —CN, —SOn5R5D, —SOv5NR5AR5B, —NHC(O)NR5AR5B, —N(O)m5, —NR5AR5B, —C(O)R5C, —C(O)—OR5C, —C(O)NR5AR5B, —OR5D, —NR5ASO2R5D, —NR5AC(O)R5C, —NR5AC(O)OR5C, —NR5AOR5C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R6is hydrogen, halogen, —CX63, —CHX62, —CH2X6, —OCX63, —OCH2X6, —OCHX62, —N3, —CN, —SOn6R6D, —SOv6NR6AR6B, —NHC(O)NR6AR6B, —N(O)m6, —NR6AR6B, —C(O)R6C, —C(O)—OR6C, —C(O)NR6AR6B, —OR6D, —NR6ASO2R6D, —NR6AC(O)R6C, —NR6AC(O)OR6C, —NR6AOR6C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R7is hydrogen, halogen, —CX73, —CHX72, —CH2X7, —OCX73, —OCH2X7, —OCHX72, —N3, —CN, —SOn7R7D, —SOv7NR7AR7B, —NHC(O)NR7AR7B, —N(O)m7, —NR7AR7B, —C(O)R7C, —C(O)—OR7C, —C(O)NR7AR7B, —OR7D, —NR7ASO2R7D, —NR7AC(O)R7C, —NR7AC(O)OR7C, —NR7AOR7C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R8is hydrogen, halogen, —CX83, —CHX82, —CH2X8, —OCX83, —OCH2X8, —OCHX82, —N3, —CN, —SOn8R8D, —SOv8NR8AR8B, —NHC(O)NR8AR8B, —N(O)m8, —NR8AR8B, —C(O)R8C, —C(O)—OR8C, —C(O)NR8AR8B, —OR8D, —NR8ASO2R8D, —NR8AC(O)R8C, —NR8AC(O)OR8C, —NR8AOR8C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R9is hydrogen, halogen, —CX93, —CHX92, —CH2X9, —OCX93, —OCH2X9, —OCHX92, —N3, —CN, —SOn9R9D, —SOv9NR9AR9B, —NHC(O)NR9AR9B, —N(O)m9, —NR9AR9B, —C(O)R9C, —C(O)—OR9C, —C(O)NR9AR9B, —OR9D, —NR9ASO2R9D, —NR9AC(O)R9C, —NR9AC(O)OR9C, —NR9AOR9C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R10is hydrogen, halogen, —CX103, —CHX102, —CH2X10, —OCX103, —OCH2X10, —OCHX102, —N3, —CN, —SOn10R10D, —SOv10NR10AR10B, —NHC(O)NR10AR10B, —N(O)m10, —NR10AR10B, —C(O)R10C, —C(O)—OR10C, —C(O)NR10AR10B, —OR10D, —NR10ASO2R10D, —NR10AC(O)R10C, —NR10AC(O)OR10C, —NR10AOR10C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R11is hydrogen, halogen, —CX113, —CHX112, —CH2X11, —OCX113, —OCH2X11, —OCHX112, —N3, —CN, —SOn11R11D, —SOv11NR11AR11B, —NHC(O)NR11AR11B, —N(O)m11, —NR11AR11B, —C(O)R11C, —C(O)—OR11C, —C(O)NR11AR11B, —OR11D, —NR11ASO2R11D, —NR11AC(O)R11C, —NR11AC(O)OR11C, —NR11AOR11C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R12is hydrogen, halogen, —CX123, —CHX122, —CH2X12, —OCX123, —OCH2X12, —OCHX122, —N3, —CN, —SOnl2R12D, —SOv12NR12AR12B, —NHC(O)NR12AR12B, —N(O)m12, —NR12AR12B, —C(O)R12C, —C(O)—OR12C, —C(O)NR12AR12B, —OR12D, —NR12ASO2R12D, —NR12AC(O)R12C, —NR12AC(O)O R12C, —NR12AOR12C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R13is hydrogen, —CX133, —CHX132, —CH2X13, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12Cand R12Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R1and R2together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4and R5together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n1, n2, n3, n4, n5, n6, n7, n8, n9, n10, n11 and n12 are independently an integer from 0 to 4;m1, m2, m3, m4, m5, m6, m7, m8, m9, m10, m11, m12, v1, v2, v3, v4, v5, v6, v7, v8, v9, v10, v11 and v12 are independently an integer from 1 to 2; andX, X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, and X13are independently —F, —Cl, —Br, or —I, or a salt thereof. Embodiment P14. The method of Embodiment P13, wherein the compound has a formula (II): wherein:R14is hydrogen, halogen, —CX143, —CHX142, —CH2X14, —OCX143, —OCH2X14, —OCHX142, —N3, —CN, —SOn14R14D, —SOv14NR14AR14B, —NHC(O)NR14AR14B, —N(O)m14, —NR14AR14B, —C(O)R14C, —C(O)—OR14C, —C(O)NR14AR14B, —OR14D, —NR14ASO2R14D, —NR14AC(O)R14C, —NR14AC(O)O R14C, —NR14AOR14C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R15is hydrogen, halogen, —CX153, —CHX152, —CH2X15, —OCX153, —OCH2X15, —OCHX152, —N3, —CN, —SOnl5R15D, —SOv15NR15AR15B, —NHC(O)NR15AR15B, —N(O)m15, —NR15AR15B, —C(O)R15C, —C(O)—OR15C, —C(O)NR15AR15B, —OR15D, —NR15ASO2R15D, —NR15AC(O)R15C, —NR15AC(O)O R15C, —NR15AOR15C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R16is hydrogen, halogen, —CX163, —CHX162, —CH2X16, —OCX163, —OCH2X16, —OCHX162, —N3, —CN, —SOn16R16D, —SOv16NR16AR16B, —NHC(O)NR16AR16B, —N(O)m16, —NR16AR16B, —C(O)R16C, —C(O)—OR16C, —C(O)NR16AR16B, —OR16D, —NR16ASO2R16D, —NR16AC(O)R16C, —NR16AC(O)O R16C, —NR16AOR16C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R17is hydrogen, halogen, —CX173, —CHX172, —CH2X17, —OCX173, —OCH2X17, —OCHX172, —N3, —CN, —SOn17R17D, —SOv17NR17AR17B, —NHC(O)NR17AR17B, —N(O)m17, —NR17AR17B, —C(O)R17C, —C(O)—OR17C, —C(O)NR17AR17B, —OR17D, —NR17ASO2R17D, —NR17AC(O)R17C, —NR17AC(O)OR17C, —NR17AOR17C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R14A, R14B, R14C, R14D, R15A, R15B, R15C, R15D, R16A, R16B, R16C, R16D, R17A, R17B, R17C, and R17Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n14, n15, n16, and n17 are independently an integer from 0 to 4;m14, m15, m16, m17, v14, v15, v16, and v17 are independently an integer from 1 to 2; andX14, X15, X16, and X17are independently —F, —Cl, —Br, or —I. Embodiment P15. The method of any one of Embodiments P13-P14, wherein L1is —O— or —S—. Embodiment P16. The method of any one of Embodiments P13-P15, wherein at least one of R1, R2and R3are —OH. Embodiment P17. The method of any one of Embodiments P13-P16, wherein R7and R9are hydrogen. Embodiment P18. The method of any one of Embodiments P13-P17, wherein each R6, R8, and R10is independently hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, or substituted or unsubstituted C1-C3alkyl. Embodiment P19. The method of any one of Embodiments P13-P18, wherein the compound has a formula (III), Embodiment P20. The method of any one of Embodiments P13-P18, wherein the compound has a formula (IV). Embodiment P21. The method of any one of Embodiments P13-P20, wherein the compound is Embodiment P22. The method of any one of Embodiments P13-P21, wherein the compound inhibits the poly(ADP-ribose) glycohydrolase (PARG) in a cancer cell. Embodiment P23. The method of Embodiment P22, wherein the cancer cell is from breast cancer, ovarian cancer, lung cancer, pancreatic cancer, glioblastoma, uterine cancer, bladder cancer, esophagus cancer, gastric cancer, head and neck cancer, cholangiocarcinoma, mesothelioma, prostate cancer, colon carcinoma, fallopian tube cancer, lymphoma and leukemia. Embodiment P24. A compound having a formula (I), wherein,L1is-CR11R12—, —NR13—, —O—, or —S—;R1is hydrogen, halogen, —CX13, —CHX12, —CH2X1, —OCX13, —OCH2X1, —OCHX12, —N3, —CN, —SOn1R1D, —SOv1NR1AR1B, —NHC(O)NR1AR1B, —N(O)m1, —NR1AR1B, —C(O)R1C, —C(O)—OR1C, —C(O)NR1AR1B, —OR1D, —NR1ASO2R1D, —NR1AC(O)R1C, —NR1AC(O)OR1C, —NR1AOR1C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R2is hydrogen, halogen, —CX23, —CHX22, —CH2X2, —OCX23, —OCH2X2, —OCHX22, —N3, —CN, —SOn2R2D. —SOv2NR2AR2B, —NHC(O)NR2AR2B, —N(O)m2, —NR2AR2B, —C(O)R2C, —C(O)—OR2C, —C(O)NR2AR2B, —OR2D, —NR2ASO2R2D, —NR2AC(O)R2C, —NR2AC(O)OR2C, —NR2AOR2C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R3is hydrogen, halogen, —CX33, —CHX32, —CH2X3, —OCX33, —OCH2X3, —OCHX32, —N3, —CN, —SOn3R3D. —SOv3NR3AR3B, —NHC(O)NR3AR3B, —N(O)m3, —NR3AR3B, —C(O)R3C, —C(O)—OR3C, —C(O)NR3AR3B, —OR3D, —NR3ASO2R3D, —NR3AC(O)R3C, —NR3AC(O)OR3C, —NR3AOR3C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4is hydrogen, halogen, —CX43, —CHX42, —CH2X4, —OCX43, —OCH2X4, —OCHX42, —N3, —CN, —SOn4R4D, —SOv4NR4AR4B, —NHC(O)NR4AR4B, —N(O)m4, —NR4AR4B, —C(O)R4C, —C(O)—OR4C, —C(O)NR4AR4B, —OR4D, —NR4ASO2R4D, —NR4AC(O)R4C, —NR4AC(O)OR4C, —NR4AOR4C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R5is hydrogen, halogen, —CX53, —CHX52, —CH2X5, —OCX53, —OCH2X5, —OCHX52, —N3, —CN, —SOn5R5D, —SOv5NR5AR5B, —NHC(O)NR5AR5B, —N(O)m5, —NR5AR5B, —C(O)R5C, —C(O)—OR5C, —C(O)NR5AR5B, —OR5D, —NR5ASO2R5D, —NR5AC(O)R5C, —NR5AC(O)OR5C, —NR5AOR5C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R6is hydrogen, halogen, —CX63, —CHX62, —CH2X6, —OCX63, —OCH2X6, —OCHX62, —N3, —CN, —SOn6R6D, —SOv6NR6AR6B, —NHC(O)NR6AR6B, —N(O)m6, —NR6AR6B, —C(O)R6C, —C(O)—OR6C, —C(O)NR6AR6B, —OR6D, —NR6ASO2R6D, —NR6AC(O)R6C, —NR6AC(O)OR6C, —NR6AOR6C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R7is hydrogen, halogen, —CX73, —CHX72, —CH2X7, —OCX73, —OCH2X7, —OCHX72, —N3, —CN, —SOn7R7D, —SOv7NR7AR7B, —NHC(O)NR7AR7B, —N(O)m7, —NR7AR7B, —C(O)R7C, —C(O)—OR7C, —C(O)NR7AR7B, —OR7D, —NR7ASO2R7D, —NR7AC(O)R7C, —NR7AC(O)OR7C, —NR7AOR7C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R8is hydrogen, halogen, —CX83, —CHX82, —CH2X8, —OCX83, —OCH2X8, —OCHX82, —N3, —CN, —SOn8R8D, —SOv8NR8AR8B, —NHC(O)NR8AR8B, —N(O)m8, —NR8AR8B, —C(O)R8C, —C(O)—OR8C, —C(O)NR8AR8B, —OR8D, —NR8ASO2R8D, —NR8AC(O)R8C, —NR8AC(O)OR8C, —NR8AOR8C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R9is hydrogen, halogen, —CX93, —CHX92, —CH2X9, —OCX93, —OCH2X9, —OCHX92, —N3, —CN, —SOn9R9D, —SOv9NR9AR9B, —NHC(O)NR9AR9B, —N(O)m9, —NR9AR9B, —C(O)R9C, —C(O)—OR9C, —C(O)NR9AR9B, —OR9D, —NR9ASO2R9D, —NR9AC(O)R9C, —NR9AC(O)OR9C, —NR9AOR9C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R10is hydrogen, halogen, —CX103, —CHX102, —CH2X10, —OCX103, —OCH2X10, —OCHX102, —N3, —CN, —SOn10R10D, —SOv10NR10AR10B, —NHC(O)NR10AR10B, —N(O)m10, —NR10AR10B, —C(O)R10C, —C(O)—OR10C, —C(O)NR10AR10B, —OR10D, —NR10ASO2R10D, —NR10AC(O)R10C, —NR10AC(O)OR10C, —NR10AOR10C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R11is hydrogen, halogen, —CX113, —CHX112, —CH2X11, —OCX113, —OCH2X11, —OCHX112, —N3, —CN, —SOn11R11D, —SOv11NR11AR11B, —NHC(O)NR11AR11B, —N(O)m11, —NR11AR11B, —C(O)R11C, —C(O)—OR11C, —C(O)NR11AR11B, —OR11D, —NR11ASO2R11D, —NR11AC(O) R11C, —NR11AC(O)OR11C, —NR11AOR11C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R12is hydrogen, halogen, —CX123, —CHX122, —CH2X12, —OCX123, —OCH2X12, —OCHX122, —N3, —CN, —SOnl2R12D, —SOv12NR12AR12B, —NHC(O)NR12AR12B, —N(O)m12, —NR12AR12B, —C(O)R12C, —C(O)—OR12C, —C(O)NR12AR12B, —OR12D, —NR12ASO2R12D, —NR12AC(O) R12C, —NR12AC(O)OR12C, —NR12AOR12C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R13is hydrogen, —CX133, —CHX132, —CH2X13, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12Cand R12Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R1and R2together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4and R5together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n1, n2, n3, n4, n5, n6, n7, n8, n9, n10, n11 and n12 are independently an integer from 0 to 4;m1, m2, m3, m4, m5, m6, m7, m8, m9, m10, m11, m12, v1, v2, v3, v4, v5, v6, v7, v8, v9, v10, v11 and v12 are independently an integer from 1 to 2; andX, X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, and X13are independently —F, —Cl, —Br, or —I,or a salt thereof, provided that when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH3; and when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH3. Embodiment P25. A compound having a formula (I), wherein,L1is-CR11R12—, —NR13—, —O—, or —S—;R1is hydrogen, halogen, —CX13, —CHX12, —CH2X1, —OCX13, —OCH2X1, —OCHX12, —N3, —CN, —SOn1R1D, —SOv1NR1AR1B, —NHC(O)NR1AR1B, —N(O)m1, —NR1AR1B, —C(O)R1C, —C(O)—OR1C, —C(O)NR1AR1B, —OR1D, —NR1ASO2R1D, —NR1AC(O)R1C, —NR1AC(O)OR1C, —NR1AOR1C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R2is hydrogen, halogen, —CX23, —CHX22, —CH2X2, —OCX23, —OCH2X2, —OCHX22, —N3, —CN, —SOn2R2D. —SOv2NR2AR2B, —NHC(O)NR2AR2B, —N(O)m2, —NR2AR2B, —C(O)R2C, —C(O)—OR2C, —C(O)NR2AR2B, —OR2D, —NR2ASO2R2D, —NR2AC(O)R2C, —NR2AC(O)OR2C, —NR2AOR2C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R3is hydrogen, halogen, —CX33, —CHX32, —CH2X3, —OCX33, —OCH2X3, —OCHX32, —N3, —CN, —SOn3R3D. —SOv3NR3AR3B, —NHC(O)NR3AR3B, —N(O)m3, —NR3AR3B, —C(O)R3C, —C(O)—OR3C, —C(O)NR3AR3B, —OR3D, —NR3ASO2R3D, —NR3AC(O)R3C, —NR3AC(O)OR3C, —NR3AOR3C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4is hydrogen, halogen, —CX43, —CHX42, —CH2X4, —OCX43, —OCH2X4, —OCHX42, —N3, —CN, —SOn4R4D, —SOv4NR4AR4B, —NHC(O)NR4AR4B, —N(O)m4, —NR4AR4B, —C(O)R4C, —C(O)—OR4C, —C(O)NR4AR4B, —OR4D, —NR4ASO2R4D, —NR4AC(O)R4C, —NR4AC(O)OR4C, —NR4AOR4C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R5is hydrogen, halogen, —CX53, —CHX52, —CH2X5, —OCX53, —OCH2X5, —OCHX52, —N3, —CN, —SOn5R5D, —SOv5NR5AR5B, —NHC(O)NR5AR5B, —N(O)m5, —NR5AR5B, —C(O)R5C, —C(O)—OR5C, —C(O)NR5AR5B, —OR5D, —NR5ASO2R5D, —NR5AC(O)R5C, —NR5AC(O)OR5C, —NR5AOR5C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R6is hydrogen, halogen, —CX63, —CHX62, —CH2X6, —OCX63, —OCH2X6, —OCHX62, —N3, —CN, —SOn6R6D, —SOv6NR6AR6B, —NHC(O)NR6AR6B, —N(O)m6, —NR6AR6B, —C(O)R6C, —C(O)—OR6C, —C(O)NR6AR6B, —OR6D, —NR6ASO2R6D, —NR6AC(O)R6C, —NR6AC(O)OR6C, —NR6AOR6C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R7is hydrogen, halogen, —CX73, —CHX72, —CH2X7, —OCX73, —OCH2X7, —OCHX72, —N3, —CN, —SOn7R7D, —SOv7NR7AR7B, —NHC(O)NR7AR7B, —N(O)m7, —NR7AR7B, —C(O)R7C, —C(O)—OR7C, —C(O)NR7AR7B, —OR7D, —NR7ASO2R7D, —NR7AC(O)R7C, —NR7AC(O)OR7C, —NR7AOR7C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R8is hydrogen, halogen, —CX83, —CHX82, —CH2X8, —OCX83, —OCH2X8, —OCHX82, —N3, —CN, —SOn8R8D, —SOv8NR8AR8B, —NHC(O)NR8AR8B, —N(O)m8, —NR8AR8B, —C(O)R8C, —C(O)—OR8C, —C(O)NR8AR8B, —OR8D, —NR8ASO2R8D, —NR8AC(O)R8C, —NR8AC(O)OR8C, —NR8AOR8C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R9is hydrogen, halogen, —CX93, —CHX92, —CH2X9, —OCX93, —OCH2X9, —OCHX92, —N3, —CN, —SOn9R9D, —SOv9NR9AR9B, —NHC(O)NR9AR9B, —N(O)m9, —NR9AR9B, —C(O)R9C, —C(O)—OR9C, —C(O)NR9AR9B, —OR9D, —NR9ASO2R9D, —NR9AC(O)R9C, —NR9AC(O)OR9C, —NR9AOR9C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R10is hydrogen, halogen, —CX103, —CHX102, —CH2X10, —OCX103, —OCH2X10, —OCHX102, —N3, —CN, —SOn10R10D, —SOv10NR10AR10B, —NHC(O)NR10AR10B, —N(O)m10, —NR10AR10B, —C(O)R10C, —C(O)—OR10C, —C(O)NR10AR10B, —OR10D, —NR10ASO2R10D, —NR10AC(O) R10C, —NR10AC(O)OR10C, —NR10AOR10C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R11is hydrogen, halogen, —CX113, —CHX112, —CH2X11, —OCX113, —OCH2X11, —OCHX112, —N3, —CN, —SOn11R11D, —SOv11NR11AR11B, —NHC(O)NR11AR11B, —N(O)m11, —NR11AR11B, —C(O)R11C, —C(O)—OR11C, —C(O)NR11AR11B, —OR11D, —NR11ASO2R11D, —NR11AC(O) R11C, —NR11AC(O)OR11C, —NR11AOR11C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R12is hydrogen, halogen, —CX123, —CHX122, —CH2X12, —OCX123, —OCH2X12, —OCHX122, —N3, —CN, —SOnl2R12D, —SOv12NR12AR12B, —NHC(O)NR12AR12B, —N(O)m12, —NR12AR12B, —C(O)R12C, —C(O)—OR12C, —C(O)NR12AR12B, —OR12D, —NR12ASO2R12D, —NR12AC(O) R12C, —NR12AC(O)OR12C, —NR12AOR12C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R13is hydrogen, —CX133, —CHX132, —CH2X13, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12Cand R12Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R1and R2together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4and R5together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n1, n2, n3, n4, n5, n6, n7, n8, n9, n10, n11 and n12 are independently an integer from 0 to 4;m1, m2, m3, m4, m5, m6, m7, m8, m9, m10, m11, m12, v1, v2, v3, v4, v5, v6, v7, v8, v9, v10, v11 and v12 are independently an integer from 1 to 2; andX, X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, and X13are independently —F, —Cl, —Br, or —I,or a salt thereof,provided that when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH3; and when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH3. Embodiment P26. The compound of any one of Embodiments P24-P25, wherein L1is —O— or —S—. Embodiment P27. The compound of any one of Embodiments P24-P26, wherein at least one of R1, R2and R3are —OH. Embodiment P28. The compound of any one of Embodiments P24-P27, wherein R7and R9are hydrogen. Embodiment P29. The compound of any one of Embodiments P24-P28, wherein each R6, R8, and R10is independently hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, or substituted or unsubstituted C1-C3alkyl. Embodiment P30. The compound of any one of Embodiments P24-P29, wherein the compound has a formula (III), Embodiment P31. The compound of any one of Embodiments P24-P29, wherein the compound has a formula (IV), Embodiment P32. The compound of any one of Embodiments P24-P31, wherein the compound is Embodiment P33. A pharmaceutical composition comprising a compound having a formula (I), wherein,L1is-CR11R12—, —NR13—, —O—, or —S—;R1is hydrogen, halogen, —CX13, —CHX12, —CH2X1, —OCX13, —OCH2X1, —OCHX12, —N3, —CN, —SOn1R1D, —SOv1NR1AR1B, —NHC(O)NR1AR1B, —N(O)m1, —NR1AR1B, —C(O)R1C, C(O)—OR1C, —C(O)NR1AR1B, —OR1D, —NR1ASO2R1D, —NR1AC(O)R1C, —NR1AC(O)OR1C, —NR1AOR1C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R2is hydrogen, halogen, —CX23, —CHX22, —CH2X2, —OCX23, —OCH2X2, —OCHX22, —N3, —CN, —SOn2R2D, —SOv2NR2AR2B, —NHC(O)NR2AR2B, —N(O)m2, —NR2AR2B, —C(O)R2C, C(O)—OR2C, —C(O)NR2AR2B, —OR2D, —NR2ASO2R2D, —NR2AC(O)R2C, —NR2AC(O)OR2C, —NR2AOR2C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R3is hydrogen, halogen, —CX33, —CHX32, —CH2X3, —OCX33, —OCH2X3, —OCHX32, —N3, —CN, —SOn3R3D, —SOv3NR3AR3B, —NHC(O)NR3AR3B, —N(O)m3, —NR3AR3B, —C(O)R3C, —C(O)—OR3C, —C(O)NR3AR3B, —OR3D, —NR3ASO2R3D, —NR3AC(O)R3C, —NR3AC(O)OR3C, —NR3AOR3C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4is hydrogen, halogen, —CX43, —CHX42, —CH2X4, —OCX43, —OCH2X4, —OCHX42, —N3, —CN, —SOn4R4D, —SOv4NR4AR4B, —NHC(O)NR4AR4B, —N(O)m4, —NR4AR4B, —C(O)R4C, —C(O)—OR4C, —C(O)NR4AR4B, —OR4D, —NR4ASO2R4D, —NR4AC(O)R4C, —NR4AC(O)OR4C, —NR4AOR4C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R5is hydrogen, halogen, —CX53, —CHX52, —CH2X5, —OCX53, —OCH2X5, —OCHX52, —N3, —CN, —SOn5R5D, —SOv5NR5AR5B, —NHC(O)NR5AR5B, —N(O)m5, —NR5AR5B, —C(O)R5C, —C(O)—OR5C, —C(O)NR5AR5B, —OR5D, —NR5ASO2R5D, —NR5AC(O)R5C, —NR5AC(O)OR5C, —NR5AOR5C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R6is hydrogen, halogen, —CX63, —CHX62, —CH2X6, —OCX63, —OCH2X6, —OCHX62, —N3, —CN, —SOn6R6D, —SOv6NR6AR6B, —NHC(O)NR6AR6B, —N(O)m6, —NR6AR6B, —C(O)R6C, —C(O)—OR6C, —C(O)NR6AR6B, —OR6D, —NR6ASO2R6D, —NR6AC(O)R6C, —NR6AC(O)OR6C, —NR6AOR6C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R7is hydrogen, halogen, —CX73, —CHX72, —CH2X7, —OCX73, —OCH2X7, —OCHX72, —N3, —CN, —SOn7R7D, —SOv7NR7AR7B, —NHC(O)NR7AR7B, —N(O)m7, —NR7AR7B, —C(O)R7C, —C(O)—OR7C, —C(O)NR7AR7B, —OR7D, —NR7ASO2R7D, —NR7AC(O)R7C, —NR7AC(O)OR7C, —NR7AOR7C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R8is hydrogen, halogen, —CX83, —CHX82, —CH2X8, —OCX83, —OCH2X8, —OCHX82, —N3, —CN, —SOn8R8D, —SOv8NR8AR8B, —NHC(O)NR8AR8B, —N(O)m8, —NR8AR8B, —C(O)R8C, —C(O)—OR8C, —C(O)NR8AR8B, —OR8D, —NR8ASO2R8D, —NR8AC(O)R8C, —NR8AC(O)OR8C, —NR8AOR8C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R9is hydrogen, halogen, —CX93, —CHX92, —CH2X9, —OCX93, —OCH2X9, —OCHX92, —N3, —CN, —SOn9R9D, —SOv9NR9AR9B, —NHC(O)NR9AR9B, —N(O)m9, —NR9AR9B, —C(O)R9C, —C(O)—OR9C, —C(O)NR9AR9B, —OR9D, —NR9ASO2R9D, —NR9AC(O)R9C, —NR9AC(O)OR9C, —NR9AOR9C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R10is hydrogen, halogen, —CX103, —CHX102, —CH2X10, —OCX103, —OCH2X10, —OCHX102, —N3, —CN, —SOn10R10D, —SOv10NR10AR10B, —NHC(O)NR10AR10B, —N(O)m10, —NR10AR10B, —C(O)R10C, —C(O)—OR10C, —C(O)NR10AR10B, —OR10D, —NR10ASO2R10D, —NR10AC(O)R10C, —NR10AC(O)OR10C, —NR10AOR10C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R11is hydrogen, halogen, —CX113, —CHX112, —CH2X11, —OCX113, —OCH2X11, —OCHX112, —N3, —CN, —SOn11R11D, —SOv11NR11AR11B, —NHC(O)NR11AR11B, —N(O)m11, —NR11AR11B, —C(O)R11C, —C(O)—OR11C, —C(O)NR11AR11B, —OR11D, —NR11ASO2R11D, —NR11AC(O)R11C, —NR11AC(O)OR11C, —NR11AOR11C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R12is hydrogen, halogen, —CX123, —CHX122, —CH2X12, —OCX123, —OCH2X12, —OCHX122, —N3, —CN, —SOnl2R12D, —SOv12NR12AR12B, —NHC(O)NR12AR12B, —N(O)m12, —NR12AR12B, —C(O)R12C, —C(O)—OR12C, —C(O)NR12AR12B, —OR12D, —NR12ASO2R12D, —NR12AC(O)R12C, —NR12AC(O)OR12C, —NR12AOR12C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R13is hydrogen, —CX133, —CHX132, —CH2X13, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12Cand R12Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R1and R2together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4and R5together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n1, n2, n3, n4, n5, n6, n7, n8, n9, n10, n11 and n12 are independently an integer from 0 to 4;m1, m2, m3, m4, m5, m6, m7, m8, m9, m10, m11, m12, v1, v2, v3, v4, v5, v6, v7, v8, v9, v10, v11 and v12 are independently an integer from 1 to 2; andX, X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, and X13are independently —F, —Cl, —Br, or —I,or a salt thereof, and a pharmaceutically acceptable carrier. Embodiment P34. The pharmaceutical composition of Embodiment P33, wherein the compound has a formula (II): wherein:R14is hydrogen, halogen, —CX143, —CHX142, —CH2X14, —OCX143, —OCH2X14, —OCHX142, —N3, —CN, —SOn14R14D, —SOv14NR14AR14B, —NHC(O)NR14AR14B, —N(O)m14, —NR14AR14B, C(O)R14C, —C(O)—OR14C, —C(O)NR14AR14B, —OR14D, —NR14ASO2R14D, —NR14AC(O)R14C, —NR14AC(O)OR14C, —NR14AOR14C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R15is hydrogen, halogen, —CX153, —CHX152, —CH2X15, —OCX153, —OCH2X15, —OCHX152, —N3, —CN, —SOnl5R15D, —SOv15NR15AR15B, —NHC(O)NR15AR15B, —N(O)m15, —NR15AR15B, —C(O)R15C, —C(O)—OR15C, —C(O)NR15AR15B, —OR15D, —NR15ASO2R15D, —NR15AC(O)R15C, —NR15AC(O)O R15C, —NR15AOR15C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R16is hydrogen, halogen, —CX163, —CHX162, —CH2X16, —OCX163, —OCH2X16, —OCHX162, —N3, —CN, —SOn16R16D, —SOv16NR16AR16B, —NHC(O)NR16AR16B, —N(O)m16, —NR16AR16B, —C(O)R16C, —C(O)—OR16C, —C(O)NR16AR16B, —OR16D, —NR16ASO2R16D, —NR16AC(O)R16C, —NR16AC(O)OR16C, —NR16AOR16C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R17is hydrogen, halogen, —CX173, —CHX172, —CH2X17, —OCX173, —OCH2X17, —OCHX172, —N3, —CN, —N3, —SOn17R17D, —SOv17NR17AR17B, —NHC(O)NR17AR17B, —N(O)m17, —NR17AR17B, —C(O)R17C, —C(O)—OR17C, —C(O)NR17AR17B, —OR17D, —NR17ASO2R17D, —NR17AC(O) R17C, —NR17AC(O)OR17C, —NR17AOR17C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R14A, R14B, R14C, R14D, R15A, R15B, R15C, R15D, R16A, R16B, R16C, R16D, R17A, R17B, R17C, and R17Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n14, n15, n16, and n17 are independently an integer from 0 to 4;m14, m15, m16, m17, v14, v15, v16, and v17 are independently an integer from 1 to 2; andX14, X15, X16, and X17are independently —F, —Cl, —Br, or —I. Embodiment P35. The pharmaceutical composition of any one of Embodiments P33-P34, wherein L1is —O— or —S—. Embodiment P36. The pharmaceutical composition pound of any one of Embodiments P33-P35, wherein at least one of R1, R2and R3are —OH. Embodiment P37. The pharmaceutical composition of any one of Embodiments P33-P36, wherein R7and R9are hydrogen. Embodiment P38. The pharmaceutical composition of any one of Embodiments P33-P37, wherein each R6, R8, and R10is independently hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, or substituted or unsubstituted C1-C3alkyl. Embodiment P39. The pharmaceutical composition of any one of Embodiments P33-P38, wherein the compound has a formula (III), Embodiment P40. The pharmaceutical composition of any one of Embodiments P33-P38, wherein the compound has a formula (IV). Embodiment P41. The pharmaceutical composition of any one of Embodiments P33-P40, wherein the compound is Embodiments Q Embodiment Q1. A method of treating cancer in a subject in need thereof, the method comprising administering to the subject an effective amount of a compound having a formula (I), wherein:L1is a bond, —CR11R12—, —NR13—, —O—, —S—, —S(O)2—, —NR13S(O)2—, or —NR13C(O)—;R1is hydrogen, halogen, —CX13, —CHX12, —CH2X1, —OCX13, —OCH2X1, —OCHX12, —N3, —CN, —SOn1R1D, —SOv1NR1AR1B, —NHC(O)NR1AR1B, —N(O)m1, —NR1AR1B, —C(O)R1C, C(O)—OR1C, —C(O)NR1AR1B, —OR1D, —NR1ASO2R1D, —NR1AC(O)R1C, —NR1AC(O)OR1C, —NR1AOR1C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R2is hydrogen, halogen, —CX23, —CHX22, —CH2X2, —OCX23, —OCH2X2, —OCHX22, —N3, —CN, —SOn2R2D, —SOv2NR2AR2B, —NHC(O)NR2AR2B, —N(O)m2, —NR2AR2B, —C(O)R2C, —C(O)—OR2C, —C(O)NR2AR2B, —OR2D, —NR2ASO2R2D, —NR2AC(O)R2C, —NR2AC(O)OR2C, —NR2AOR2C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R3is hydrogen, halogen, —CX33, —CHX32, —CH2X3, —OCX33, —OCH2X3, —OCHX32, —N3, —CN, —SOn3R3D, —SOv3NR3AR3B, —NHC(O)NR3AR3B, —N(O)m3, —NR3AR3B, —C(O)R3C, C(O)—OR3C, —C(O)NR3AR3B, —OR3D, —NR3ASO2R3D, —NR3AC(O)R3C, —NR3AC(O)OR3C, —NR3AOR3C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4is hydrogen, halogen, —CX43, —CHX42, —CH2X4, —OCX43, —OCH2X4, —OCHX42, —N3, —CN, —SOn4R4D, —SOv4NR4AR4B, —NHC(O)NR4AR4B, —N(O)m4, —NR4AR4B, —C(O)R4C, C(O)—OR4C, —C(O)NR4AR4B, —OR4D, —NR4ASO2R4D, —NR4AC(O)R4C, —NR4AC(O)OR4C, —NR4AOR4C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R5is hydrogen, halogen, —CX53, —CHX52, —CH2X5, —OCX53, —OCH2X5, —OCHX52, —N3, —CN, —SOn5R5D, —SOv5NR5AR5B, —NHC(O)NR5AR5B, —N(O)m5, —NR5AR5B, —C(O)R5C, C(O)—OR5C, —C(O)NR5AR5B, —OR5D, —NR5ASO2R5D, —NR5AC(O)R5C, —NR5AC(O)OR5C, —NR5AOR5C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R6is hydrogen, halogen, —CX63, —CHX62, —CH2X6, —OCX63, —OCH2X6, —OCHX62, —N3, —CN, —SOn6R6D, —SOv6NR6AR6B, —NHC(O)NR6AR6B, —N(O)m6, —NR6AR6B, —C(O)R6C, C(O)—OR6C, —C(O)NR6AR6B, —OR6D, —NR6ASO2R6D, —NR6AC(O)R6C, —NR6AC(O)OR6C, —NR6AOR6C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R7is hydrogen, halogen, —CX73, —CHX72, —CH2X7, —OCX73, —OCH2X7, —OCHX72, —N3, —CN, —SOn7R7D, —SOv7NR7AR7B, —NHC(O)NR7AR7B, —N(O)m7, —NR7AR7B, —C(O)R7C, C(O)—OR7C, —C(O)NR7AR7B, —OR7D, —NR7ASO2R7D, —NR7AC(O)R7C, —NR7AC(O)OR7C, —NR7AOR7C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R8is hydrogen, halogen, —CX83, —CHX82, —CH2X8, —OCX83, —OCH2X8, —OCHX82, —N3, —CN, —SOn8R8D, —SOv8NR8AR8B, —NHC(O)NR8AR8B, —N(O)m8, —NR8AR8B, —C(O)R8C, C(O)—OR8C, —C(O)NR8AR8B, —OR8D, —NR8ASO2R8D, —NR8AC(O)R8C, —NR8AC(O)OR8C, —NR8AOR8C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R9is hydrogen, halogen, —CX93, —CHX92, —CH2X9, —OCX93, —OCH2X9, —OCHX92, —N3, —CN, —SOn9R9D, —SOv9NR9AR9B, —NHC(O)NR9AR9B, —N(O)m9, —NR9AR9B, —C(O)R9C, C(O)—OR9C, —C(O)NR9AR9B, —OR9D, —NR9ASO2R9D, —NR9AC(O)R9C, —NR9AC(O)OR9C, —NR9AOR9C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R10is hydrogen, halogen, —CX103, —CHX102, —CH2X10, —OCX103, —OCH2X10, —OCHX102, —N3, —CN, —SOn10R10D, —SOv10NR10AR10B, —NHC(O)NR10AR10B, —N(O)m10, —NR10AR10B, —C(O)R10C, —C(O)—OR10C, —C(O)NR10AR10B, —OR10D, —NR10ASO2R10D, —NR10AC(O)R10C, —NR10AC(O)OR10C, —NR10AOR10C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R11is hydrogen, halogen, —CX113, —CHX112, —CH2X11, —OCX113, —OCH2X11, —OCHX112, —N3, —CN, —SOn11R11D, —SOv11NR11AR11B, —NHC(O)NR11AR11B, —N(O)m11, —NR11AR11B, —C(O)R11C, —C(O)—OR11C, —C(O)NR11AR11B, —OR11D, —NR11ASO2R11D, —NR11AC(O)R11C, —NR11AC(O)OR11C, —NR11AOR11C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R12is hydrogen, halogen, —CX123, —CHX122, —CH2X12, —OCX123, —OCH2X12, —OCHX122, —N3, —CN, —SOnl2R12D, —SOv12NR12AR12B, —NHC(O)NR12AR12B, —N(O)m12, —NR12AR12B, —C(O)R12C, —C(O)—OR12C, —C(O)NR12AR12B, —OR12D, —NR12ASO2R12D, —NR12AC(O) R12C, —NR12AC(O)OR12C, —NR12AOR12C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R13is hydrogen, —CX133, —CHX132, —CH2X13, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12Cand R12Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R1and R2together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4and R5together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n1, n2, n3, n4, n5, n6, n7, n8, n9, n10, n11 and n12 are independently an integer from 0 to 4;m1, m2, m3, m4, m5, m6, m7, m8, m9, m10, m11, m12, v1, v2, v3, v4, v5, v6, v7, v8, v9, v10, v11 and v12 are independently an integer from 1 to 2; andX, X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, and X13are independently —F, —Cl, —Br, or —I,or a salt thereof. Embodiment Q2. The method of Embodiment Q1, wherein the compound has a formula (II): wherein:R14is hydrogen, halogen, —CX143, —CHX142, —CH2X14, —OCX143, —OCH2X14, —OCHX142, —N3, —CN, —SOn14R14D, —SOv14NR14AR14B, —NHC(O)NR14AR14B, —N(O)m14, —NR14AR14B, —C(O)R14C, —C(O)—OR14C, —C(O)NR14AR14B, —OR14D, —NR14ASO2R14D, —NR14AC(O) R14C, —NR14AC(O)OR14C, —NR14AOR14C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R15is hydrogen, halogen, —CX153, —CHX152, —CH2X15, —OCX153, —OCH2X15, —OCHX152, —N3, —CN, —SOnl5R15D, —SOv15NR15AR15B, —NHC(O)NR15AR15B, —N(O)m14, —NR15AR15B, —C(O)R15C, —C(O)—OR15C, —C(O)NR15AR15B, —OR15D, —NR15ASO2R15D, —NR15AC(O) R15C, —NR15AC(O)OR15C, —NR15AOR15C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R16is hydrogen, halogen, —CX163, —CHX162, —CH2X16, —OCX163, —OCH2X16, —OCHX162, —N3, —CN, —SOn16R16D, —SOv16NR16AR16B, —NHC(O)NR16AR16B, —N(O)m16, —NR16AR16B, —C(O)R16C, —C(O)—OR16C, —C(O)NR16AR16B, —OR16D, —NR16ASO2R16D, —NR16AC(O) R16C, —NR16AC(O)OR16C, —NR16AOR16C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R17is hydrogen, halogen, —CX173, —CHX172, —CH2X17, —OCX173, —OCH2X17, —OCHX172, —N3, —CN, —SOn17R17D, —SOv17NR17AR17B, —NHC(O)NR17AR17B, —N(O)m17, —NR17AR17B, —C(O)R17C, —C(O)—OR17C, —C(O)NR17AR17B, —OR17D, —NR17ASO2R17D, —NR17AC(O) R17C, —NR17AC(O)OR17C, —NR17AOR17C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R14A, R14B, R14C, R14D, R15A, R15B, R15C, R15D, R16A, R16B, R16C, R16D, R17A, R17B, R17C, and R17Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n14, n15, n16, and n17 are independently an integer from 0 to 4;m14, m15, m16, m17, v14, v15, v16, and v17 are independently an integer from 1 to 2; and X14, X15, X16, and X17are independently —F, —Cl, —Br, or —I. Embodiment Q3. The method of any one of Embodiments Q1-Q2, wherein L1is —O— or —S—. Embodiment Q4. The method of any one of Embodiments Q1-Q2, wherein L1is a bond. Embodiment Q5. The method of any one of Embodiments Q1-Q2, wherein L1is —S(O)2—, —NR13S(O)2— or —NR13C(O)—. Embodiment Q6. The method of any one of Embodiments Q1-Q5, wherein at least one of R1, R2and R3are —OH or —OCH3. Embodiment Q7. The method of any one of Embodiments Q1-Q6, wherein R7and R9are hydrogen. Embodiment Q8. The method of any one of Embodiments Q1-Q7, wherein each R6, R8, and R10is independently hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, or substituted or unsubstituted C1-C3alkyl. Embodiment Q9 The method of any one of Embodiments Q1-Q8, wherein the compound has a formula (III), Embodiment Q10. The method of any one of Embodiments Q1-Q8, wherein the compound has a formula (IV), Embodiment Q11. The method of any one of Embodiments Q1-Q8, wherein the compound has a formula (V), Embodiment Q12. The method of any one of Embodiments Q1-Q8, wherein the compound has a formula (VI), Embodiment Q13. The method of any one of Embodiments Q1-Q8, wherein the compound has a formula (VII), Embodiment Q14. The method of any one of Embodiments Q1-Q13, wherein the compound is Embodiment Q15. The method of any one of Embodiments Q1-Q14, wherein the compound inhibits poly(ADP-ribose) glycohydrolase (PARG) in a cancer cell. Embodiment Q16. The method of any one of Embodiments Q1-Q15, wherein the cancer is selected from: breast cancer, ovarian cancer, lung cancer, pancreatic cancer, glioblastoma, uterine cancer, bladder cancer, esophagus cancer, gastric cancer, head and neck cancer, cholangiocarcinoma, mesothelioma, prostate cancer, colon carcinoma, fallopian tube cancer, lymphoma and leukemia. Embodiment Q17. The method of Embodiment Q16, wherein the cancer is lymphoma. Embodiment Q18. A method of inhibiting a poly(ADP-ribose) glycohydrolase (PARG), the method comprising contacting the PARG with a compound having a formula (I), wherein:L1is a bond, —CR11R12—, —NR13—, —O—, —S—, —S(O)2—, —NR13S(O)2—, or —NR13C(O)—;R1is hydrogen, halogen, —CX13, —CHX12, —CH2X1, —OCX13, —OCH2X1, —OCHX12, —N3, —CN, —SOn1R1D, —SOv1NR1AR1B, —NHC(O)NR1AR1B, —N(O)m1, —NR1AR1B, —C(O)R1C, —C(O)—OR1C, —C(O)NR1AR1B, —OR1D, —NR1ASO2R1D, —NR1AC(O)R1C, —NR1AC(O)OR1C, —NR1AOR1C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R2is hydrogen, halogen, —CX23, —CHX22, —CH2X2, —OCX23, —OCH2X2, —OCHX22, —N3, —CN, —SOn2R2D. —SOv2NR2AR2B, —NHC(O)NR2AR2B, —N(O)m2, —NR2AR2B, —C(O)R2C, —C(O)—OR2C, —C(O)NR2AR2B, —OR2D, —NR2ASO2R2D, —NR2AC(O)R2C, —NR2AC(O)OR2C, —NR2AOR2C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R3is hydrogen, halogen, —CX33, —CHX32, —CH2X3, —OCX33, —OCH2X3, —OCHX32, —N3, —CN, —SOn3R3D. —SOv3NR3AR3B, —NHC(O)NR3AR3B, —N(O)m3, —NR3AR3B, —C(O)R3C, —C(O)—OR3C, —C(O)NR3AR3B, —OR3D, —NR3ASO2R3D, —NR3AC(O)R3C, —NR3AC(O)OR3C, —NR3AOR3C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4is hydrogen, halogen, —CX43, —CHX42, —CH2X4, —OCX43, —OCH2X4, —OCHX42, —N3, —CN, —SOn4R4D, —SOv4NR4AR4B, —NHC(O)NR4AR4B, —N(O)m4, —NR4AR4B, —C(O)R4C, —C(O)—OR4C, —C(O)NR4AR4B, —OR4D, —NR4ASO2R4D, —NR4AC(O)R4C, —NR4AC(O)OR4C, —NR4AOR4C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R5is hydrogen, halogen, —CX53, —CHX52, —CH2X5, —OCX53, —OCH2X5, —OCHX52, —N3, —CN, —SOn5R5D, —SOv5NR5AR5B, —NHC(O)NR5AR5B, —N(O)m5, —NR5AR5B, —C(O)R5C, —C(O)—OR5C, —C(O)NR5AR5B, —OR5D, —NR5ASO2R5D, —NR5AC(O)R5C, —NR5AC(O)OR5C, —NR5AOR5C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R6is hydrogen, halogen, —CX63, —CHX62, —CH2X6, —OCX63, —OCH2X6, —OCHX62, —N3, —CN, —SOn6R6D, —SOv6NR6AR6B, —NHC(O)NR6AR6B, —N(O)m6, —NR6AR6B, —C(O)R6C, —C(O)—OR6C, —C(O)NR6AR6B, —OR6D, —NR6ASO2R6D, —NR6AC(O)R6C, —NR6AC(O)OR6C, —NR6AOR6C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R7is hydrogen, halogen, —CX73, —CHX72, —CH2X7, —OCX73, —OCH2X7, —OCHX72, —N3, —CN, —SOn7R7D, —SOv7NR7AR7B, —NHC(O)NR7AR7B, —N(O)m7, —NR7AR7B, —C(O)R7C, —C(O)—OR7C, —C(O)NR7AR7B, —OR7D, —NR7ASO2R7D, —NR7AC(O)R7C, —NR7AC(O)OR7C, —NR7AOR7C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R8is hydrogen, halogen, —CX83, —CHX82, —CH2X8, —OCX83, —OCH2X8, —OCHX82, —N3, —CN, —SOn8R8D, —SOv8NR8AR8B, —NHC(O)NR8AR8B, —N(O)m8, —NR8AR8B, —C(O)R8C, —C(O)—OR8C, —C(O)NR8AR8B, —OR8D, —NR8ASO2R8D, —NR8AC(O)R8C, —NR8AC(O)OR8C, —NR8AOR8C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R9is hydrogen, halogen, —CX93, —CHX92, —CH2X9, —OCX93, —OCH2X9, —OCHX92, —N3, —CN, —SOn9R9D, —SOv9NR9AR9B, —NHC(O)NR9AR9B, —N(O)m9, —NR9AR9B, —C(O)R9C, —C(O)—OR9C, —C(O)NR9AR9B, —OR9D, —NR9ASO2R9D, —NR9AC(O)R9C, —NR9AC(O)OR9C, —NR9AOR9C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R10is hydrogen, halogen, —CX103, —CHX102, —CH2X10, —OCX103, —OCH2X10, —OCHX102, —N3, —CN, —SOn10R10D, —SOv10NR10AR10B, —NHC(O)NR10AR10B, —N(O)m10, —NR10AR10B, —C(O)R10C, —C(O)—OR10C, —C(O)NR10AR10B, —OR10D, —NR10ASO2R10D, —NR10AC(O)R10C, —NR10AC(O)OR10C, —NR10AOR10C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R11is hydrogen, halogen, —CX113, —CHX112, —CH2X11, —OCX113, —OCH2X11, —OCHX112, —N3, —CN, —SOn11R11D, —SOv11NR11AR11B, —NHC(O)NR11AR11B, —N(O)m11, —NR11AR11B, —C(O)R11C, —C(O)—OR11C, —C(O)NR11AR11B, —OR11D, —NR11ASO2R11D, —NR11AC(O)R11C, —NR11AC(O)OR11C, —NR11AOR11C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R12is hydrogen, halogen, —CX123, —CHX122, —CH2X12, —OCX123, —OCH2X12, —OCHX122, —N3, —CN, —SOnl2R12D, —SOv12NR12AR12B, —NHC(O)NR12AR12B, —N(O)m12, —NR12AR12B, —C(O)R12C, —C(O)—OR12C, —C(O)NR12AR12B, —OR12D, —NR12ASO2R12D, —NR12AC(O)R12C, —NR12AC(O)OR12C, —NR12AOR12C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R13is hydrogen, —CX133, —CHX132, —CH2X13, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12Cand R12Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R1and R2together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4and R5together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n1, n2, n3, n4, n5, n6, n7, n8, n9, n10, n11 and n12 are independently an integer from 0 to 4;m1, m2, m3, m4, m5, m6, m7, m8, m9, m10, m11, m12, v1, v2, v3, v4, v5, v6, v7, v8, v9, v10, v11 and v12 are independently an integer from 1 to 2; andX, X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, and X13are independently —F, —Cl, —Br, or —I,or a salt thereof. Embodiment Q19. The method of Embodiment Q18, wherein the compound has a formula (II): wherein:R14is hydrogen, halogen, —CX143, —CHX142, —CH2X14, —OCX143, —OCH2X14, —OCHX142, —N3, —CN, —SOn14R14D, —SOv14NR14AR14B, —NHC(O)NR14AR14B, —N(O)m14, —NR14AR14B, —C(O)R14C, —C(O)—OR14C, —C(O)NR14AR14B, —OR14D, —NR14ASO2R14D, —NR14AC(O)R14C, —NR14AC(O)OR14C, —NR14AOR14C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R15is hydrogen, halogen, —CX153, —CHX152, —CH2X15, —OCX153, —OCH2X15, —OCHX152, —N3, —CN, —SOnl5R15D, —SOv15NR15AR15B, —NHC(O)NR15AR15B, —N(O)m15, —NR15AR15B, —C(O)R15C, —C(O)—OR15C, —C(O)NR15AR15B, —OR15D, —NR15ASO2R15D, —NR15AC(O)R15C, —NR15AC(O)OR15C, —NR15AOR15C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R16is hydrogen, halogen, —CX163, —CHX162, —CH2X16, —OCX163, —OCH2X16, —OCHX162, —N3, —CN, —SOn16R16D, —SOv16NR16AR16B, —NHC(O)NR16AR16B, —N(O)m16, —NR16AR16B, —C(O)R16C, —C(O)—OR16C, —C(O)NR16AR16B, —OR16D, —NR16ASO2R16D, —NR16AC(O)R16C, —NR16AC(O)OR16C, —NR16AOR16C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R17is hydrogen, halogen, —CX173, —CHX172, —CH2X17, —OCX173, —OCH2X17, —OCHX172, —N3, —CN, —SOn17R17D, —SOv17NR17AR17B, —NHC(O)NR17AR17B, —N(O)m17, —NR17AR17B, —C(O)R17C, —C(O)—OR17C, —C(O)NR17AR17B, —OR17D, —NR17ASO2R17D, —NR17AC(O)R17C, —NR17AC(O)OR17C, —NR17AOR17C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R14A, R14B, R14C, R14D, R15A, R15B, R15C, R15D, R16A, R16B, R16C, R16D, R17A, R17B, R17C, and R17Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n14, n15, n16, and n17 are independently an integer from 0 to 4;m14, m15, m16, m17, v14, v15, v16, and v17 are independently an integer from 1 to 2; andX14, X15, X16, and X17are independently —F, —Cl, —Br, or —I. Embodiment Q20. The method of any one of Embodiments Q18-Q19, wherein L1is —O— or —S—. Embodiment Q21. The method of any one of Embodiments Q18-Q19, wherein L1is a bond. Embodiment Q22. The method of any one of Embodiments Q18-Q19, wherein L1is —S(O)2—, —NR13S(O)2— or —NR13C(O)—. Embodiment Q23. The method of any one of Embodiments Q18-Q22, wherein at least one of R1, R2and R3are —OH or —OCH3. Embodiment Q24. The method of any one of Embodiments Q18-Q23, wherein R7and R9are hydrogen. Embodiment Q25. The method of any one of Embodiments Q18-Q24, wherein each R6, R8, and R10is independently hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, or substituted or unsubstituted C1-C3alkyl. Embodiment Q26. The method of any one of Embodiments Q18-Q25, wherein the compound has a formula (III), Embodiment Q27. The method of any one of Embodiments Q18-Q25, wherein the compound has a formula (IV), Embodiment Q28. The method of any one of Embodiments Q18-Q25, wherein the compound has a formula (V), Embodiment Q29. The method of any one of Embodiments Q18-Q25, wherein the compound has a formula (VI). Embodiment Q30. The method of any one of Embodiments Q18-Q25, wherein the compound has a formula (VII), Embodiment Q31. he method of any one of Embodiments Q18-Q30, wherein the compound is Embodiment Q32. The method of any one of Embodiments Q18-Q31, wherein the compound inhibits the poly(ADP-ribose) glycohydrolase (PARG) in a cancer cell. Embodiment Q33. The method of Embodiment Q32, wherein the cancer cell is from breast cancer, ovarian cancer, lung cancer, pancreatic cancer, glioblastoma, uterine cancer, bladder cancer, esophagus cancer, gastric cancer, head and neck cancer, cholangiocarcinoma, mesothelioma, prostate cancer, colon carcinoma, fallopian tube cancer, lymphoma and leukemia. Embodiment Q34. A compound having a formula (I), wherein,L1is a bond, —CR11R12—, —NR13—, —O—, —S—, —S(O)2—, —NR13S(O)2—, or —NR13C(O)—;R1is hydrogen, halogen, —CX13, —CHX12, —CH2X1, —OCX13, —OCH2X1, —OCHX12, —N3, —CN, —SOn1R1D, —SOv1NR1AR1B, —NHC(O)NR1AR1B, —N(O)m1, —NR1AR1B, —C(O)R1C, —C(O)—OR1C, —C(O)NR1AR1B, —OR1D, —NR1ASO2R1D, —NR1AC(O)R1C, —NR1AC(O)OR1C, —NR1AOR1C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R2is hydrogen, halogen, —CX23, —CHX22, —CH2X2, —OCX23, —OCH2X2, —OCHX22, —N3, —CN, —SOn2R2D. —SOv2NR2AR2B, —NHC(O)NR2AR2B, —N(O)m2, —NR2AR2B, —C(O)R2C, —C(O)—OR2C, —C(O)NR2AR2B, —OR2D, —NR2ASO2R2D, —NR2AC(O)R2C, —NR2AC(O)OR2C, —NR2AOR2C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R3is hydrogen, halogen, —CX33, —CHX32, —CH2X3, —OCX33, —OCH2X3, —OCHX32, —N3, —CN, —SOn3R3D. —SOv3NR3AR3B, —NHC(O)NR3AR3B, —N(O)m3, —NR3AR3B, —C(O)R3C, —C(O)—OR3C, —C(O)NR3AR3B, —OR3D, —NR3ASO2R3D, —NR3AC(O)R3C, —NR3AC(O)OR3C, —NR3AOR3C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4is hydrogen, halogen, —CX43, —CHX42, —CH2X4, —OCX43, —OCH2X4, —OCHX42, —N3, —CN, —SOn4R4D, —SOv4NR4AR4B, —NHC(O)NR4AR4B, —N(O)m4, —NR4AR4B, —C(O)R4C, —C(O)—OR4C, —C(O)NR4AR4B, —OR4D, —NR4ASO2R4D, —NR4AC(O)R4C, —NR4AC(O)OR4C, —NR4AOR4C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R5is hydrogen, halogen, —CX53, —CHX52, —CH2X5, —OCX53, —OCH2X5, —OCHX52, —N3, —CN, —SOn6R6D, —SOv5NR5AR5B, —NHC(O)NR5AR5B, —N(O)m5, —NR5AR5B, —C(O)R5C, —C(O)—OR5C, —C(O)NR5AR5B, —OR5D, —NR5ASO2R5D, —NR5AC(O)R5C, —NR5AC(O)OR5C, —NR5AOR5C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R6is hydrogen, halogen, —CX63, —CHX62, —CH2X6, —OCX63, —OCH2X6, —OCHX62, —N3, —CN, —SOn6R®, —SOv6NR6AR6B, —NHC(O)NR6AR6B, —N(O)m6, —NR6AR6B, —C(O)R6C, —C(O)—OR6C, —C(O)NR6AR6B, —OR6D, —NR6ASO2R6D, —NR6AC(O)R6C, —NR6AC(O)OR6C, —NR6AOR6C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R7is hydrogen, halogen, —CX73, —CHX72, —CH2X7, —OCX73, —OCH2X7, —OCHX72, —N3, —CN, —SOn7R7D, —SOv7NR7AR7B, —NHC(O)NR7AR7B, —N(O)m7, —NR7AR7B, —C(O)R7C, —C(O)—OR7C, —C(O)NR7AR7B, —OR7D, —NR7ASO2R7D, —NR7AC(O)R7C, —NR7AC(O)OR7C, —NR7AOR7C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R8is hydrogen, halogen, —CX83, —CHX82, —CH2X8, —OCX83, —OCH2X8, —OCHX82, —N3, —CN, —SOn8R8D, —SOv8NR8AR8B, —NHC(O)NR8AR8B, —N(O)m8, —NR8AR8B, —C(O)R8C, —C(O)—OR8C, —C(O)NR8AR8B, —OR8D, —NR8ASO2R8D, —NR8AC(O)R8C, —NR8AC(O)OR8C, —NR8AOR8C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R9is hydrogen, halogen, —CX93, —CHX92, —CH2X9, —OCX93, —OCH2X9, —OCHX92, —N3, —CN, —SOn9R9D, —SOv9NR9AR9B, —NHC(O)NR9AR9B, —N(O)m9, —NR9AR9B, —C(O)R9C, —C(O)—OR9C, —C(O)NR9AR9B, —OR9D, —NR9ASO2R9D, —NR9AC(O)R9C, —NR9AC(O)OR9C, —NR9AOR9C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R10is hydrogen, halogen, —CX103, —CHX102, —CH2X10, —OCX103, —OCH2X10, —OCHX102, —N3, —CN, —SOn10R10D, —SOv10NR10AR10B, —NHC(O)NR10AR10B, —N(O)m10, —NR10AR10B, —C(O)R10C, —C(O)—OR10C, —C(O)NR10AR10B, —OR10D, —NR10ASO2R10D, —NR10AC(O)R10C, —NR10AC(O)OR10C, —NR10AOR10C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R11is hydrogen, halogen, —CX113, —CHX112, —CH2X11, —OCX113, —OCH2X11, —OCHX112, —N3, —CN, —SOn11R11D, —SOv11NR11AR11B, —NHC(O)NR11AR11B, —N(O)m11, —NR11AR11B, —C(O)R11C, —C(O)—OR11C, —C(O)NR11AR11B, —OR11D, —NR11ASO2R11D, —NR11AC(O) R11C, —NR11AC(O)OR11C, —NR11AOR11C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R12is hydrogen, halogen, —CX123, —CHX122, —CH2X12, —OCX123, —OCH2X12, —OCHX122, —N3, —CN, —SOnl2R12D, —SOv12NR12AR12B, —NHC(O)NR12AR12B, —N(O)m12, —NR12AR12B, —C(O)R12C, —C(O)—OR12C, —C(O)NR12AR12B, —OR12D, —NR12ASO2R12D, —NR12AC(O) R12C, —NR12AC(O)OR12C, —NR12AOR12C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R13is hydrogen, —CX133, —CHX132, —CH2X13, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12Cand R12Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R1and R2together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4and R5together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n1, n2, n3, n4, n5, n6, n7, n8, n9, n10, n11 and n12 are independently an integer from 0 to 4;m1, m2, m3, m4, m5, m6, m7, m8, m9, m10, m11, m12, v1, v2, v3, v4, v5, v6, v7, v8, v9, v10, v11 and v12 are independently an integer from 1 to 2; andX, X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, and X13are independently —F, —Cl, —Br, or —I,or a salt thereof, provided that when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R6is not —CH3; when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R8is not —CH3; and when L1is —S—, R1is —OH, and R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, then R10is not —CH3. Embodiment Q35. The compound of Embodiment Q34, wherein the compound has a formula (II): wherein:R14is hydrogen, halogen, —CX143, —CHX142, —CH2X14, —OCX143, —OCH2X14, OCHX142, —N3, —CN, —SOn14R14D, —SOv14NR14AR14B, —NHC(O)NR14AR14B, —N(O)m14, —NR14AR14B, —C(O)R14C, —C(O)—OR14C, —C(O)NR14AR14B, —OR14D, —NR14ASO2R14D, —NR14AC(O)R14C, —NR14AC(O)OR14C, —NR14AOR14C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R15is hydrogen, halogen, —CX153, —CHX152, —CH2X15, —OCX153, —OCH2X15, —OCHX152, —N3, —CN, —SOnl5R15D, —SOv15NR15AR15B, —NHC(O)NR15AR15B, —N(O)m15, —NR15AR15B, —C(O)R15C, —C(O)—OR15C, —C(O)NR15AR15B, —OR15D, —NR15ASO2R15D, —NR15AC(O)R15C, —NR15AC(O)OR15C, —NR15AOR15C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R16is hydrogen, halogen, —CX163, —CHX162, —CH2X16, —OCX163, —OCH2X16, —OCHX162, —N3, —CN, —SOn16R16D, —SOv16NR16AR16B, —NHC(O)NR16AR16B, —N(O)m16, —NR16AR16B, —C(O)R16C, —C(O)—OR16C, —C(O)NR16AR16B, —OR16D, —NR16ASO2R16D, —NR16AC(O)R16C, —NR16AC(O)OR16C, —NR16AOR16C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R17is hydrogen, halogen, —CX173, —CHX172, —CH2X17, —OCX173, —OCH2X17, —OCHX172, —N3, —CN, —SOn17R17D, —SOv17NR17AR17B, —NHC(O)NR17AR17B, —N(O)m17, —NR17AR17B, —C(O)R17C, —C(O)—OR17C, —C(O)NR17AR17B, —OR17D, —NR17ASO2R17D, —NR17AC(O)R17C, —NR17AC(O)OR17C, —NR17AOR17C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R14A, R14B, R14C, R14D, R15A, R15B, R15C, R15D, R16A, R16B, R16C, R16D, R17A, R17B, R17C, and R17Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n14, n15, n16, and n17 are independently an integer from 0 to 4;m14, m15, m16, m17, v14, v15, v16, and v17 are independently an integer from 1 to 2; andX14, X15, X16, and X17are independently —F, —Cl, —Br, or —I. Embodiment Q36. The compound of any one of claims1-2, wherein L1is —O— or —S—. Embodiment Q37. The compound of any one of Embodiments Q34-Q35, wherein L1is a bond. Embodiment Q38. The compound of any one of Embodiments Q34-Q35, wherein L1is —S(O)2—, —NR13S(O)2— or —NR13C(O)—. Embodiment Q39. The compound of any one of Embodiments Q34-Q38, wherein at least one of R1, R2and R3are —OH or —OCH3. Embodiment Q40. The compound of any one of Embodiments Q34-Q39, wherein R7and R9are hydrogen. Embodiment Q41. The compound of any one of Embodiments Q34-Q40, wherein each R6, R8, and R10is independently hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, or substituted or unsubstituted C1-C3alkyl. Embodiment Q42. The compound of any one of Embodiments Q34-Q41, wherein the compound has a formula (III), Embodiment Q43. The compound of any one of Embodiments Q34-Q41, wherein the compound has a formula (IV), Embodiment Q44. The compound of any one of Embodiments Q34-Q41, wherein the compound has a formula (V), Embodiment Q45. The compound of any one of Embodiments Q34-Q41, wherein the compound has a formula (VI), Embodiment Q46. The compound of any one of Embodiments Q34-Q41, wherein the compound has a formula (VII), Embodiment Q46. The compound of any one of Embodiments Q34-Q46, wherein the compound is Embodiment Q48. A pharmaceutical composition comprising a compound having a formula (I), wherein,L1is a bond, —CR11R12—, —NR13—, —O—, —S—, —S(O)2—, —NR13S(O)2—, or —NR13C(O)—;R1is hydrogen, halogen, —CX13, —CHX12, —CH2X1, —OCX13, —OCH2X1, —OCHX12, —N3, —CN, —SOn1R1D, —SOv1NR1AR1B, —NHC(O)NR1AR1B, —N(O)m1, —NR1AR1B, —C(O)R1C, C(O)—OR1C, —C(O)NR1AR1B, —OR1D, —NR1ASO2R1D, —NR1AC(O)R1C, —NR1AC(O)OR1C, —NR1AOR1C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R2is hydrogen, halogen, —CX23, —CHX22, —CH2X2, —OCX23, —OCH2X2, —OCHX22, —N3, —CN, —SOn2R2D, —SOv2NR2AR2B, —NHC(O)NR2AR2B, —N(O)m2, —NR2AR2B, —C(O)R2C, C(O)—OR2C, —C(O)NR2AR2B, —OR2D, —NR2ASO2R2D, —NR2AC(O)R2C, —NR2AC(O)OR2C, —NR2AOR2C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R3is hydrogen, halogen, —CX33, —CHX32, —CH2X3, —OCX33, —OCH2X3, —OCHX32, —N3, —CN, —SOn3R3D, —SOv3NR3AR3B, —NHC(O)NR3AR3B, —N(O)m3, —NR3AR3B, —C(O)R3C, —C(O)—OR3C, —C(O)NR3AR3B, —OR3D, —NR3ASO2R3D, —NR3AC(O)R3C, —NR3AC(O)OR3C, —NR3AOR3C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4is hydrogen, halogen, —CX43, —CHX42, —CH2X4, —OCX43, —OCH2X4, —OCHX42, —N3, —CN, —SOn4R4D, —SOv4NR4AR4B, —NHC(O)NR4AR4B, —N(O)m4, —NR4AR4B, —C(O)R4C, —C(O)—OR4C, —C(O)NR4AR4B, —OR4D, —NR4ASO2R4D, —NR4AC(O)R4C, —NR4AC(O)OR4C, —NR4AOR4C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R5is hydrogen, halogen, —CX53, —CHX52, —CH2X5, —OCX53, —OCH2X5, —OCHX52, —N3, —CN, —SOn5R5D, —SOv5NR5AR5B, —NHC(O)NR5AR5B, —N(O)m5, —NR5AR5B, —C(O)R5C, —C(O)—OR5C, —C(O)NR5AR5B, —OR5D, —NR5ASO2R5D, —NR5AC(O)R5C, —NR5AC(O)OR5C, —NR5AOR5C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R6is hydrogen, halogen, —CX63, —CHX62, —CH2X6, —OCX63, —OCH2X6, —OCHX62, —N3, —CN, —SOn6R6D, —SOv6NR6AR6B, —NHC(O)NR6AR6B, —N(O)m6, —NR6AR6B, —C(O)R6C, —C(O)—OR6C, —C(O)NR6AR6B, —OR6D, —NR6ASO2R6D, —NR6AC(O)R6C, —NR6AC(O)OR6C, —NR6AOR6C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R7is hydrogen, halogen, —CX73, —CHX72, —CH2X7, —OCX73, —OCH2X7, —OCHX72, —N3, —CN, —SOn77D, —SOv7NR7AR7B, —NHC(O)NR7AR7B, —N(O)m7, —NR7AR7B, —C(O)R7C, —C(O)—OR7C, —C(O)NR7AR7B, —OR7D, —NR7ASO2R7D, —NR7AC(O)R7C, —NR7AC(O)OR7C, —NR7AOR7C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R8is hydrogen, halogen, —CX83, —CHX82, —CH2X8, —OCX83, —OCH2X8, —OCHX82, —N3, —CN, —SOn8R8D, —SOv8NR8AR8B, —NHC(O)NR8AR8B, —N(O)m8, —NR8AR8B, —C(O)R8C, —C(O)—OR8C, —C(O)NR8AR8B, —OR8D, —NR8ASO2R8D, —NR8AC(O)R8C, —NR8AC(O)OR8C, —NR8AOR8C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R9is hydrogen, halogen, —CX93, —CHX92, —CH2X9, —OCX93, —OCH2X9, —OCHX92, —N3, —CN, —SOn9R9D, —SOv9NR9AR9B, —NHC(O)NR9AR9B, —N(O)m9, —NR9AR9B, —C(O)R9C, —C(O)—OR9C, —C(O)NR9AR9B, —OR9D, —NR9ASO2R9D, —NR9AC(O)R9C, —NR9AC(O)OR9C, —NR9AOR9C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R10is hydrogen, halogen, —CX103, —CHX102, —CH2X10, —OCX103, —OCH2X10, —OCHX102, —N3, —CN, —SOn10R10D, —SOv10NR10AR10B, —NHC(O)NR10AR10B, —N(O)m10, —NR10AR10B, —C(O)R10C, —C(O)—OR10C, —C(O)NR10AR10B, —OR10D, —NR10ASO2R10D, —NR10AC(O)R10C, —NR10AC(O)OR10C, —NR10AOR10C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R11is hydrogen, halogen, —CX113, —CHX112, —CH2X11, —OCX113, —OCH2X11, —OCHX112, —N3, —CN, —SOn11R11D, —SOv11NR11AR11B, —NHC(O)NR11AR11B, —N(O)m11, —NR11AR11B, —C(O)R11C, —C(O)—OR11C, —C(O)NR11AR11B, —OR11D, —NR11ASO2R11D, —NR11AC(O)R11C, —NR11AC(O)OR11C, —NR11AOR11C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R12is hydrogen, halogen, —CX123, —CHX122, —CH2X12, —OCX123, —OCH2X12, —OCHX122, —N3, —CN, —SOnl2R12D, —SOv12NR12AR12B, —NHC(O)NR12AR12B, —N(O)m12, —NR12AR12B, —C(O)R12C, —C(O)—OR12C, —C(O)NR12AR12B, —OR12D, —NR12ASO2R12D, —NR12AC(O)R12C, —NR12AC(O)OR12C, —NR12AOR12C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R13is hydrogen, —CX133, —CHX132, —CH2X13, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12Cand R12Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R1and R2together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4and R5together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n1, n2, n3, n4, n5, n6, n7, n8, n9, n10, n11 and n12 are independently an integer from 0 to 4;m1, m2, m3, m4, m5, m6, m7, m8, m9, m10, m11, m12, v1, v2, v3, v4, v5, v6, v7, v8, v9, v10, v11 and v12 are independently an integer from 1 to 2; andX, X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, and X13are independently —F, —Cl, —Br, or —I,or a salt thereof, and a pharmaceutically acceptable carrier. Embodiment Q49. The pharmaceutical composition of Embodiment Q48, wherein the compound has a formula (II): wherein:R14is hydrogen, halogen, —CX143, —CHX142, —CH2X14, —OCX143, —OCH2X14, —OCHX142, —N3, —CN, —SOn14R14D, —SOv14NR14AR14B, —NHC(O)NR14AR14B, —N(O)m14, —NR14AR14B, C(O)R14C, —C(O)—OR14C, —C(O)NR14AR14B, —OR14D, —NR14ASO2R14D, —NR14AC(O)R14C, —NR14AC(O)OR14C, —NR14AOR14C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R15is hydrogen, halogen, —CX153, —CHX152, —CH2X15, —OCX153, —OCH2X15, —OCHX152, —N3, —CN, —SOnl5R15D, —SOv15NR15AR15B, —NHC(O)NR15AR15B, —N(O)m15, —NR15AR15B, —C(O)R15C, —C(O)—OR15C, —C(O)NR15AR15B, —OR15D, —NR15ASO2R15D, —NR15AC(O)R15C, —NR15AC(O)O R15C, —NR15AOR15C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R16is hydrogen, halogen, —CX163, —CHX162, —CH2X16, —OCX163, —OCH2X16, —OCHX162, —N3, —CN, —SOn16R16D, —SOv16NR16AR16B, —NHC(O)NR16AR16B, —N(O)m16, —NR16AR16B, —C(O)R16C, —C(O)—OR16C, —C(O)NR16AR16B, —OR16D, —NR16ASO2R16D, —NR16AC(O)R16C, —NR16AC(O)OR16C, —NR16AOR16C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R17is hydrogen, halogen, —CX173, —CHX172, —CH2X17, —OCX173, —OCH2X17, —OCHX172, —N3, —CN, —N3, —SOn17R17D, —SOv17NR17AR17B, —NHC(O)NR17AR17B, —N(O)m17, —NR17AR17B, —C(O)R17C, —C(O)—OR17C, —C(O)NR17AR17B, —OR17D, —NR17ASO2R17D, —NR17AC(O) R17C, —NR17AC(O)OR17C, —NR17AOR17C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R14A, R14B, R14C, R14D, R15A, R15B, R15C, R15D, R16A, R16B, R16C, R16D, R17A, R17B, R17C, and R17Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n14, n15, n16, and n17 are independently an integer from 0 to 4;m14, m15, m16, m17, v14, v15, v16, and v17 are independently an integer from 1 to 2; andX14, X15, X16, and X17are independently —F, —Cl, —Br, or —I. Embodiment Q50. The pharmaceutical composition of any one of Embodiments Q48-Q49, wherein L1is —O— or —S—. Embodiment Q51. The pharmaceutical composition of any one of Embodiments Q48-Q49, wherein L1is a bond. Embodiment Q52. The pharmaceutical composition of any one of Embodiments Q48-Q49, wherein L1is —S(O)2—, —NR13S(O)2— or —NR13C(O)—. Embodiment Q53. The pharmaceutical composition of any one of Embodiments Q48-Q52, wherein at least one of R1, R2and R3are —OH or —OCH3. Embodiment Q54. The pharmaceutical composition of any one of Embodiments Q48-Q53, wherein R7and R9are hydrogen. Embodiment Q55. The pharmaceutical composition of any one of Embodiments Q48-Q54, wherein each R6, R8, and R10is independently hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, or substituted or unsubstituted C1-C3alkyl. Embodiment Q56. The pharmaceutical composition of any one of Embodiments Q48-Q55, wherein the compound has a formula (III) Embodiment Q57. The pharmaceutical composition of any one of Embodiments Q48-Q55, wherein the compound has a formula (IV), Embodiment Q58. The pharmaceutical composition of any one of Embodiments Q48-Q55, wherein the compound has a formula (V), Embodiment Q59. The pharmaceutical composition of any one of Embodiments Q48-Q55, wherein the compound has a formula (VI), Embodiment Q60. The pharmaceutical composition of any one of Embodiments Q48-Q55, wherein the compound has a formula (VII), Embodiment Q61. The pharmaceutical composition of any one of Embodiments Q48-Q60, wherein the compound is EMBODIMENTS Embodiment 1. A compound having a formula (I), wherein,L1is a bond, —CR11R12—, —NR13—, —O—, —S—, —S(O)—, —S(O)2—, —NR13S(O)—, —NR13S(O)2—, or —NR13C(O)—;R1is hydrogen, halogen, —CX33, —CHX12, —CH2X1, —OCX13, —OCH2X1, —OCHX12, —N3, —CN, —SOn1R1D, —SOv1NR1AR1B, —NHC(O)NR1AR1B, —N(O)m1, —NR1AR1B, —C(O)R1C, —C(O)—OR1C, —C(O)NR1AR1B, —OR1D, —NR1ASO2R1D, —NR1AC(O)R1C, —NR1AC(O)OR1C, —NR1AOR1C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R2is hydrogen, halogen, —CX23, —CHX22, —CH2X2, —OCX23, —OCH2X2, —OCHX22, —N3, —CN, —SOn2R2D. —SOv2NR2AR2B, —NHC(O)NR2AR2B, —N(O)m2, —NR2AR2B, —C(O)R2C, —C(O)—OR2C, —C(O)NR2AR2B, —OR2D, —NR2ASO2R2D, —NR2AC(O)R2C, —NR2AC(O)OR2C, —NR2AOR2C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R3is hydrogen, halogen, —CX33, —CHX32, —CH2X3, —OCX33, —OCH2X3, —OCHX32, —N3, —CN, —SOn3R3D. —SOv3NR3AR3B, —NHC(O)NR3AR3B, —N(O)m3, —NR3AR3B, —C(O)R3C, —C(O)—OR3C, —C(O)NR3AR3B, —OR3D, —NR3ASO2R3D, —NR3AC(O)R3C, —NR3AC(O)OR3C, —NR3AOR3C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4is hydrogen, halogen, —CX43, —CHX42, —CH2X4, —OCX43, —OCH2X4, —OCHX42, —N3, —CN, —SOn4R4D, —SOv4NR4AR4B, —NHC(O)NR4AR4B, —N(O)m4, —NR4AR4B, —C(O)R4C, —C(O)—OR4C, —C(O)NR4AR4B, —OR4D, —NR4ASO2R4D, —NR4AC(O)R4C, —NR4AC(O)OR4C, —NR4AOR4C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R5is hydrogen, halogen, —CX53, —CHX52, —CH2X5, —OCX53, —OCH2X5, —OCHX52, —N3, —CN, —SOn5R5D, —SOv5NR5AR5B, —NHC(O)NR5AR5B, —N(O)m5, —NR5AR5B, —C(O)R5C, —C(O)—OR5C, —C(O)NR5AR5B, —OR5D, —NR5ASO2R5D, —NR5AC(O)R5C, —NR5AC(O)OR5C, —NR5AOR5C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R6is hydrogen, halogen, —CX63, —CHX62, —CH2X6, —OCX63, —OCH2X6, —OCHX62, —N3, —CN, —SOn6R6D, —SOv6NR6AR6B, —NHC(O)NR6AR6B, —N(O)m6, —NR6AR6B, —C(O)R6C, —C(O)—OR6C, —C(O)NR6AR6B, —OR6D, —NR6ASO2R6D, —NR6AC(O)R6C, —NR6AC(O)OR6C, —NR6AOR6C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R7is hydrogen, halogen, —CX73, —CHX72, —CH2X7, —OCX73, —OCH2X7, —OCHX72, —N3, —CN, —SOn7R7D, —SOv7NR7AR7B, —NHC(O)NR7AR7B, —N(O)m7, —NR7AR7B, —C(O)R7C, —C(O)—OR7C, —C(O)NR7AR7B, —OR7D, —NR7ASO2R7D, —NR7AC(O)R7C, —NR7AC(O)OR7C, —NR7AOR7C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R8is hydrogen, halogen, —CX83, —CHX82, —CH2X8, —OCX83, —OCH2X8, —OCHX82, —N3, —CN, —SOn8R8D, —SOv8NR8AR8B, —NHC(O)NR8AR8B, —N(O)m8, —NR8AR8B, —C(O)R8C, —C(O)—OR8C, —C(O)NR8AR8B, —OR8D, —NR8ASO2R8D, —NR8AC(O)R8C, —NR8AC(O)OR8C, —NR8AOR8C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R9is hydrogen, halogen, —CX93, —CHX92, —CH2X9, —OCX93, —OCH2X9, —OCHX92, —N3, —CN, —SOn9R9D, —SOv9NR9AR9B, —NHC(O)NR9AR9B, —N(O)m9, —NR9AR9B, —C(O)R9C, —C(O)—OR9C, —C(O)NR9AR9B, —OR9D, —NR9ASO2R9D, —NR9AC(O)R9C, —NR9AC(O)OR9C, —NR9AOR9C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R10is hydrogen, halogen, —CX103, —CHX102, —CH2X10, —OCX103, —OCH2X10, —OCHX102, —N3, —CN, —SOn10R10D, —SOv10NR10AR10B, —NHC(O)NR10AR10B, —N(O)m10, —NR10AR10B, —C(O)R10C, —C(O)—OR10C, —C(O)NR10AR10B, —OR10D, —NR10ASO2R10D, —NR10AC(O)R10C, —NR10AC(O)OR10C, —NR10AOR10C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R11is hydrogen, halogen, —CX113, —CHX112, —CH2X11, —OCX113, —OCH2X11, —OCHX112, —N3, —CN, —SOn11R11D, —SOv11NR11AR11B, —NHC(O)NR11AR11B, —N(O)m11, —NR11AR11B, —C(O)R11C, —C(O)—OR11C, —C(O)NR11AR11B, —OR11D, —NR11ASO2R11D, —NR11AC(O) R11C, —NR11AC(O)OR11C, —NR11AOR11C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R12is hydrogen, halogen, —CX123, —CHX122, —CH2X12, —OCX123, —OCH2X12, —OCHX122, —N3, —CN, —SOnl2R12D, —SOv12NR12AR12B, —NHC(O)NR12AR12B, —N(O)m12, —NR12AR12B, —C(O)R12C, —C(O)—OR12C, —C(O)NR12AR12B, —OR12D, —NR12ASO2R12D, —NR12AC(O) R12C, —NR12AC(O)OR12C, —NR12AOR12C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R13is hydrogen, —CX133, —CHX132, —CH2X13, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12Cand R12Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R1and R2together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4and R5together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n1, n2, n3, n4, n5, n6, n7, n8, n9, n10, n11 and n12 are independently an integer from 0 to 4;m1, m2, m3, m4, m5, m6, m7, m8, m9, m10, m11, m12, v1, v2, v3, v4, v5, v6, v7, v8, v9, v10, v11 and v12 are independently an integer from 1 to 2; andX, X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, and X13are independently —F, —Cl, —Br, or —I,or a salt thereof,provided that:when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is a bond, R1is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —C(O)NH2;when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S— or —S(O)2—, R1is —OH, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3;when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —S(O)2—, R1is —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen or —CH3;when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHS(O)2— or —NH—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl or —CH3;when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3;when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R7, R9and R10are hydrogen, then R8is not hydrogen, —Cl, —Br, —CH3, —C(CH3)3, —OH, or —OCH3;when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R6, R8and R10are hydrogen, then R7or R9is not —Cl, —Br, —CH3, —OH, or —OCH3;when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, R1is —OH or —OCH3, and R7, R8and R9are hydrogen, then R6or R10is not —Cl, —Br, —CH3, —OH, or —OCH3;when R4and R5together with atoms attached thereto are joined to form unsubstituted phenyl, L1is —NHC(O)—, and R1is —OH or —OCH3, then at least one of R6, R7and R8are not —OCH3, or at least one of R8, R9and R10are not —OCH3. Embodiment 2. The compound of Embodiment 1, wherein the compound has a formula (IIA): wherein:R14is hydrogen, halogen, —CX143, —CHX142, —CH2X14, —OCX143, —OCH2X14, OCHX142, —N3, —CN, —SOn14R14D, —SOv14NR14AR14B, —NHC(O)NR14AR14B, —N(O)m14, —NR14AR14B, —C(O)R14C, —C(O)—OR14C, —C(O)NR14AR14B, —OR14D, —NR14ASO2R14D, —NR14AC(O)R14C, —NR14AC(O)OR14C, —NR14AOR14C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R15is hydrogen, halogen, —CX153, —CHX152, —CH2X15, —OCX153, —OCH2X15, —OCHX152, —N3, —CN, —SOnl5R15D, —SOv15NR15AR15B, —NHC(O)NR15AR15B, —N(O)m15, —NR15AR15B, —C(O)R15C, —C(O)—OR15C, —C(O)NR15AR15B, —OR15D, —NR15ASO2R15D, —NR15AC(O)R15C, —NR15AC(O)OR15C, —NR15AOR15C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R16is hydrogen, halogen, —CX163, —CHX162, —CH2X16, —OCX163, —OCH2X16, —OCHX162, —N3, —CN, —SOn16R16D, —SOv16NR16AR16B, —NHC(O)NR16AR16B, —N(O)m16, —NR16AR16B, —C(O)R16C, —C(O)—OR16C, —C(O)NR16AR16B, —OR16D, —NR16ASO2R16D, —NR16AC(O)R16C, —NR16AC(O)OR16C, —NR16AOR16C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R17is hydrogen, halogen, —CX173, —CHX172, —CH2X17, —OCX173, —OCH2X17, —OCHX172, —N3, —CN, —SOn17R17D, —SOv17NR17AR17B, —NHC(O)NR17AR17B, —N(O)m17, —NR17AR17B, —C(O)R17C, —C(O)—OR17C, —C(O)NR17AR17B, —OR17D, —NR17ASO2R17D, —NR17AC(O)R17C, —NR17 AC(O)OR17C, —NR17AOR17C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; Each R14A, R14B, R14C, R14D, R15A, R15B, R15C, R15D, R16A, R16B, R16C, R16D, R17A, R17B, R17C, and R17Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n14, n15, n16, and n17 are independently an integer from 0 to 4;m14, m15, m16, m17, v14, v15, v16, and v17 are independently an integer from 1 to 2; and X14, X15, X16, and X17are independently —F, —Cl, —Br, or —I. Embodiment 3. The compound of any one of Embodiments 1-2, wherein L1is —O— or —S—. Embodiments 4. The compound of any one of Embodiments 1-2, wherein L1is a bond. Embodiment 5. The compound of any one of Embodiments 1-2, wherein L1is —S(O)—, —S(O)2—, —NR13S(O)—, —NR13S(O)2— or —NR13C(O)—. Embodiment 6. The compound of any one of Embodiments 1-5, wherein at least one of R1, R2and R3are —OH or —OCH3. Embodiment 7. The compound of any one of Embodiments 1-6, wherein R7and R9are hydrogen. Embodiment 8. The compound of any one of Embodiments 1-7, wherein each R6, R8, and R10is independently hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, or substituted or unsubstituted C1-C3alkyl. Embodiment 9. The compound of any one of Embodiments 1-8, wherein the compound has a formula (III), Embodiment 10. The compound of any one of Embodiments 1-8, wherein the compound has a formula (IV), Embodiment 11. The compound of any one of Embodiments 1-8, wherein the compound has a formula (V), Embodiment 12. The compound of any one of Embodiments 1-8, wherein the compound has a formula (VI), Embodiment 13. The compound of any one of Embodiments 1-8, wherein the compound has a formula (VII), Embodiment 14. The compound of Embodiment 1, wherein the compound has a formula (VIII), wherein:R1Dis hydrogen or unsubstituted C1-C4alkyl;R6is hydrogen or —C(O)—OR6C;R7is hydrogen or halogen; and R8is halogen, —OR8D, —C(O)—OR8C, or unsubstituted C2-C4alkyl. Embodiment 15. The compound of Embodiment 14, wherein R1D, R6C, R8C, and R8Dare independently hydrogen or —CH3. Embodiment 16. The compound of Embodiment 15, wherein:R1Dis hydrogen;R6and R7are hydrogen; and R8is —OH, —OCH3, —COOH, —Br, or —C(CH3)3. Embodiment 17. The compound of Embodiment 15, wherein:R1Dis —CH3;R6and R7are hydrogen; and R8is —OH, —OCH3, —COOH, —COOCH3, —Cl, —Br, or —C(CH3)3. Embodiment 18. The compound of Embodiment 15, wherein:R1Dis hydrogen or —CH3;R6is hydrogen; andR7and R8are halogen. Embodiment 19. The compound of Embodiment 15, wherein:R1Dis hydrogen or —CH3;R7is halogen; andR7and R8are hydrogen. Embodiment 20. The compound of Embodiment 15, wherein:R1Dis hydrogen or —CH3;R6is —C(O)—OR6C; andR7and R8are hydrogen. Embodiment 21. The compound of Embodiment 1, wherein the compound has a formula (IX), wherein:R1D, R2D, and R3Dare independently hydrogen or unsubstituted C1-C4alkyl; and R6is hydrogen, halogen, —C(O)—OR6C, —OR6D, or unsubstituted C1-C4alkyl. Embodiment 22. The compound of Embodiment 21, wherein:R1D, R2D, and R3Dare independently hydrogen or —CH3; and R6Cand R6Dare independently hydrogen or —CH3. Embodiment 23. The compound of any one of Embodiments 1-22, wherein the compound is: Embodiment 24. A method of treating cancer in a subject in need thereof, the method comprising administering to the subject an effective amount of a compound having a formula (I), wherein:L1is a bond, —CR11R12—, —NR13—, —O—, —S—, —S(O)—, —S(O)2—, —NR13S(O)—, —NR13S(O)2—, or —NR13C(O)—;R1is hydrogen, halogen, —CX33, —CHX12, —CH2X1, —OCX13, —OCH2X1, —OCHX12, —N3, —CN, —SOn1R1D, —SOv1NR1AR1B, —NHC(O)NR1AR1B, —N(O)m1, —NR1AR1B, —C(O)R1C, C(O)—OR1C, —C(O)NR1AR1B, —OR1D, —NR1ASO2R1D, —NR1AC(O)R1C, —NR1AC(O)OR1C, —NR1AOR1C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R2is hydrogen, halogen, —CX23, —CHX22, —CH2X2, —OCX23, —OCH2X2, —OCHX22, —N3, —CN, —SOn2R2D, —SOv2NR2AR2B, —NHC(O)NR2AR2B, —N(O)m2, —NR2AR2B, —C(O)R2C, C(O)—OR2C, —C(O)NR2AR2B, —OR2D, —NR2ASO2R2D, —NR2AC(O)R2C, —NR2AC(O)OR2C, —NR2AOR2C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R3is hydrogen, halogen, —CX33, —CHX32, —CH2X3, —OCX33, —OCH2X3, —OCHX32, —N3, —CN, —SOn3R3D, —SOv3NR3AR3B, —NHC(O)NR3AR3B, —N(O)m3, —NR3AR3B, —C(O)R3C, C(O)—OR3C, —C(O)NR3AR3B, —OR3D, —NR3ASO2R3D, —NR3AC(O)R3C, —NR3AC(O)OR3C, —NR3AOR3C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4is hydrogen, halogen, —CX43, —CHX42, —CH2X4, —OCX43, —OCH2X4, —OCHX42, —N3, —CN, —SOn4R4D, —SOv4NR4AR4B, —NHC(O)NR4AR4B, —N(O)m4, —NR4AR4B, —C(O)R4C, C(O)—OR4C, —C(O)NR4AR4B, —OR4D, —NR4ASO2R4D, —NR4AC(O)R4C, —NR4AC(O)OR4C, —NR4AOR4C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R5is hydrogen, halogen, —CX53, —CHX52, —CH2X5, —OCX53, —OCH2X5, —OCHX52, —N3, —CN, —SOn5R5D, —SOv5NR5AR5B, —NHC(O)NR5AR5B, —N(O)m5, —NR5AR5B, —C(O)R5C, C(O)—OR5C, —C(O)NR5AR5B, —OR5D, —NR5ASO2R5D, —NR5AC(O)R5C, —NR5AC(O)OR5C, —NR5AOR5C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R6is hydrogen, halogen, —CX63, —CHX62, —CH2X6, —OCX63, —OCH2X6, —OCHX82, —N3, —CN, —SOn6R6D, —SOv6NR6AR6B, —NHC(O)NR6AR6B, —N(O)m6, —NR6AR6B, —C(O)R6C, C(O)—OR6C, —C(O)NR6AR6B, —OR6D, —NR6ASO2R6D, —NR6AC(O)R6C, —NR6AC(O)OR6C, —NR6AOR6C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R7is hydrogen, halogen, —CX73, —CHX72, —CH2X7, —OCX73, —OCH2X7, —OCHX72, —N3, —CN, —SOn7R7D, —SOv7NR7AR7B, —NHC(O)NR7AR7B, —N(O)m7, —NR7AR7B, —C(O)R7C, C(O)—OR7C, —C(O)NR7AR7B, —OR7D, —NR7ASO2R7D, —NR7AC(O)R7C, —NR7AC(O)OR7C, —NR7AOR7C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R8is hydrogen, halogen, —CX83, —CHX82, —CH2X8, —OCX83, —OCH2X8, —OCHX82, —N3, —CN, —SOn8R8D, —SOv8NR8AR8B, —NHC(O)NR8AR8B, —N(O)m8, —NR8AR8B, —C(O)R8C, C(O)—OR8C, —C(O)NR8AR8B, —OR8D, —NR8ASO2R8D, —NR8AC(O)R8C, —NR8AC(O)OR8C, —NR8AOR8C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R9is hydrogen, halogen, —CX93, —CHX92, —CH2X9, —OCX93, —OCH2X9, —OCHX92, —N3, —CN, —SOn9R9D, —SOv9NR9AR9B, —NHC(O)NR9AR9B, —N(O)m9, —NR9AR9B, —C(O)R9C, C(O)—OR9C, —C(O)NR9AR9B, —OR9D, —NR9ASO2R9D, —NR9AC(O)R9C, —NR9AC(O)OR9C, —NR9AOR9C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R10is hydrogen, halogen, —CX103, —CHX102, —CH2X10, —OCX103, —OCH2X10, —OCHX102, —N3, —CN, —SOn10R10D, —SOv10NR10AR10B, —NHC(O)NR10AR10B, —N(O)m10, —NR10AR10B, —C(O)R10C, —C(O)—OR10C, —C(O)NR10AR10B, —OR10D, —NR10ASO2R10D, —NR10AC(O)R10C, —NR10AC(O)OR10C, —NR10AOR10C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R11is hydrogen, halogen, —CX113, —CHX112, —CH2X11, —OCX113, —OCH2X11, —OCHX112, —N3, —CN, —SOn11R11D, —SOv11NR11AR11B, —NHC(O)NR11AR11B, —N(O)m11, —NR11AR11B, —C(O)R11C, —C(O)—OR11C, —C(O)NR11AR11B, —OR11D, —NR11ASO2R11D, —NR11AC(O)R11C, —NR11AC(O)OR11C, —NR11AOR11C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R12is hydrogen, halogen, —CX123, —CHX122, —CH2X12, —OCX123, —OCH2X12, —OCHX122, —N3, —CN, —SOnl2R12D, —SOv12NR12AR12B, —NHC(O)NR12AR12B, —N(O)m12, —NR12AR12B, —C(O)R12C, —C(O)—OR12C, —C(O)NR12AR12B, —OR12D, —NR12ASO2R12D, —NR12AC(O) R12C, —NR12AC(O)OR12C, —NR12AOR12C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R13is hydrogen, —CX133, —CHX132, —CH2X13, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12Cand R12Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R1and R2together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4and R5together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n1, n2, n3, n4, n5, n6, n7, n8, n9, n10, n11 and n12 are independently an integer from 0 to 4;m1, m2, m3, m4, m5, m6, m7, m8, m9, m10, m11, m12, v1, v2, v3, v4, v5, v6, v7, v8, v9, v10, v11 and v12 are independently an integer from 1 to 2; andX, X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, and X13are independently —F, —Cl, —Br, or —I,or a salt thereof. Embodiment 25. The method of Embodiment 24, wherein the compound has a formula (II): wherein:R14is hydrogen, halogen, —CX143, —CHX142, —CH2X14, —OCX143, —OCH2X14, —OCHX142, —N3, —CN, —SOnl4R14D, —SOv14NR14AR14B, —NHC(O)NR14AR14B, —N(O)m14, —NR14AR14B, —C(O)R14C, —C(O)—OR14C, —C(O)NR14AR14B, —OR14D, —NR14ASO2R14D, —NR14AC(O) R14C, —NR14AC(O)OR14C, —NR14AOR14C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R15is hydrogen, halogen, —CX153, —CHX152, —CH2X15, —OCX153, —OCH2X15, —OCHX152, —N3, —CN, —SOnl5R15D, —SOv15NR15AR15B, —NHC(O)NR15AR15B, —N(O)m15, —NR15AR15B, —C(O)R15C, —C(O)—OR15C, —C(O)NR15AR15B, —OR15D, —NR15ASO2R15D, —NR15AC(O) R15C, —NR15AC(O)OR15C, —NR15AOR15C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R16is hydrogen, halogen, —CX163, —CHX162, —CH2X16, —OCX163, —OCH2X16, —OCHX162, —N3, —CN, —SOn16R16D, —SOv16NR16AR16B, —NHC(O)NR16AR16B, —N(O)m16, —NR16AR16B, —C(O)R16C, —C(O)—OR16C, —C(O)NR16AR16B, —OR16D, —NR16ASO2R16D, —NR16AC(O) R16C, —NR16AC(O)OR16C, —NR16AOR16C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R17is hydrogen, halogen, —CX173, —CHX172, —CH2X17, —OCX173, —OCH2X17, —OCHX172, —N3, —CN, —SOn17R17D, —SOv17NR17AR17B, —NHC(O)NR17AR17B, —N(O)m17, —NR17AR17B, —C(O)R17C, —C(O)—OR17C, —C(O)NR17AR17B, —OR17D, —NR17ASO2R17D, —NR17AC(O) R17C, —NR17AC(O)OR17C, —NR17AOR17C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R14A, R14B, R14C, R14D, R15A, R15B, R15C, R15D, R16A, R16B, R16C, R16D, R17A, R17B, R17C, and R17Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n14, n15, n16, and n17 are independently an integer from 0 to 4;m14, m15, m16, m17, v14, v15, v16, and v17 are independently an integer from 1 to 2; andX14, X15, X16, and X17are independently —F, —Cl, —Br, or —I. Embodiment 26. The method of any one of Embodiments 24-25, wherein L1is —O— or —S—. Embodiment 27. The method of any one of Embodiments 24-25, wherein L1is a bond. Embodiment 28. The method of any one of Embodiments 24-25, wherein L1is —S(O)2—, —NR13S(O)2— or —NR13C(O)—. Embodiment 29. The method of any one of Embodiments 24-28, wherein at least one of R1, R2and R3are —OH or —OCH3. Embodiment 30. The method of any one of Embodiments 24-29, wherein R7and R9are hydrogen. Embodiment 31. The method of any one of Embodiments 24-30, wherein each R6, R8, and R10is independently hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, or substituted or unsubstituted C1-C3alkyl. Embodiment 32. The method of any one of Embodiments 24-31, wherein the compound has a formula (ITT), Embodiment 33. The method of any one of Embodiments 24-31, wherein the compound has a formula (IV), Embodiment 34. The method of any one of Embodiments 24-31, wherein the compound has a formula (V), Embodiment 35. The method of any one of Embodiments 24-31, wherein the compound has a formula (VI), Embodiment 36. The method of any one of Embodiments 24-31, wherein the compound has a formula (VII), Embodiment 37. The method of Embodiment 24, wherein the compound has a formula (VIII), wherein:R1Dis hydrogen or unsubstituted C1-C4alkyl;R6is hydrogen or —C(O)—OR6C;R7is hydrogen or halogen; and R8is halogen, —OR8D, —C(O)—OR8C, or unsubstituted C2-C4alkyl. Embodiment 38. The method of Embodiment 37, wherein R1D, R6C, R8C, and R8Dare independently hydrogen or —CH3. Embodiment 39. The method of Embodiment 38, wherein:R1Dis hydrogen;R6and R7are hydrogen; and R8is —OH, —OCH3, —COOH, —Br, or —C(CH3)3. Embodiment 40. The method of Embodiment 38, wherein:R1Dis —CH3;R6and R7are hydrogen; andR8is —OH, —OCH3, —COOH, —COOCH3, —Cl, —Br, or —C(CH3)3. Embodiment 41. The method of Embodiment 38, wherein:R1Dis hydrogen or —CH3;R6is hydrogen; andR7and R8are halogen. Embodiment 42. The method of Embodiment 38, wherein:R1Dis hydrogen or —CH3;R7is halogen; andR7and R8are hydrogen. Embodiment 43. The method of Embodiment 38, wherein:R1Dis hydrogen or —CH3;R6is —C(O)—OR6C; andR7and R8are hydrogen. Embodiment 44. The method of Embodiment 24, wherein the compound has a formula (IX). wherein:R1D, R2D, and R3Dare independently hydrogen or unsubstituted C1-C4alkyl; and R6is hydrogen, halogen, —C(O)—OR6C, —OR6D, or unsubstituted C1-C4alkyl. Embodiment 45. The method of Embodiment 44, wherein:R1D, R2D, and R3Dare independently hydrogen or —CH3; andR6Cand R6Dare independently hydrogen or —CH3. Embodiment 46. The method of any one of Embodiments 24-45, wherein the compound is Embodiment 47. The method of any one of Embodiments 24-46, wherein the compound inhibits poly(ADP-ribose) glycohydrolase (PARG) in a cancer cell. Embodiment 48. The method of any one of Embodiments 24-47, wherein the cancer is selected from: breast cancer, ovarian cancer, lung cancer, pancreatic cancer, glioblastoma, uterine cancer, bladder cancer, esophagus cancer, gastric cancer, head and neck cancer, cholangiocarcinoma, mesothelioma, prostate cancer, colon carcinoma, fallopian tube cancer, lymphoma and leukemia. Embodiment 49. The method of Embodiment 48, wherein the cancer is lymphoma. Embodiment 50. A method of inhibiting a poly(ADP-ribose) glycohydrolase (PARG), the method comprising contacting the PARG with a compound having a formula (I), wherein:L1is a bond, —CR11R12—, —NR13—, —O—, —S—, —S(O)—, —S(O)2—, —NR13S(O)—, —NR13S(O)2—, or —NR13C(O)—;R1is hydrogen, halogen, —CX33, —CHX12, —CH2X1, —OCX13, —OCH2X1, —OCHX12, —N3, —CN, —SOn1R1D, —SOv1NR1AR1B, —NHC(O)NR1AR1B, —N(O)m1, —NR1AR1B, —C(O)R1C, —C(O)—OR1C, —C(O)NR1AR1B, —OR1D, —NR1ASO2R1D, —NR1AC(O)R1C, —NR1AC(O)OR1C, —NR1AOR1C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R2is hydrogen, halogen, —CX23, —CHX22, —CH2X2, —OCX23, —OCH2X2, —OCHX22, —N3, —CN, —SOv2R2D. —SOv2NR2AR2B, —NHC(O)NR2AR2B, —N(O)m2, —NR2AR2B, —C(O)R2C, —C(O)—OR2C, —C(O)NR2AR2B, —OR2D, —NR2ASO2R2D, —NR2AC(O)R2C, —NR2AC(O)OR2C, —NR2AOR2C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R3is hydrogen, halogen, —CX33, —CHX32, —CH2X3, —OCX33, —OCH2X3, —OCHX32, —N3, —CN, —SOn3R3D. —SOv3NR3AR3B, —NHC(O)NR3AR3B, —N(O)m3, —NR3AR3B, —C(O)R3C, —C(O)—OR3C, —C(O)NR3AR3B, —OR3D, —NR3ASO2R3D, —NR3AC(O)R3C, —NR3AC(O)OR3C, —NR3AOR3C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4is hydrogen, halogen, —CX43, —CHX42, —CH2X4, —OCX43, —OCH2X4, —OCHX42, —N3, —CN, —SOn4R4D, —SOv4NR4AR4B, —NHC(O)NR4AR4B, —N(O)m4, —NR4AR4B, —C(O)R4C, —C(O)—OR4C, —C(O)NR4AR4B, —OR4D, —NR4ASO2R4D, —NR4AC(O)R4C, —NR4AC(O)OR4C, —NR4AOR4C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R5is hydrogen, halogen, —CX53, —CHX52, —CH2X5, —OCX53, —OCH2X5, —OCHX52, —N3, —CN, —SOn5R5D, —SOv5NR5AR5B, —NHC(O)NR5AR5B, —N(O)m5, —NR5AR5B, —C(O)R5C, —C(O)—OR5C, —C(O)NR5AR5B, —OR5D, —NR5ASO2R5D, —NR5AC(O)R5C, —NR5AC(O)OR5C, —NR5AOR5C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R6is hydrogen, halogen, —CX63, —CHX62, —CH2X6, —OCX63, —OCH2X6, —OCHX62. —N3, —CN, —SOn6R6D, —SOv6NR6AR6B, —NHC(O)NR6AR6B, —N(O)m6, —NR6AR6B, —C(O)R6C, —C(O)—OR6C, —C(O)NR6AR6B, —OR6D, —NR6ASO2R6D, —NR6AC(O)R6C, —NR6AC(O)OR6C, —NR6AOR6C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R7is hydrogen, halogen, —CX73, —CHX72, —CH2X7, —OCX73, —OCH2X7, —OCHX72, —N3, —CN, —SOn7R7D, —SOv7NR7AR7B, —NHC(O)NR7AR7B, —N(O)m7, —NR7AR7B, —C(O)R7C, —C(O)—OR7C, —C(O)NR7AR7B, —OR7D, —NR7ASO2R7D, —NR7AC(O)R7C, —NR7AC(O)OR7C, —NR7AOR7C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R8is hydrogen, halogen, —CX83, —CHX82, —CH2X8, —OCX83, —OCH2X8, —OCHX82, —N3, —CN, —SOn8R8D, —SOv8NR8AR8B, —NHC(O)NR8AR8B, —N(O)m8, —NR8AR8B, —C(O)R8C, —C(O)—OR8C, —C(O)NR8AR8B, —OR8D, —NR8ASO2R8D, —NR8AC(O)R8C, —NR8AC(O)OR8C, —NR8AOR8C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R9is hydrogen, halogen, —CX93, —CHX92, —CH2X9, —OCX93, —OCH2X9, —OCHX92, —N3, —CN, —SOv9R9D, —SOv9NR9AR9B, —NHC(O)NR9AR9B, —N(O)m9, —NR9AR9B, —C(O)R9C, —C(O)—OR9C, —C(O)NR9AR9B, —OR9D, —NR9ASO2R9D, —NR9AC(O)R9C, —NR9AC(O)OR9C, —NR9AOR9C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R10is hydrogen, halogen, —CX103, —CHX102, —CH2X10, —OCX103, —OCH2X10, —OCHX102, —N3, —CN, —SOn10R10D, —SOv10NR10AR10B, —NHC(O)NR10AR10B, —N(O)m10, —NR10AR10B, —C(O)R10C, —C(O)—OR10C, —C(O)NR10AR10B, —OR10D, —NR10ASO2R10D, —NR10AC(O)R10C, —NR10AC(O)OR10C, —NR10AOR10C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R11is hydrogen, halogen, —CX113, —CHX112, —CH2X11, —OCX113, —OCH2X11, —OCHX112, —N3, —CN, —SOn11R11D, —SOv11NR11AR11B, —NHC(O)NR11AR11B, —N(O)m11, —NR11AR11B, —C(O)R11C, —C(O)—OR11C, —C(O)NR11AR11B, —OR11D, —NR11ASO2R11D, —NR11AC(O)R11C, —NR11AC(O)OR11C, —NR11AOR11C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R12is hydrogen, halogen, —CX123, —CHX122, —CH2X12, —OCX123, —OCH2X12, —OCHX122, —N3, —CN, —SOnl2R12D, —SOv12NR12AR12B, —NHC(O)NR12AR12B, —N(O)m12, —NR12AR12B, —C(O)R12C, —C(O)—OR12C, —C(O)NR12AR12B, —OR12D, —NR12ASO2R12D, —NR12AC(O)R12C, —NR12AC(O)OR12C, —NR12AOR12C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R13is hydrogen, —CX133, —CHX132, —CH2X13, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12Cand R12Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R1and R2together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4and R5together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n1, n2, n3, n4, n5, n6, n7, n8, n9, n10, n11 and n12 are independently an integer from 0 to 4;m1, m2, m3, m4, m5, m6, m7, m8, m9, m10, m11, m12, v1, v2, v3, v4, v5, v6, v7, v8, v9, v10, v11 and v12 are independently an integer from 1 to 2; andX, X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, and X13are independently —F, —Cl, —Br, or —I,or a salt thereof. Embodiment 51. The method of Embodiment 50, wherein the compound has a formula (II): wherein:R14is hydrogen, halogen, —CX143, —CHX142, —CH2X14, —OCX143, —OCH2X14, —OCHX142, —N3, —CN, —SOn14R14D, —SOv14NR14AR14B, —NHC(O)NR14AR14B, —N(O)m14, —NR14AR14B, —C(O)R14C, —C(O)—OR14C, —C(O)NR14AR14B, —OR14D, —NR14ASO2R14D, —NR14AC(O)R14C, —NR14AC(O)OR14C, —NR14AOR14C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R15is hydrogen, halogen, —CX153, —CHX152, —CH2X15, —OCX153, —OCH2X15, —OCHX152, —N3, —CN, —SOnl5R15D, —SOv15NR15AR15B, —NHC(O)NR15AR15B, —N(O)m15, —NR15AR15B, —C(O)R15C, —C(O)—OR15C, —C(O)NR15AR15B, —OR15D, —NR15ASO2R15D, —NR15AC(O)R15C, —NR15AC(O)OR15C, —NR15AOR15C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R16is hydrogen, halogen, —CX163, —CHX162, —CH2X16, —OCX163, —OCH2X16, —OCHX162, —N3, —CN, —SOn16R16D, —SOv16NR16AR16B, —NHC(O)NR16AR16B, —N(O)m16, —NR16AR16B, —C(O)R16C, —C(O)—OR16C, —C(O)NR16AR16B, —OR16D, —NR16ASO2R16D, —NR16AC(O)R16C, —NR16AC(O)OR16C, —NR16AOR16C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R17is hydrogen, halogen, —CX173, —CHX172, —CH2X17, —OCX173, —OCH2X17, —OCHX172, —N3, —CN, —SOn17R17D, —SOv17NR17AR17B, —NHC(O)NR17AR17B, —N(O)m17, —NR17AR17B, —C(O)R17C, —C(O)—OR17C, —C(O)NR17AR17B, —OR17D, —NR17ASO2R17D, —NR17AC(O)R17C, —NR17AC(O)OR17C, —NR17AOR17C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R14A, R14B, R14C, R14D, R15A, R15B, R15C, R15D, R16A, R16B, R16C, R16D, R17A, R17B, R17C, and R17Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n14, n15, n16, and n17 are independently an integer from 0 to 4;m14, m15, m16, m17, v14, v15, v16, and v17 are independently an integer from 1 to 2; andX14, X15, X16, and X17are independently —F, —Cl, —Br, or —I. Embodiment 52. The method of any one of Embodiments 50-51, wherein L1is —O— or —S—. Embodiment 53. The method of any one of Embodiments 50-51, wherein L1is a bond. Embodiment 54. The method of any one of Embodiments 50-51, wherein L1is —S(O)2—, —NR13S(O)2— or —NR13C(O)— Embodiment 55. The method of any one of Embodiments 50-51, wherein L1is —S(O)2—, —NR13S(O)2— or —NR13C(O)—. Embodiment 56. The method of any one of Embodiments 50-55, wherein R7and R9are hydrogen. Embodiment 57. The method of any one of Embodiments 50-56, wherein each R6, R8, and R10is independently hydrogen, halogen, —N3, —CN, —NO2, —NEB, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, or substituted or unsubstituted C1-C3alkyl. Embodiment 58. The method of any one of Embodiments 50-57, wherein the compound has a formula (III), Embodiment 59. The method of any one of Embodiments 50-57, wherein the compound has a formula (IV), Embodiment 60. The method of any one of Embodiments 50-57, wherein the compound has a formula (V), Embodiment 61. The method of any one of Embodiments 50-57, wherein the compound has a formula (VI), Embodiment 62. The method of any one of Embodiments 50-57, wherein the compound has a formula (VII). Embodiment 63. The method of Embodiment 50, wherein the compound has a formula (VIII), wherein:R1Dis hydrogen or unsubstituted C1-C4alkyl;R6is hydrogen or —C(O)—OR6C;R7is hydrogen or halogen; and R8is halogen, —OR8D, —C(O)—OR8C, or unsubstituted C2-C4alkyl. Embodiment 64. The method of Embodiment 63, wherein R1D, R6C, R8C, and R8Dare independently hydrogen or —CH3. Embodiment 65. The method of Embodiment 64, wherein:R1Dis hydrogen;R6and R7are hydrogen; andR8is —OH, —OCH3, —COOH, —Br, or —C(CH3)3. Embodiment 66. The method of Embodiment 64, wherein:R1Dis —CH3;R6and R7are hydrogen; andR8is —OH, —OCH3, —COOH, —COOCH3, —Cl, —Br, or —C(CH3)3. Embodiment 67. The compound of Embodiment 64, wherein:R1Dis hydrogen or —CH3;R6is hydrogen; andR7and R8are halogen. Embodiment 68. The method of Embodiment 64, wherein:R1Dis hydrogen or —CH3;R7is halogen; andR7and R8are hydrogen. Embodiment 69. The method of Embodiment 64, wherein:R1Dis hydrogen or —CH3;R6is —C(O)—OR6C; andR7and R8are hydrogen. Embodiment 70. The method of Embodiment 50, wherein the compound has a formula (IX), wherein:R1D, R2D, and R3Dare independently hydrogen or unsubstituted C1-C4alkyl; andR6is hydrogen, halogen, —C(O)—OR6C, —OR6D, or unsubstituted C1-C4alkyl. Embodiment 71. The method of Embodiment 70, wherein:R1D, R2D, and R3Dare independently hydrogen or —CH3; andR6Cand R6Dare independently hydrogen or —CH3. Embodiment 72. The method of any one of Embodiments 50-71, wherein the compound is Embodiment 73. The method of any one of Embodiments 52-72, wherein the compound inhibits the poly(ADP-ribose) glycohydrolase (PARG) in a cancer cell. Embodiment 74. The method of Embodiment 73, wherein the cancer cell is from breast cancer, ovarian cancer, lung cancer, pancreatic cancer, glioblastoma, uterine cancer, bladder cancer, esophagus cancer, gastric cancer, head and neck cancer, cholangiocarcinoma, mesothelioma, prostate cancer, colon carcinoma, fallopian tube cancer, lymphoma and leukemia. Embodiment 75. A pharmaceutical composition comprising a pharmaceutically acceptable excipient and compound having a formula (I), wherein,L1is a bond, —CR11R12—, —NR13—, —O—, —S—, —S(O)—, —S(O)2—, —NR13S(O)—, —NR13S(O)2—, or —NR13C(O)—;R1is hydrogen, halogen, —CX12, —CHX12, —CH2X1, —OCX13, —OCH2X1, —OCHX22, —N3, —CN, —SOn1R1D, —SOv1NR1AR1B, —NHC(O)NR1AR1B, —N(O)m1, —NR1AR1B, —C(O)R1C, —C(O)—OR1C, —C(O)NR1AR1B, —OR1D, —NR1ASO2R1D, —NR1AC(O)R1C, —NR1AC(O)OR1C, —NR1AOR1C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R2is hydrogen, halogen, —CX23, —CHX22, —CH2X2, —OCX23, —OCH2X2, —OCHX22, —N3, —CN, —SOn2R2D, —SOv2NR2AR2B, —NHC(O)NR2AR2B, —N(O)m2, —NR2AR2B, —C(O)R2C, C(O)—OR2C, —C(O)NR2AR2B, —OR2D, —NR2ASO2R2D, —NR2AC(O)R2C, —NR2AC(O)OR2C, —NR2AOR2C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R3is hydrogen, halogen, —CX33, —CHX32, —CH2X3, —OCX33, —OCH2X3, —OCHX32, —N3, —CN, —SOn3R3D, —SOv3NR3AR3B, —NHC(O)NR3AR3B, —N(O)m3, —NR3AR3B, —C(O)R3C, —C(O)—OR3C, —C(O)NR3AR3B, —OR3D, —NR3ASO2R3D, —NR3AC(O)R3C, —NR3AC(O)OR3C, —NR3AOR3C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4is hydrogen, halogen, —CX43, —CHX42, —CH2X4, —OCX43, —OCH2X4, —OCHX42, —N3, —CN, —SOn4R4D, —SOv4NR4AR4B, —NHC(O)NR4AR4B, —N(O)m4, —NR4AR4B, —C(O)R4C, —C(O)—OR4C, —C(O)NR4AR4B, —OR4D, —NR4ASO2R4D, —NR4AC(O)R4C, —NR4AC(O)OR4C, —NR4AOR4C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R5is hydrogen, halogen, —CX53, —CHX52, —CH2X5, —OCX53, —OCH2X5, —OCHX52, —N3, —CN, —SOn5R5D, —SOv5NR5AR5B, —NHC(O)NR5AR5B, —N(O)m5, —NR5AR5B, —C(O)R5C, —C(O)—OR5C, —C(O)NR5AR5B, —OR5D, —NR5ASO2R5D, —NR5AC(O)R5C, —NR5AC(O)OR5C, —NR5AOR5C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R6is hydrogen, halogen, —CX63, —CHX62, —CH2X6, —OCX63, —OCH2X6, —OCHX62. —N3, —CN, —SOn6R6D, —SOv6NR6AR6B, —NHC(O)NR6AR6B, —N(O)m6, —NR6AR6B, —C(O)R6C, —C(O)—OR6C, —C(O)NR6AR6B, —OR6D, —NR6ASO2R6D, —NR6AC(O)R6C, —NR6AC(O)OR6C, —NR6AOR6C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R7is hydrogen, halogen, —CX73, —CHX72, —CH2X7, —OCX73, —OCH2X7, —OCHX72, —N3, —CN, —SOn7R7D, —SOv7NR7AR7B, —NHC(O)NR7AR7B, —N(O)m7, —NR7AR7B, —C(O)R7C, —C(O)—OR7C, —C(O)NR7AR7B, —OR7D, —NR7ASO2R7D, —NR7AC(O)R7C, —NR7AC(O)OR7C, —NR7AOR7C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R8is hydrogen, halogen, —CX83, —CHX82, —CH2X8, —OCX83, —OCH2X8, —OCHX82, —N3, —CN, —SOn8R8D, —SOv8NR8AR8B, —NHC(O)NR8AR8B, —N(O)m8, —NR8AR8B, —C(O)R8C, —C(O)—OR8C, —C(O)NR8AR8B, —OR8D, —NR8ASO2R8D, —NR8AC(O)R8C, —NR8AC(O)OR8C, —NR8AOR8C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R9is hydrogen, halogen, —CX93, —CHX92, —CH2X9, —OCX93, —OCH2X9, —OCHX92, —N3, —CN, —SOn9R9D, —SOv9NR9AR9B, —NHC(O)NR9AR9B, —N(O)m9, —NR9AR9B, —C(O)R9C, —C(O)—OR9C, —C(O)NR9AR9B, —OR9D, —NR9ASO2R9D, —NR9AC(O)R9C, —NR9AC(O)OR9C, —NR9AOR9C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R10is hydrogen, halogen, —CX103, —CHX102, —CH2X10, —OCX103, —OCH2X10, —OCHX102, —N3, —CN, —SOn10R10D, —SOv10NR10AR10B, —NHC(O)NR10AR10B, —N(O)m10, —NR10AR10B, —C(O)R10C, —C(O)—OR10C, —C(O)NR10AR10B, —OR10D, —NR10ASO2R10D, —NR10AC(O)R10C, —NR10AC(O)OR10C, —NR10AOR10C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R11is hydrogen, halogen, —CX113, —CHX112, —CH2X11, —OCX113, —OCH2X11, —OCHX112, —N3, —CN, —SOn11R11D, —SOv11NR11AR11B, —NHC(O)NR11AR11B, —N(O)m11, —NR11AR11B, —C(O)R11C, —C(O)—OR11C, —C(O)NR11AR11B, —OR11D, —NR11ASO2R11D, —NR11AC(O)R11C, —NR11AC(O)OR11C, —NR11AOR11C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R12is hydrogen, halogen, —CX123, —CHX122, —CH2X12, —OCX123, —OCH2X12, —OCHX122, —N3, —CN, —SOnl2R12D, —SOv12NR12AR12B, —NHC(O)NR12AR12B, —N(O)m12, —NR12AR12B, —C(O)R12C, —C(O)—OR12C, —C(O)NR12AR12B, —OR12D, —NR12ASO2R12D, —NR12AC(O)R12C, —NR12AC(O)OR12C, —NR12AOR12C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R13is hydrogen, —CX133, —CHX132, —CH2X13, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R1A, R1B, R1C, R1D, R2A, R2B, R2C, R2D, R3A, R3B, R3C, R3D, R4A, R4B, R4C, R4D, R5A, R5B, R5C, R5D, R6A, R6B, R6C, R6D, R7A, R7B, R7C, R7D, R8A, R8B, R8C, R8D, R9A, R9B, R9C, R9D, R10A, R10B, R10C, R10D, R11A, R11B, R11C, R11D, R12A, R12B, R12Cand R12Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R1and R2together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R4and R5together with atoms attached thereto are optionally joined to form a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n1, n2, n3, n4, n5, n6, n7, n8, n9, n10, n11 and n12 are independently an integer from 0 to 4;m1, m2, m3, m4, m5, m6, m7, m8, m9, m10, m11, m12, v1, v2, v3, v4, v5, v6, v7, v8, v9, v10, v11 and v12 are independently an integer from 1 to 2; andX, X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, and X13are independently —F, —Cl, —Br, or —I, or a salt thereof, and a pharmaceutically acceptable carrier. Embodiment 76. The pharmaceutical composition of Embodiment 75, wherein the compound has a formula (II): wherein:R14is hydrogen, halogen, —CX143, —CHX142, —CH2X14, —OCX143, —OCH2X14, —OCHX142, —N3, —CN, —SOn14R14D, —SOv14NR14AR14B, —NHC(O)NR14AR14B, —N(O)m14, —NR14AR14B, C(O)R14C, —C(O)—OR14C, —C(O)NR14AR14B, —OR14D, —NR14ASO2R14D, —NR14AC(O)R14C, —NR14AC(O)OR14C, —NR14AOR14C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R15is hydrogen, halogen, —CX153, —CHX152, —CH2X15, —OCX153, —OCH2X15, —OCHX152, —N3, —CN, —SOnl5R15D, —SOv15NR15AR15B, —NHC(O)NR15AR15B, —N(O)m15, —NR15AR15B, —C(O)R15C, —C(O)—OR15C, —C(O)NR15AR15B, —OR15D, —NR15ASO2R15D, —NR15AC(O)R15C, —NR15AC(O)O R15C, —NR15AOR15C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R16is hydrogen, halogen, —CX163, —CHX162, —CH2X16, —OCX163, —OCH2X16, —OCHX162, —N3, —CN, —SOn16R16D, —SOv16NR16AR16B, —NHC(O)NR16AR16B, —N(O)m16, —NR16AR16B, —C(O)R16C, —C(O)—OR16C, —C(O)NR16AR16B, —OR16D, —NR16ASO2R16D, —NR16AC(O)R16C, —NR16AC(O)OR16C, —NR16AOR16C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;R17is hydrogen, halogen, —CX173, —CHX172, —CH2X17, —OCX173, —OCH2X17, —OCHX172, —N3, —CN, —N3, —SOnl7R17D, —SOv17NR17AR17B, —NHC(O)NR17AR17B, —N(O)m17, —NR17AR17B, —C(O)R17C, —C(O)—OR17C, —C(O)NR17AR17B, —OR17D, —NR17ASO2R17D, —NR17AC(O) R17C, —NR17AC(O)OR17C, —NR17AOR17C, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;Each R14A, R14B, R14C, R14D, R15A, R15B, R15C, R15D, R16A, R16B, R16C, R16D, R17A, R17B, R17C, and R17Dis independently hydrogen, —CX3, —CHX2, —CH2X, —COOH, —CONH2, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;n14, n15, n16, and n17 are independently an integer from 0 to 4;m14, m15, m16, m17, v14, v15, v16, and v17 are independently an integer from 1 to 2; andX14, X15, X16, and X17are independently —F, —Cl, —Br, or —I. Embodiment 77. The pharmaceutical composition of any one of Embodiments 75-76, wherein L1is —O— or —S—. Embodiment 78. The pharmaceutical composition of any one of Embodiments 75-76, wherein L1is a bond. Embodiment 79. The pharmaceutical composition of any one of Embodiments 75-76, wherein L1is —S(O)2—, —NR13S(O)2— or —NR13C(O)—. Embodiment 80. The pharmaceutical composition of any one of Embodiments 75-79, wherein at least one of R1, R2and R3are —OH or —OCH3. Embodiment 81. The pharmaceutical composition of any one of Embodiments 75-80, wherein R7 and R9 are hydrogen. Embodiment 82. The pharmaceutical composition of any one of Embodiments 75-81, wherein each R6, R8, and R10is independently hydrogen, halogen, —N3, —CN, —NO2, —NH2, —C(O)H, —C(O)CH3, —C(O)OH, —C(O)OCH3, —C(O)NH2, —OH, —OCH3, or substituted or unsubstituted C1-C3alkyl. Embodiment 83. The pharmaceutical composition of any one of Embodiments 75-82, wherein the compound has a formula (III), Embodiment 84. The pharmaceutical composition of any one of Embodiments 75-82, wherein the compound has a formula (IV), Embodiment 85. The pharmaceutical composition of any one of Embodiments 75-82, wherein the compound has a formula (V), Embodiment 86. The pharmaceutical composition of any one of Embodiments 75-82, wherein the compound has a formula (VI), Embodiment 87. The pharmaceutical composition of any one of Embodiments 75-82, wherein the compound has a formula (VII), Embodiment 88. The pharmaceutical composition of Embodiment 75, wherein the compound has a formula (VIII), wherein:R1Dis hydrogen or unsubstituted C1-C4alkyl;R6is hydrogen or —C(O)—OR6C;R7is hydrogen or halogen; andR8is halogen, —OR8D, —C(O)—OR8C, or unsubstituted C2-C4alkyl. Embodiment 89. The pharmaceutical composition of Embodiment 88, wherein R1D, R6C, R8C, and R8Dare independently hydrogen or —CH3. Embodiment 90. The pharmaceutical composition of Embodiment 89, wherein:R1Dis hydrogen;R6and R7are hydrogen; andR8is —OH, —OCH3, —COOH, —Br, or —C(CH3)3. Embodiment 91. The pharmaceutical composition of Embodiment 89, wherein:R1Dis —CH3;R6and R7are hydrogen; andR8is —OH, —OCH3, —COOH, —COOCH3, —Cl, —Br, or —C(CH3)3. Embodiment 92. The pharmaceutical composition of Embodiment 89, wherein:R1Dis hydrogen or —CH3;R6is hydrogen; andR7and R8are halogen. Embodiment 93. The pharmaceutical composition of Embodiment 89, wherein:R1Dis hydrogen or —CH3;R7is halogen; andR7and R8are hydrogen. Embodiment 94. The pharmaceutical composition of Embodiment 89, wherein:R1Dis hydrogen or —CH3;R6is —C(O)—OR6C; andR7and R8are hydrogen. Embodiment 95. The pharmaceutical composition of Embodiment 75, wherein the compound has a formula (IX), wherein:R1D, R2D, and R3Dare independently hydrogen or unsubstituted C1-C4alkyl; andR6is hydrogen, halogen, —C(O)—OR6C, —OR6D, or unsubstituted C1-C4alkyl. Embodiment 96. The pharmaceutical composition of Embodiment 95, wherein:R1D, R2D, and R3Dare independently hydrogen or —CH3; andR6Cand R6Dare independently hydrogen or —CH3. Embodiment 97. The pharmaceutical composition of any one of Embodiments 75-96, wherein the compound is VI. Examples Although the foregoing section has been described in some detail by way of illustration and example for purposes of clarity of understanding, it is apparent to those skilled in the art that certain minor changes and modifications will be practiced in light of the above teaching. Therefore, the description and examples should not be construed as limiting the scope of any invention described herein. All references cited herein, including patent applications and publications, are hereby incorporated by reference in their entirety. Example 1: Cancer Caused by PARylation and/or dePARylation A cancer can be caused by defective DNA damage repair system in the cancer/tumor cell. Among other things, the cancer can be caused by defective PARP-dependent DNA damage repair system or PARylation. For instance, suppression of PARylation weakens DNA damage repair in the tumor cells with defective DNA repair machinery, and PARP inhibitor treatment further disrupt DNA damage repair in the tumor cells. In addition, the cancer may be related to defective PARG-dependent DNA damage repair system or dePARylation. For instance, suppression of de PARylation weakens DNA damage repair in the tumor cells with defective DNA repair machinery, and PARG inhibitor treatment disrupt downstream of PARylation in DNA damage repair in the tumor cells. PARylation is a transient posttranslational modification and quickly degraded by PARG, the major dePARylation enzyme. Our recent study suggests that PARylation and dePARylation are not antagonistic processes during DNA damage repair. Instead, transient PARylation and quick dePARylation are sequential events to mediate the recruitment of DNA damage machineries to the sites of DNA damage. We have shown that a number of DNA damage response factors recognize PARylation and is recruited by PARylation to the proximity of DNA lesions. However, PARylation has to be digested so that DNA damage machineries recognize DNA lesions and repair lesions. Thus, dePARylation is an immediate downstream step of PARP-dependent DNA damage repair. And suppression of dePARylation also abolishes PARP-dependent DNA damage repair. Thus, it is very likely that targeting PARG, the dePARylation enzyme, to specifically kill tumor cells. Example 2: Identification of Novel PARG Inhibitors Development of potent and cell-permeant PARG inhibitors via multi-step virtual screening and hierarchical selection. Forty candidates from National Cancer Institute (NCI) were selected to examine the efficacy of PARG inhibition by dot blot assay. PARG was incubated with PAR for 20 min at room temperature with or without inhibitors. PAR-digestion results were analyzed using dot blotting with anti-PAR antibody. Two compounds, #5 and #34, showed the good inhibitory activity for PARG. PC and NC mean positive control (PAR only) and negative control (no inhibitor), respectively. IC50value of compound 34 was measured by dot blotting with anti-PAR antibody in a dose course of compound 34. PAR digestion assay: Recombinant PARG protein were incubated with PAR (10 μM, calculated as the ADP-ribose unit) and DMSO (Negative control, NC) or small molecules for 20 minutes at room temperature. Positive control (PC) only contains PAR in PBS. Samples were spotted onto a nitrocellulose membrane. The membrane was blocked with TBST buffer (0.15 M NaCl, 0.01 M Tris-HCl at pH 7.4, 0.1% Tween 20) supplemented with 5% milk and extensively washed with TBST. The membrane was examined by anti-PAR antibody. Example 3: Inhibiting De-PARylation Traps Massive PAR-Dependent Factors of DNA Damage Response Recruitment of PAR-dependent CHFR in U2OS cells without or with 100 nM PARG inhibitor (#34) treatment after laser scissor. We used CHRF as a readout for monitoring the level of poly(ADP-ribosyl)ation. Laser microirradiation and imaging of cells: U2OS cells with transfection of GFP-CHFR were plated on glass-bottomed culture dishes (Mat Tek Corporation) and treated with or without 100 nM PARG inhibitor (#34). Laser microirradiation was performed using an IX 71 microscope (Olympus) coupled with the MicoPoint laser illumination and ablation system (Photonic Instruments, Inc.). A 337.1-nm laser diode (3.4 mW) transmitted through a specific dye cell and then yielded a 365-nm wavelength laser beam that was focused through 603 UPlanSApo/1.35 oil objective to yield a spot size of 0.5-1 mm. The time of cell exposure to the laser beam was ˜3.5 nsec. The pulse energy was 170 mJ at 10 Hz. Images were taken by the same microscope with the CellSens software (Olympus). GFP fluorescence at the laser line was converted into a numerical value using Image J. Normalized fluorescent curves from 50 cells from three independent experiments were averaged. The error bars represent the standard deviation. Example 4: PARG Inhibitor Selectively Kills BRCA-Mutant Cancer Cells Colony formation assay was performed using HCC1937 (BRCA1-deficient breast cancer cells), HCC1937 BRCA1 (BRCA1-reconstituted HCC1937 cells) cells, PEO-1 (BRCA2-deficient ovarian cancer cells), and PEO-4 (BRCA2-reconstituted PEO-1 cells) with indicated concentrations of PARG inhibitor (#34). Colony formation assay: HCC1937, HCC1937-BRCA1, PEO-1 or PEO-4 (˜1000 cells) were seeded into six-well plates and then treated by various doses of PARG inhibitor (#34). After 14-21 days of culture, the viable cells were fixed by methanol and stained with crystal violet. The number of colonies (>50 cells for each colony) was calculated. Example 5: Synthesis Compound 34 can be synthesized as depicted in the following Scheme 1. Compound 1414 can be synthesized as depicted in the following Scheme 2. Compound 1429 can be synthesized as depicted in the following Scheme 3. Compound 6 can be synthesized as depicted in the following Scheme 4. Synthesis of the compounds was verified by NMR spectra and mass spectroscopy (MS). Example 6: PAR Digestion Assay Recombinant full length PARG protein is generated from Sf9 insect cells. Recombinant PAR is purified from a biochemical assay using PARP1. PARG is incubated with PAR in the presence of DMSO (Negative control, NC) or small chemical compounds for 20 minutes at room temperature. Positive control (PC) only contains PAR. Samples (1 μl) were spotted onto a nitrocellulose membrane. Then, the membrane was baked for 30 minutes at 60° C. and blocked with TBST buffer (0.15 M NaCl, 0.01 M Tris-HCl at pH 7.4, 0.1% Tween 20) supplemented with 5% milk for 30 minutes at room temperature. After washing with TBST, the membrane was incubated with monoclonal anti-PAR antibody (Trevigen, Inc.) for overnight at 4° C. Following standard western blot method, the signals were visualized by chemiluminescent detection. With the chemical inhibition of the dePARylation activity of PARG, we are able to detect the dot signals of PAR. Example 7: Compounds Exemplary compounds having a formula (VIII) are shown in the following Table 1. TABLE 1CompoundEntryR1R201A—OCH32A3A4A5A6A7A8A9A10A11A12A13A14A1B—OH2B3B4B5B (melting point 236.8-237.9° C.)6B7B8B9B10B11B12B13B14B Example 8: PARG Inhibition and Cell Viability Assays The efficacy of CHP20-25 against PARG activity was examined by dot blot assays. PARG was incubated with PAR for 20 min at room temperature with or without inhibitors. PAR-digestion results were analyzed using dot blotting with anti-PAR antibody. IC50values of CHP20-25 were measured by dot blotting with anti-PAR antibody in a dose course of CHP20-25. Colony formation assays were performed using HCC1937 (BRCA1-mutant breast cancer cells) and PARPi-resistant UWB1.289 (BRCA1-mutant ovarian cancer cells) with 2.5-20 μM PARG inhibitors (CHP20-25,FIG.6A). The IC50and EC50values of CHP20-25 were summarized in the table (FIG.6B). Example 9: PAR Digestion Assay Recombinant PAR was purified from a biochemical assay using PARP1. The concentration of PAR was calculated as the ADP-ribose unit. Recombinant full length PARG was incubated with 10 μM PAR in the presence of DMSO (negative control) or small molecule compounds (CHP20-25) in a 10 μl reaction for 20 minutes at room temperature. Positive control only contains PAR in PBS. For dot blotting analysis, samples (1 μl) were spotted onto a nitrocellulose membrane. Then, the membrane was baked for 30 minutes at 60° C. and blocked with TBST buffer (0.15 M NaCl, 0.01 M Tris-HCl at pH 7.4, 0.1% Tween 20) supplemented with 5% milk for 30 minutes at room temperature. After washing with TBST, the membrane was incubated with anti-PAR monoclonal antibody (Trevigen) overnight at 4° C. Following standard western blot method, the signals were visualized by chemiluminescent detection and results are shown inFIG.7A-FIG.7F. Example 10: Colony Formation Assay HCC1937 and PARPi-resistant UWB1.289 (˜1000 cells) were seeded into six-well plates and then treated by various doses of PARG inhibitors (CHP20-25). After a 14˜21-d culture, the viable cells were fixed by methanol and stained with crystal violet. The number of colonies (>50 cells for each colony) was calculated. Example 11: Colony Formation Assay Suppressing de-PARylation traps massive PAR-dependent factor of DNA damage repair. Recruitment of PAR-dependent CHFR in U2OS cells without or with PARG inhibitors (COH34 and CHP20-25) treatments after laser scissor. Example 12: Laser Microirradiation and Imaging of Cells U2OS cells with transfection of GFP-CHFR were plated on glass-bottomed culture dishes (Mat Tek Corporation) and treated with or without 100 nM COH34 (control) or 1 μM CHP20-25. Laser microirradiation was performed using an IX 71 microscope (Olympus) coupled with the MicoPoint laser illumination and ablation system (Photonic Instruments, Inc.). A 337.1-nm laser diode (3.4 mW) transmitted through a specific dye cell and then yielded a 365-nm wavelength laser beam that was focused through 603 UPlanSApo/1.35 oil objective to yield a spot size of 0.5-1 mm. The time of cell exposure to the laser beam was ˜3.5 nsec. The pulse energy was 170 mJ at 10 Hz. Images (FIG.8) were taken by the same microscope with the CellSens software (Olympus). It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims. All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety for all purposes. | 594,894 |
11858880 | DETAILED DESCRIPTION OF THE INVENTION The present invention provides a compound having the structure whereinR1is —H, alkyl, alkenyl, or alkynyl;R2is —H, alkyl, alkenyl, or alkynyl;R3, R4, R5, and R6are each independently —H, halogen, C1-C6alkyl, —OH, —O— (C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3, orR3and R4are each independently —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3, and R5and R6combine to form a fused aryl or fused heteroaryl, which are each unsubstituted or substituted, orR3and R6are each independently —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3, and R4and R5combine to form a fused aryl or fused heteroaryl, which are each unsubstituted or substitute, orR5and R6are each independently —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3, and R3and R4combine to form a fused aryl or fused heteroaryl, which are each unsubstituted or substituted; andA is an aryl or heteroaryl, which are each unsubstituted or substituted,wherein when R3, R4, and R6are each —H and R5is —OH or —OCH3or R3, R5, and R6are each —H and R4is —Br, then A is other than ortho-tolyl or meta-bromophenyl,or a pharmaceutically acceptable salt or ester thereof. The present invention provides a compound having the structure: whereinR1is —H;R2is —H;R3, R4, R5, and R6are each independently —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3, orR3and R4are each independently —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3, and R5and R6combine to form a fused aryl or fused heteroaryl, which are each unsubstituted or substituted, orR3and R6are each independently —H, halogen, C3-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3, and R4and R5combine to form a fused aryl or fused heteroaryl, which are each unsubstituted or substitute, orR5and R6are each independently —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3, and R3and R4combine to form a fused aryl or fused heteroaryl, which are each unsubstituted or substituted; andA is a phenyl, which is unsubstituted or substituted,wherein when R3, R4, and R6are each —H and R5is —OH or —OCH3, or R3, R5, and R6are each —H and R4is —Br, then A is other than ortho-tolyl or meta-bromophenyl,or a pharmaceutically acceptable salt or ester thereof. The present invention provides a compound having the structure: whereinR1is —H;R2is —H;R3, R4, R5, and R6are each independently —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3; andA is a phenyl, which is unsubstituted or substituted,wherein when R3, R4, and R6are each —H and R5is —OH or —OCH3, or R3, R5, and R6are each —H and R4is —Br, then A is other than ortho-tolyl or meta-bromophenyl,or a pharmaceutically acceptable salt or ester thereof. The present invention provides a compound having the structure: whereinR1is —H;R2is —H;R3, R4, R5, and R6are each independently —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3; andA is a phenyl, which disubstituted,or a pharmaceutically acceptable salt or ester thereof. The present invention provides a compound having the structure: whereinR1is —H;R2is —H;R3, R4, R5, and R6are each independently —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3; andA is a phenyl, which trisubstituted,or a pharmaceutically acceptable salt or ester thereof. In some embodiments, wherein when R3and R5are each —H and R4and R6are each —Br, then A is other than para-bromophenyl, meta-bromophenyl, ortho-tolyl or 3-quinolinyl. In some embodiments, wherein when R3, R5and R6are each —H and R4is —Br, then A is other than 3,5-dibromo-ortho-hydorxyphenyl, para-bromophenyl, meta-bromophenyl or ortho-tolyl. In some embodiments, wherein when R3and R5are each —H and R4and R6are each —Br, then A is other than para-bromophenyl, meta-bromophenyl, ortho-tolyl or 3-quinolinyl; and when R3, R5and R6are each —H and R4is —Br, then A is other than 3,5-dibromo-ortho-hydorxy, para-bromophenyl, meta-bromophenyl or ortho-tolyl. In some embodiments, wherein when R3and R5are each —H and R4and R6are each —Br, then A is other than para-bromophenyl; and when R3, R5and R6are each —H and R4is —Br, then A is other than 3,5-dibromo-ortho-hydorxyphenyl. In some embodiments, A is other than para-bromophenyl, meta-bromophenyl, ortho-tolyl or 3-quinolinyl. In some embodiments, A is other than 3,5-dibromo-ortho-hydorxyphenyl, para-bromophenyl, meta-bromophenyl or ortho-tolyl In some embodiments, A is other than ortho-tolyl or meta-bromophenyl. In some embodiments, A is other than 3,5-dibromo-ortho-hydorxyphenyl, para-bromophenyl, meta-bromophenyl, ortho-tolyl or 3-quinolinyl. In some embodiments, wherein the aryl or heteroaryl is substituted with halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3. In some embodiments, wherein the fused aryl or fused heteroaryl is substituted with halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3. In some embodiments, the compound wherein one of R3-R6is other than —H. In some embodiments, the compound wherein two of R3-R6is other than —H. In some embodiments, the compound, wherein A is monosubstituted. In some embodiments, the compound wherein A is disubstituted. In some embodiments, the compound wherein A is trisubstituted. In some embodiments, the compound wherein R3, R4, R5, and R6are each independently —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3. In some embodiments, the compound wherein R3, R4, R5, and R6are each independently halogen, —O—(C1-C6alkyl), —OCF3or —CF3. In some embodiments, the compound wherein R3, R4, R5, and R6are each independently halogen or —O—(C1-C6alkyl). In some embodiments, the compound wherein R3, R4, R5, and R6are each independently —Cl, —Br, —F, —O—(C1-C6alkyl), —OCF3or —CF3. In some embodiments, the compound wherein R3, R4. R5, and R6are each independently —Cl, —Br, or —O—(C1-C6alkyl). In some embodiments, the compound whereinR3is —H, R4is —CH3, Cl or Br, R5is —H, and R6is —CH3, Cl or Br; orR3is —H, R4is —CH3, Cl or Br, R5is and R6is H; orR3is —H, R4is —H, R5is —CH3, Cl or Br, and R6is —H. In some embodiments, the compound having the structure: In some embodiments, the compound whereinR3is —H, R4is —F, —OCF3or —CF3, R5is —H, and R6is —H; orR3is —H, R4is —H, R5is —H, and R6is Cl or Br. In some embodiments, the compound having the structure: In some embodiments, the compound wherein R3and R4are each independently —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3, and R5and R6combine to form a fused aryl or fused heteroaryl, which are each unsubstituted or substituted with halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3. In some embodiments, the compound wherein R3and R4are each independently —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3, and R5and R6combine to form a fused unsubstituted phenyl. In some embodiments, the compound wherein R3and R6are each independently —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3, and R4and R5combine to form a fused aryl or fused heteroaryl, which are each unsubstituted or substituted with halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3. In some embodiments, the compound wherein R3, and R6are each independently —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3, and R4and R5combine to form a fused unsubstituted phenyl. In some embodiments, the compound wherein R5and R6are each independently —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3, and R3and R4combine to form a fused aryl or fused heteroaryl, which are each unsubstituted or substituted with halogen, C1-C6, alkyl, —OH, —O—(C2-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3. In some embodiments, the compound wherein R5and R6are each independently —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3, and R3and R4combine to form a fused unsubstituted phenyl. In some embodiments, the compound having the structure: In some embodiments, the compound wherein A is an unsubstituted aryl. In some embodiments, the compound wherein A is a substituted aryl. In some embodiments, the compound wherein A is an unsubstituted heteroaryl. In some embodiments the compound wherein A is an substituted heteroaryl. In some embodiments, the compound wherein the aryl is a phenyl, 1-naphthyl or 2-naphthyl. In some embodiments, the compound wherein the heteroaryl is a pyridinyl, pyrrolyl, thienyl, furyl, quinolyl, isoquinolyl, indolyl, benzothienyl or benzofuryl. In some embodiments, the compound wherein A has the structure: wherein R7, R8, R9, R10and R11are each, independently, —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2, —OCF3, —CN, —CH2OCH3, —N(CH)2, —CH2F, —N3or —CCH. In some embodiments, the compound wherein A has the structure: wherein R7, R8, R9, R10and R11are each, independently, —H, halogen, C1-C6alkyl, —OH, —O—(C1-C6alkyl), —CHF2, —CF3, —OCHF2or —OCF3. In some embodiments, the compound wherein R7, R8, R9, R10and R11are each, independently, halogen or —O—(C1-C6alkyl). In some embodiments, the compound wherein R7, R8, R9, R10and R11are each, independently, —Cl, —Br, or —O—(C1-C6alkyl). In some embodiments, the compound wherein one of R7or R11is —H. In some embodiments, the compound wherein A has the structure: In some embodiments, the compound wherein A has the structure: In some embodiments, the compound wherein A has the structure: In some embodiments, the compound wherein A has the structure: In some embodiments, the compound having the structure: In some embodiments, the compound wherein R1is —H or —CH3; and R2is —H or —CH3. In some embodiments, the compound wherein R1is —H; and R2is —H. In some embodiments, the compound having the structure: or a pharmaceutically acceptable salt or ester thereof. In some embodiments, the compound having the structure or a pharmaceutically acceptable salt or ester thereof. In some embodiments, the compound having the structure: or a pharmaceutically acceptable salt or ester thereof. In some embodiments, a pharmaceutical composition comprising the compound of the present invention and a pharmaceutically acceptable carrier. In some embodiments, a pharmaceutical composition comprising the compound of the present invention, an anti-fungal agent and a pharmaceutically acceptable carrier. In some embodiments, a pharmaceutical composition the anti-fungal agent is fluconazole, amphotericin B, caspofungin, tunicamycin or aureobasidin A. The present invention provides a method of inhibiting the growth of a fungus comprising contacting the fungus with an effective amount of the compound of the present invention or a pharmaceutically acceptable salt or ester thereof, so as to thereby inhibit the growth of the fungus. The present invention also provides a method of inhibiting fungal sphingolipid synthesis in a fungus comprising contacting the fungus with an effective amount of the compound of the present invention or a pharmaceutically acceptable salt or ester thereof, so as to thereby inhibit sphingolipid synthesis in the fungus. The present invention further provides a method of inhibiting fungal sphingolipid synthesis in a fungus in a mammal without substantially inhibiting mammalian sphingolipid synthesis comprising administering to the mammal an effective amount of the compound of the present invention or a pharmaceutically acceptable salt or ester thereof, so as to thereby inhibit fungal sphingolipid synthesis in the fungus in the mammal without substantially inhibiting mammalian sphingolipid synthesis. In some embodiments of the method, the compound has the structure: or a pharmaceutically acceptable salt thereof. In some embodiments of the method, the compound has the structure: or a pharmaceutically acceptable salt thereof. In some embodiments of the method, the compound has the structure: or a pharmaceutically acceptable salt thereof. In some embodiments of the method, further comprising contacting the fungus with an effective amount of an anti-fungal agent. In some embodiments of the method, further comprising administering to the mammal an effective amount of an anti-fungal agent. In some embodiments of the method, wherein the amount of the compound and the amount of the anti-fungal agent when taken together is more effective to inhibit the growth of the fungus than the anti-fungal agent alone, or more effective to inhibit fungal sphingolipid synthesis than the anti-fungal agent alone. In some embodiments of the method, wherein the amount of the compound and the amount of the anti-fungal agent when taken together is more effective to inhibit fungal sphingolipid synthesis without substantially inhibiting mammalian sphingolipid synthesis in the mammal than the anti-fungal agent alone. In some embodiments of the method, wherein the anti-fungal agent is fluconazole, amphotericin B, caspofungin, tunicamycin or aureobasidin A. In some embodiments of the method, wherein the fungus isCryptococcus Neoformans, Cryptococcus gattii, Candida albicans, Candida krusei, Candida glabrata, Candida parapsilosis, Candida guilliermondii, Aspergillus fumigatus, Rhizopus oryzae, Rhizopusspp.,Blastomyces dermatitis, Histoplasma capsulatum, Coccidioidesspp.,Paecilomyces variotii, Pneumocystis murina, Pneumocystis jiroveci, Histoplasma capsulatum, Aspergillusspp., dimorphic fungi or mucorales fungi. In some embodiments of the method, wherein the fungus is other thanCryptococcus Neoformans. In some embodiments of the method, wherein the fungus isCryptococcus gattii, Candida albicans, Candida krusei, Candida glabrata, Candida parapsilosis, Candida guilliermondii, Aspergillus fumigatus, Rhizopus oryzae, Rhizopusspp.,Blastomyces dermatitis, Histoplasma capsulatum, Coccidioidesspp.,Paecilomyces variotii, Pneumocystis murina, Pneumocystis jiroveci, Histoplasma capsulatum, Aspergillusspp., dimorphic fungi or mucorales fungi. In some embodiments of the method, wherein the fungal sphingolipid is glucosylceramide (GlcCer). The present invention yet further provides a method of inhibiting the growth of or killing a fungus in a subject or treating a subject afflicted with a fungal infection comprising administering to the subject an effective amount of the compound of the present invention, or a pharmaceutically acceptable salt or ester thereof, so as to thereby inhibiting the growth of or kill the fungus in the subject or treat the subject afflicted with the fungal infection. In some embodiments of the method, further comprising administering an effective amount of an anti-fungal agent. In some embodiments of the method, wherein the amount of the compound and the amount of the anti-fungal agent when taken together is more effective to treat the subject than when the anti-fungal agent is administered alone. In some embodiments of the method, wherein the amount of the compound and the amount of the anti-fungal agent when taken together is effective to reduce a clinical symptom of the fungal infection in the subject. In some embodiments of the method, wherein the anti-fungal agent is fluconazole, amphotericin B, caspofungin, tunicamycin or aureobasidin A. In some embodiments of the method, wherein the fungal infection caused byCandida, Aspergillus, Cryptococcus, Histoplasma, Pneumocystis StachybotrysorMycroralesfungus. In some embodiments of the method, wherein the fungal infection is caused byCryptococcus Neoformans. In some embodiments the method, wherein the fungal infection isCryptococcus neoformanscryptococcosis. In some embodiments of the method, wherein the fungal infection is caused by a fungus other thanCryptococcus Neoformans. In some embodiments of the method, wherein the fungal infection is a fungal infection other thanCryptococcus neoformanscryptococcosis. In some embodiments of the method, wherein the fungal infection isAspergillosis, Blastomycosis, Candidiasis, Coccidioidomycosis, Cryptococcus gattiicryptococcosis, Fungal Keratitis, Dermatophytes, Histoplasmosis, Mucormycosis,Pneumocystis pneumonia(PCP), or Sporotrichosis. In some embodiments of the method, wherein the fungal infection is caused byCryptococcus gattii, Candida albicans, Candida krusei, Candida glabrata, Candida parapsilosis, Candida guilliermondii, Aspergillus fumigatus, Rhizopus oryzae, Rhizopusspp.,Blastomyces dermatitis, Histoplasma capsulatum, Coccidioidesspp.,Paecilomyces variotii, Pneumocystis murina, Pneumocystis jiroveci, Histoplasma capsulatum, Aspergillusspp., or dimorphic fungi. The present invention yet further provides a compound having the following structure: or a pharmaceutically acceptable salt thereof, for use in inhibiting the growth of a fungus. The present invention yet further provides a compound having the following structure: or a pharmaceutically acceptable salt thereof, for use in inhibiting fungal sphingolipid synthesis in a fungus. The present invention yet further provides a compound having the following structure: or a pharmaceutically acceptable salt thereof, for use in inhibiting fungal sphingolipid synthesis in a fungus in a mammal. The present invention yet further provides a compound having the following structure: or a pharmaceutically acceptable salt thereof, for use in inhibiting the growth of or killing a fungus in a subject or treating a subject afflicted with a fungal infection caused by the fungus. In some embodiments the compound for use wherein the fungus is other thanCryptococcus Neoformans. In some embodiments the compound for use wherein the fungal infection is caused by a fungus other thanCryptococcus Neoformans. In some embodiments the compound for use wherein the fungal infection is a fungal infection other thanCryptococcus neoformanscryptococcosis. In some embodiments the compound for use further comprising an anti-fungal agent. In some embodiments the compound for use wherein the anti-fungal agent is fluconazole, amphotericin B, caspofungin, tunicamycin or aureobasidin A. The present invention yet further provides a pharmaceutical composition comprising the compound having the following structure: or a pharmaceutically acceptable salt thereof, an anti-fungal agent and a pharmaceutically acceptable carrier. In some embodiments, the pharmaceutical composition wherein the anti-fungal agent is fluconazole, amphotericin B, caspofungin, tunicamycin or aureobasidin A. The present invention yet further provides a pharmaceutical composition comprising a compound having the following structure: or a pharmaceutically acceptable salt thereof, for use in inhibiting the growth of a fungus. The present invention yet further provides a pharmaceutical composition comprising a compound having the following structure: or a pharmaceutically acceptable salt thereof, for use in inhibiting fungal sphingolipid synthesis in a fungus. The present invention yet further provides a pharmaceutical composition comprising a compound having the following structure: or a pharmaceutically acceptable salt thereof, for use in inhibiting fungal sphingolipid synthesis in a fungus in a mammal. The present invention yet further provides a pharmaceutical composition comprising a compound having the following structure: or a pharmaceutically acceptable salt thereof, for use in inhibiting the growth of or killing a fungus in a subject or treating a subject afflicted with a fungal infection caused by the fungus. The present invention yet further provides a pharmaceutical composition comprising a compound having the following structure: or a pharmaceutically acceptable salt thereof, and an anti-fungal agent for use in inhibiting the growth of a fungus. The present invention yet further provides a pharmaceutical composition comprising a compound having the following structure: or a pharmaceutically acceptable salt thereof, and an anti-fungal agent for use in inhibiting fungal sphingolipid synthesis in a fungus. The present invention yet further provides a pharmaceutical composition comprising a compound having the following structure: or a pharmaceutically acceptable salt thereof, and an anti-fungal agent for use in inhibiting fungal sphingolipid synthesis in a fungus in a mammal. The present invention yet further provides a pharmaceutical composition comprising a compound having the following structure: or a pharmaceutically acceptable salt thereof, and an anti-fungal agent for use in inhibiting the growth of or killing a fungus in a subject or treating a subject afflicted with a fungal infection caused by the fungus. In some embodiments, the method wherein the anti-fungal agent is fluconazole, amphotericin B, caspofungin, tunicamycin or aureobasidin A. In some embodiments, the method wherein the fungal infection is caused byCandida, Aspergillus, Cryptococcus, Histoplasma, Pneumocystis, Stachybotrys or Mycrorales fungus. In some embodiments, the method wherein the fungal infection is Aspergillosis, Blastomycosis, Candidiasis, Coccidioidomycosis,Cryptococcus gattiicryptococcosis, Fungal Keratitis, Dermatophytes, Histoplasmosis, Mucormycosis,Pneumocystis pneumonia(PCP), or Sporotrichosis. In some embodiments, the method wherein the fungal infection is caused byCryptococcus gattii, Candida albicans, Candida krusei, Candida glabrata, Candida parapsilosis, Candida guilliermondii, Aspergillus fumigatus, Rhizopus oryzae, Rhizopusspp.,Blastomyces dermatitis, Histoplasma capsulatum, Coccidioidesspp.Paecilomyces variotii, Pneumocystis murina, Pneumocystis jiroveci, Histoplasma capsulatum, or dimorphic fungi. In some embodiments, the fungal infection is an internal fungal infection. In some embodiments, the fungal infection is an invasive fungal infection. In some embodiments, the fungal infection is a fungal infection of the skin or lung. In some embodiments, the compound has a fungistatic effect on the fungus. In some embodiments, the compound has a fungicidal effect on the fungus. In some embodiments, the compound is administered orally to the subject. In some embodiments, the compound is administered topically to the subject. In some embodiments, the subject is also afflicted with an immunodeficiency disorder. In some embodiments, the subject is also afflicted with human immunodeficiency virus (HIV). In some embodiments, the antifungal agent is Amphotericin B, Candicidin, Filipin, Hamycin, Natamycin, Nystatin, Rimocidin, Clotrimazole, Bifonazole, Butoconazole, Clotrimazole, Econazole, Fenticonazole, Isoconazole, Ketoconazole, Luliconazole, Miconazole, Omoconazole, Oxiconazole, Sertaconazole, Sulconazole, Tioconazole, Albaconazole, Fluconazole, Isavuconazole, itraconazole, Posaconazole, Ravuconazole, Terconazole, Voriconazole, Abafungin, Amorolfin, Butenafine, Naftifine, Terbinafine, Anidulafungin, Caspofungin, Micafungin, Ciclopirox, Flucytosine, Griseofulvin, Haloprogin, Tolnaftate, or Undecylenic acid. In some embodiments, a pharmaceutical composition comprising a compound of the present invention and an antifungal agent, and at least one pharmaceutically acceptable carrier for use in treating a fungal infection. In some embodiments, a pharmaceutical composition comprising an amount of the compound of the present invention for use in treating a subject afflicted with a fungal infection as an add-on therapy or in combination with, or simultaneously, contemporaneously or concomitantly with an anti-fungal agent. In some embodiments of any of the above methods or uses, the subject is a human. In some embodiments of any of the above methods or uses, the compound and/or anti-fungal agent is orally administered to the subject. In some embodiments of any of the above methods or uses, the compound and/or anti-fungal agent is topically administered to the subject. In some embodiments, the fungus or fungal infection has developed resistance to one or more drugs. For example, a drug resistant fungal infection may have developed drug-resistance to an azole antifungal drug, a polyene antifungal drug and/or an echinocandin antifungal drug. In some embodiments of any of the above methods or uses, the compound ti targets APL5, COS111, MKK1, and STE2 in the fungus. In some embodiments of any of the above methods or uses, the compound targets at least one of APL5, COS111, MKK1, or STE2 in the fungus. In some embodiments of any of the above methods or uses, the compound disrupts vesicular transport mediate by APL5. In some embodiments of any of the above methods or uses, the fungus carries non-mutated APL5, COS111, MKK2, and STE2. In some embodiments of any of the above methods or uses, the fungus carries at least one of non-mutated APL5, COS111, MKK1, and STE2. As used herein, a “symptom” associated with a fungal infection includes any clinical or laboratory manifestation associated with the fungal infection and is not limited to what the subject can feel or observe. As used herein, “treating”, e.g. of a fungal infection, encompasses inducing prevention, inhibition, regression, or stasis of the disease or a symptom or condition associated with the infection. Compound 1 (ID #5271226), Compound 2 (ID #5281029), Compound 13 (ID #5475098), and Compound 17 (ID #5275737), are available from ChemBridge™, San Diego, CA. The contents of International Application Publication No. WO/2016/094307, published Jun. 16, 2016, are hereby incorporated by reference. The compounds of the present invention include all hydrates, solvates, and complexes of the compounds used by this invention. If a chiral center or another form of an isomeric center is present in a compound of the present invention, all forms of such isomer or isomers, including enantiomers and diastereomers, are intended to be covered herein. Compounds containing a chiral center may be used as a racemic mixture, an enantiomerically enriched mixture, or the racemic mixture may be separated using well-known techniques and an individual enantiomer may be used alone. The compounds described in the present invention are in racemic form or as individual enantiomers. The enantiomers can be separated using known techniques, such as those described in Pure and Applied Chemistry 69, 1469-1474, (1997) IUPAC. In cases in which compounds have unsaturated carbon-carbon double bonds, both the cis (Z) and trans (H) isomers are within the scope of this invention. The compounds of the subject invention may have spontaneous tautomeric forms. In cases wherein compounds may exist in tautomeric forms, such as keto-enol tautomers, each tautomeric form is contemplated as being included within this invention whether existing in equilibrium or predominantly in one form. In the compound structures depicted herein, hydrogen atoms are not shown for carbon atoms having less than four bonds to non-hydrogen atoms. However, it is understood that enough hydrogen atoms exist on said carbon atoms to satisfy the octet rule. This invention also provides isotopic variants of the compounds disclosed herein, including wherein the isotopic atom is2H and/or wherein the isotopic atom13C. Accordingly, in the compounds provided herein hydrogen can be enriched in the deuterium isotope. It is to be understood that the invention encompasses all such isotopic forms. It is understood that the structures described in the embodiments of the methods hereinabove can be the same as the structures of the compounds described hereinabove. It is understood that where a numerical range is recited herein, the present invention contemplates each integer between, and including, the upper and lower limits, unless otherwise stated. Except where otherwise specified, if the structure of a compound of this invention includes an asymmetric carbon atom, it is understood that the compound occurs as a racemate, racemic mixture, and isolated single enantiomer. All such isomeric forms of these compounds are expressly included in this invention. Except where otherwise specified, each stereogenic carbon may be of the R or S configuration. It is to be understood accordingly that the isomers arising from such asymmetry (e.g., all enantiomers and diastereomers) are included within the scope of this invention, unless indicated otherwise. Such isomers can be obtained in substantially pure form by classical separation techniques and by stereochemically controlled synthesis, such as those described in “Enantiomers, Racemates and Resolutions” by J. Jacques, A. Collet and S. Wilen, Pub. John Wiley & Sons, NY, 1981. For example, the resolution may be carried out by preparative chromatography on a chiral column. The subject invention is also intended to include all isotopes of atoms occurring on the compounds disclosed herein. Isotopes include those atoms having the same atomic number but different mass numbers. By way of general example and without limitation, isotopes of hydrogen include tritium and deuterium. Isotopes of carbon include C-13 and C-14. It will be noted that any notation of a carbon in structures throughout this application, when used without further notation, are intended to represent all isotopes of carbon, such as12C,13C, or14C. Furthermore, arty compounds containing13C or14C may specifically have the structure of any of the compounds disclosed herein. It will also be noted that any notation of a hydrogen in structures throughout this application, when used without further notation, are intended to represent all isotopes of hydrogen, such as1H,2H, or3H. Furthermore, any compounds containing2H or3H may specifically have the structure of any of the compounds disclosed herein. Isotopically-labeled compounds can generally be prepared by conventional techniques known to those skilled in the art using appropriate isotopically-labeled reagents in place of the non-labeled reagents employed. In the compounds used in the method of the present invention, the substituents may be substituted or unsubstituted unless specifically defined otherwise. In the compounds used in the method of the present invention, alkyl, heteroalkyl, monocycle, bicycle, aryl, heteroaryl and heterocycle groups can be further substituted by replacing one or more hydrogen atoms with alternative non-hydrogen groups. These include, but are not limited to, halo, hydroxy, mercapto, amino, carboxy, cyano, carbamoyl and aminocarbonyl and aminothiocarbonyl. It is understood that substituents and substitution patterns on the compounds used in the method of the present invention can be selected by one of ordinary skill in the art to provide compounds that are chemically stable and that can be readily synthesized by techniques known in the art from readily available starting materials. If a substituent is itself substituted with more than one group, it is understood that these multiple groups may be on the same carbon or on different carbons, so long as a stable structure results. In choosing the compounds used in the method of the present invention, one of ordinary skill in the art will recognize that the various substituents, i.e. R1, R2, etc. are to be chosen in conformity with well-known principles of chemical structure connectivity. As used herein, “alkyl” is intended to include both branched and straight-chain saturated aliphatic hydrocarbon groups having the specified number of carbon atoms. Thus, C1-Cnas in “C1-Cnalkyl” is defined to include groups having 1, 2 . . . , n−1 or n carbons in a linear or branched arrangement, and specifically includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, sec-butyl and so on. An embodiment can be C1-C12alkyl, C2-C12alkyl, C3-C12alkyl, C4-C12alkyl and so on. “Alkoxy” represents an alkyl group as described above attached through an oxygen bridge. The term “alkenyl” refers to a non-aromatic hydrocarbon radical, straight or branched, containing at least 1 carbon to carbon double bond, and up to the maximum possible number of non-aromatic carbon-carbon double bonds may be present. Thus, C2-Cnalkenyl is defined to include groups having 1, 2 . . . , n−1 or n carbons. For example, “C2-C6alkenyl” means an alkenyl radical having 2, 3, 4, 5, or 6 carbon atoms, and at least 1 carbon-carbon double bond, and up to, for example, 3 carbon-carbon double bonds in the case of a C6alkenyl, respectively. Alkenyl groups include ethenyl, propenyl, butenyl and cyclohexenyl. As described above, with respect to alkyl, the straight, branched or cyclic portion of the alkenyl group may contain double bonds and may be substituted if a substituted alkenyl group is indicated. An embodiment can be C2-C12, alkenyl, C3-C12alkenyl, C4-C12alkenyl and so on. The term “alkynyl” refers to a hydrocarbon radical straight or branched, containing at least 1 carbon to carbon triple bond, and up to the maximum possible number of non-aromatic carbon-carbon triple bonds may be present. Thus, C2-Cnalkynyl is defined to include groups having 1, 2 . . . , n−1 or n carbons. For example, “C2-C6alkynyl” means an alkynyl radical having 2 or 3 carbon atoms, and 1 carbon-carbon triple bond, or having 4 or 5 carbon atoms, and up to 2 carbon-carbon triple bonds, or having 6 carbon atoms, and up to 3 carbon-carbon triple bonds. Alkynyl groups include ethynyl, propynyl and butynyl. As described above with respect to alkyl, the straight or branched portion of the alkynyl group may contain triple bonds and may be substituted if a substituted alkynyl group is indicated. An embodiment can be a C2-Cnalkynyl. An embodiment can be C2-C12alkynyl, C3-C12alkynyl, C4-C12alkynyl and so on “Alkylene”, “alkenylene” and, “alkynylene” shall mean, respectively, a divalent alkane, alkene and alkyne radical, respectively. It is understood that an alkylene, alkenylene, and alkynylene may be straight or branched. An alkylene, alkenylene, and alkynylene may be unsubstituted or substituted. As used herein, “heteroalkyl” includes both branched and straight-chain saturated aliphatic hydrocarbon groups having the specified number of carbon atoms and at least 1 heteroatom within the chain or branch. As used herein, “heterocycle” or “heterocyclyl” as used herein is intended to mean a 5- to 10-membered nonaromatic ring containing from 1 to 4 heteroatoms selected from the group consisting of O, N and S, and includes bicyclic groups. “Heterocyclyl” therefore includes, but is not limited to the following: imidazolyl, piperazinyl, piperidinyl, pyrrolidinyl, morpholinyl, thiomorpholinyl, tetrahydropyranyl, dihydropiperidinyl, tetrahydrothiophenyl and the like. If the heterocycle contains a nitrogen, it is understood that the corresponding N-oxides thereof are also encompassed by this definition. As herein, “cycloalkyl” shall mean cyclic rings of alkanes of three to eight total carbon atoms, or any number within this range (i.e., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl). As used herein, “monocycle” includes any stable polyatomic carbon ring of up to 10 atoms and may be unsubstituted or substituted. Examples of such non-aromatic monocycle elements include but are not limited to: cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. Examples of such aromatic monocycle elements include but are not limited to: phenyl. As used herein, “bicycle” includes any stable polyatomic carbon ring of up to 10 atoms that is fused to a polyatomic carbon ring of up to 10 atoms with each ring being independently unsubstituted or substituted. Examples of such non-aromatic bicycle elements include but are not limited to: decahydronaphthalene. Examples of such aromatic bicycle elements include but are not limited to: naphthalene. As used herein, “aryl” is intended to mean any stable monocyclic, bicyclic or polycyclic carbon ring of up to 10 atoms in each ring, wherein at least one ring is aromatic, and may be unsubstituted or substituted. Examples of such aryl elements include phenyl, p-toluenyl (4-methylphenyl), naphthyl, tetrahydro-naphthyl, indanyl, biphenyl, phenanthryl, anthryl or acenaphthyl. In cases where the aryl substituent is bicyclic and one ring is non-aromatic, it is understood that attachment is via the aromatic ring. As used herein, the term “polycyclic” refers to unsaturated or partially unsaturated multiple fused ring structures, which may be unsubstituted or substituted. The term “arylalkyl” refers to alkyl groups as described above wherein one or more bonds to hydrogen contained therein are replaced by a bond to an aryl group as described above. It is understood that an “arylalkyl” group is connected to a core molecule through a bond from the alkyl group and that the aryl group acts as a substituent on the alkyl group. Examples of arylalkyl moieties include, but are not limited to, benzyl (phenylmethyl), p-trifluoromethylbenzyl (4-trifluoromethylphenylmethyl), 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, 2-phenylpropyl and the like. The term “heteroaryl”, as used herein, represents a stable monocyclic, bicyclic or polycyclic ring of up to 10 atoms in each ring, wherein at least one ring is aromatic and contains from 1 to 4 heteroatoms selected from the group consisting of O, N and S. Bicyclic aromatic heteroaryl groups include phenyl, pyridine, pyrimidine or pyridizine rings that are (a) fused to a 6-membered aromatic (unsaturated) heterocyclic ring having one nitrogen atom; (b) fused to a 5- or 6-membered aromatic (unsaturated) heterocyclic ring having two nitrogen atoms; (c) fused to a 5-membered aromatic (unsaturated) heterocyclic ring having one nitrogen atom together with either one oxygen or one sulfur atom; or (d) fused to a 5-membered aromatic (unsaturated) heterocyclic ring having one heteroatom selected from O, N or S. Heteroaryl groups within the scope of this definition include but are not limited to: benzoimidazolyl, benzofuranyl, benzofurazanyl, benzopyrazolyl, benzotriazolyl, benzothiophenyl, benzoxazolyl, carbazolyl, carbolinyl, cinnolinyl, furanyl, indolinyl, indolyl, indolazinyl, indazolyl, isobenzofuranyl, isoindolyl, isoquinolyl, isothiazolyl, isoxazolyl, naphthpyridinyl, oxadiazolyl, oxazolyl, oxazoline, isoxazoline, oxetanyl, pyranyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridopyridinyl, pyridazinyl, pyridyl, pyrimidyl, pyrrolyl, quinazolinyl, quinolyl, quinoxalinyl, tetrazolyl, tetrazolopyridyl, thiadiazolyl, thiazolyl, thienyl, triazolyl, azetidinyl, aziridinyl, 1,4-dioxanyl, hexahydroazepinyl, dihydrobenzoimidazolyl, dihydrobenzofuranyl, dihydrobenzothiophenyl, dihydrobenzoxazolyl, dihydrofuranyl, dihydroimidazolyl, dihydroindolyl, dihydroisooxazolyl, dihydroisothiazolyl, dihydrooxadiazolyl, dihydrooxazolyl, dihydropyrazinyl, dihydropyrazolyl, dihydropyridinyl, dihydropyrimidinyl, dihydropyrrolyl, dihydroquinolinyl, dihydrotetrazolyl, dihydrothiadiazolyl, dihydrothiazolyl, dihydrothienyl, dihydrotriazolyl, dihydroazetidinyl, methylenedioxybenzoyl, tetrahydrofuranyl, tetrahydrothienyl, acridinyl, carbazolyl, cinnolinyl, quinoxalinyl, pyrrazolyl, indolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, isoxazolyl, isothiazolyl, furanyl, thienyl, benzothienyl benzofuranyl, quinolinyl, isoquinolinyl, oxazolyl, isoxazolyl, indolyl, pyrazinyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl, tetra-hydroquinoline. In cases where the heteroaryl substituent is bicyclic and one ring is non-aromatic or contains no heteroatoms, it is understood that attachment is via the aromatic ring or via the heteroatom containing ring, respectively. If the heteroaryl contains nitrogen atoms, it is understood that the corresponding N-oxides thereof are also encompassed by his definition. The term “alkylheteroaryl” refers to alkyl groups as described above wherein one or more bonds to hydrogen contained therein are replaced by a bond to an heteroaryl group as described above. It is understood that an “alkylheteroaryl” group is connected to a core molecule through a bond from the alkyl group and that the heteroaryl group acts as substituent on the alkyl group. Examples of alkylheteroaryl moieties include, but are not limited to, —CH2—(C5H4N), —CH2—CH2—(C5H4N) and the like. The term “heterocycle” or “heterocyclyl” refers to a mono- or poly-cyclic ring system which can be saturated or contains one or more degrees of unsaturation and contains one or more heteroatoms. Preferred heteroatoms include N, O, and/or S, including N-oxides, sulfur oxides, and dioxides. Preferably the ring is three to ten-membered and is either saturated or has one or more degrees of unsaturation. The heterocycle may be unsubstituted or substituted, with multiple degrees of substitution being allowed. Such rings may be optionally fused to one or more of another “heterocyclic” ring (s), heteroaryl ring(s), aryl ring (s), or cycloalkyl ring(s). Examples of heterocycles include, but are not limited to, tetrahydrofuran, pyran, 1,4-dioxane, 1,3-dioxane, piperidine, piperazine, pyrrolidine, morpholine, thiomorpholine, tetrahydrothiopyran, tetrahydrothiophene, 1,3-oxathiolane, and the like. The alkyl, alkenyl, alkynyl, aryl, heteroaryl and heterocyclyl substituents may be substituted or unsubstituted, unless specifically defined otherwise. In the compounds of the present invention, alkyl, alkenyl, alkynyl, aryl, heterocyclyl and heteroaryl groups can be further substituted by replacing one or more hydrogen atoms with alternative non-hydrogen groups. These include, but are not limited to, halo, hydroxy, mercapto, amino, carboxy, cyano and carbamoyl. As used herein, the term “halogen” refers to F, Cl, Br, and I. The terms “substitution”, “substituted” and “substituent” refer to a functional group as described above in which one or more bonds to a hydrogen atom contained therein are replaced by a bond to non-hydrogen or non-carbon atoms, provided that normal valencies are maintained and that the substitution results in a stable compound. Substituted groups also include groups in which one or more bonds to a carbon(s) or hydrogen(s) atom are replaced by one or more bonds, including double or triple bonds, to a heteroatom. Examples of substituent groups include the functional groups described above, and halogens (i.e., F, Cl, Br, and I); alkyl groups, such as methyl, ethyl, n-propyl, isopropryl, n-butyl, tert-butyl, and trifluoromethyl; hydroxyl; alkoxy groups, such as methoxy, ethoxy, n-propoxy, and isopropoxy; aryloxy groups, such as phenoxy; arylalkyloxy, such as benzyloxy (phenylmethoxy) and p-trifluoromethylbenzyloxy (4-trifluoromethylphenylmethoxy); heteroaryloxy groups; sulfonyl groups, such as trifluoromethanesulfonyl, methanesulfonyl, and p-toluenesulfonyl; nitro, nitrosyl; mercapto; sulfanyl groups, such as methylsulfanyl, ethylsulfanyl and propylsulfanyl; cyano; amino groups, such as amino, methylamino, dimethylamino, ethyl amino, and diethylamidino; and carboxyl. Where multiple substituent moieties are disclosed or claimed, the substituted compound can be independently substituted by one or more of the disclosed or claimed substituent moieties, singly or pluraly. By independently substituted, it is meant that the (two or more) substituents can be the same or different. It is understood that substituents and substitution patterns on the compounds of the instant invention can be selected by one of ordinary skill in the art to provide compounds that are chemically stable and that can be readily synthesized by techniques known in the art, as well as those methods set forth below, from readily available starting materials. If a substituent is itself substituted with more than one group, it is understood that these multiple groups may be on the same carbon or on different carbons, so long as a stable structure results. In choosing the compounds of the present invention, one of ordinary skill in the art will recognize that the various substituents, i.e. R1, R2, etc. are to be chosen in conformity with well-known principles of chemical structure connectivity. The various R groups attached to the aromatic rings of the compounds disclosed herein may be added to the rings by standard procedures, for example those set forth in Advanced Organic Chemistry: Part B: Reaction and Synthesis, Francis Carey and Richard Sundberg, (Springer) 5th ed. Edition. (2007), the content of which is hereby incorporated by reference. The compounds used in the method of the present invention may be prepared by techniques well known in organic synthesis and familiar to a practitioner ordinarily skilled in the art. However, these may not be the only means by which to synthesize or obtain the desired compounds. The compounds used in the method of the present invention may be prepared by techniques described in Vogel's Textbook of Practical Organic Chemistry, A. I. Vogel, A. R. Tatchell, B. S. Furnis, A. J. Hannaford, P. W. G. Smith, (Prentice Hall) 5thEdition (1996), March's Advanced. Organic Chemistry: Reactions, Mechanisms, and Structure, Michael B. Smith, Jerry March, (Wiley-Interscience) 5thEdition (2007), and references therein, which are incorporated by reference herein. However, these may not be the only means by which to synthesize or obtain the desired compounds. Another aspect of the invention comprises a compound used in the method of the present invention as a pharmaceutical composition. In some embodiments, a pharmaceutical composition comprising the compound of the present invention and a pharmaceutically acceptable carrier. As used herein, the term “pharmaceutically active agent” means any substance or compound suitable for administration to a subject and furnishes biological activity or other direct effect in the treatment, cure, mitigation, diagnosis, or prevention of disease, or affects the structure or any function of the subject. Pharmaceutically active agents include, but are not limited to, substances and compounds described in the Physicians' Desk Reference (PDR Network, LLC; 64th edition; Nov. 15, 2009) and “Approved Drug Products with Therapeutic Equivalence Evaluations” (U.S. Department Of Health And Human. Services, 30thedition, 2010), which are hereby incorporated by reference. Pharmaceutically active agents which have pendant carboxylic acid groups may be modified in accordance with the present invention using standard esterification reactions and methods readily available and known to those having ordinary skill in the art of chemical synthesis. Where a pharmaceutically active agent does not possess a carboxylic acid group, the ordinarily skilled artisan will be able to design and incorporate a carboxylic acid group into the pharmaceutically active agent where esterification may subsequently be carried out so long as the modification does not interfere with the pharmaceutically active agent's biological activity or effect. The compounds used in the method of the present invention may be in a salt form. As used herein, a “salt” is a salt of the instant compounds which has been modified by making acid or base salts of the compounds. In the case of compounds used to treat an infection or disease caused by a pathogen, the salt is pharmaceutically acceptable. Examples of pharmaceutically acceptable salts include, but are not limited to, mineral or organic acid salts of basic residues such as amines; alkali or organic salts of acidic residues such as phenols. The salts can be made using an organic or inorganic acid. Such acid salts are chlorides, bromides, sulfates, nitrates, phosphates, sulfonates, formates, tartrates, maleates, malates, citrates, benzoates, salicylates, ascorbates, and the like. Phenolate salts are the alkaline earth metal salts, sodium, potassium or lithium. The term “pharmaceutically acceptable salt” in this respect, refers to the relatively non-toxic, inorganic and organic acid or base addition salts of compounds of the present invention. These salts can be prepared in situ during the final isolation and purification of the compounds of the invention, or by separately reacting a purified compound of the invention in its free base or free acid form with a suitable organic or inorganic acid or base, and isolating the salt thus formed. Representative salts include the hydrobromide, hydrochloride, sulfate, bisulfate, phosphate, nitrate, acetate, valerate, oleate, palmitate, stearate, laurate, benzoate, lactate, phosphate, tosylate, citrate, maleate, fumarate, succinate, tartrate, napthylate, mesylate, glucoheptonate, lactobionate, and laurylsulphonate salts and the like. (See, e.g., Berge et al. (1977) “Pharmaceutical Salts”, J. Pharm. Sci. 66:1-19). The compounds of the present invention may also form salts with basic amino acids such a lysine, arginine, etc. and with basic sugars such as N-methylglucamine, 2-amino-2-deoxyglucose, etc. and any other physiologically non-toxic basic substance. As used herein, “administering” an agent may be performed using any of the various methods or delivery systems well known to those skilled in the art. The administering can be performed, for example, orally, parenterally, intraperitoneally, intravenously, intraarterially, transdermally, sublingually, intramuscularly, rectally, transbuccally, intranasally, liposomally, via inhalation, vaginally, intraoccularly, via local delivery, subcutaneously, intraadiposally, intraarticularly, intrathecally, into a cerebral ventricle, intraventricularly, intratumorally, into cerebral parenchyma or intraparenchchymally. The compounds used in the method of the present invention may be administered in various forms, including those detailed herein. The treatment with the compound may be a component of a combination therapy or an adjunct therapy, i.e. the subject or patient in need of the drug is treated or given another drug for the disease in conjunction with one or more of the instant compounds. This combination therapy can be sequential therapy where the patient is treated first with one drug and then the other or the two drugs are given simultaneously. These can be administered independently by the same route or by two or more different routes of administration depending on the dosage forms employed. As used herein, a “pharmaceutically acceptable carrier” is pharmaceutically acceptable solvent, suspending agent or vehicle, for delivering the instant compounds to the animal or human. The carrier may be liquid or solid and is selected with the planned manner of administration in mind. Liposomes are also a pharmaceutically acceptable carrier as are slow-release vehicles. The dosage of the compounds administered in treatment will vary depending upon factors such as the pharmacodynamic characteristics of a specific chemotherapeutic agent and its mode and route of administration; the age, sex, metabolic rate, absorptive efficiency, health and weight of the recipient; the nature and extent of the symptoms; the kind of concurrent treatment being administered; the frequency of treatment with; and the desired therapeutic effect. A dosage unit of the compounds used in the method of the present invention may comprise a single compound or mixtures thereof with additional antitumor agents. The compounds can be administered in oral dosage forms as tablets, capsules, pills, powders, grannies, elixirs, tinctures, suspensions, syrups, and emulsions. The compounds may also be administered in intravenous (bolus or infusion), intraperitoneal, subcutaneous, or intramuscular form, or introduced directly, e.g. by in topical application, or other methods, into or topically onto a site of disease or lesion, all using dosage forms well known to those of ordinary skill in the pharmaceutical arts. The compounds used in the method of the present invention can be administered in admixture with suitable pharmaceutical diluents, extenders, excipients, or in carriers such as the novel programmable sustained-release multi-compartmental nanospheres (collectively referred to herein as a pharmaceutically acceptable carrier) suitably selected with respect to the intended form of administration and as consistent with conventional pharmaceutical practices. The unit will be in a form suitable for oral, nasal, rectal, topical, intravenous or direct injection or parenteral administration. The compounds can be administered alone or mixed with a pharmaceutically acceptable carrier. This carrier can be a solid or liquid, and the type of carrier is generally chosen based on the type of administration being used. The active agent can be co-administered in the form, of a tablet or capsule, liposome, as an agglomerated powder or in a liquid form. Examples of suitable solid carriers include lactose, sucrose, gelatin and agar. Capsule or tablets can be easily formulated and can be made easy to swallow or chew; other solid forms include granules, and hulk powders. Tablets may contain suitable binders, lubricants, diluents, disintegrating agents, coloring agents, flavoring agents, flow-inducing agents, and melting agents. Examples of suitable liquid dosage forms include solutions or suspensions in water, pharmaceutically acceptable fats and oils, alcohols or other organic solvents, including esters, emulsions, syrups or elixirs, suspensions, solutions and/or suspensions reconstituted from non-effervescent granules and effervescent preparations reconstituted from effervescent granules. Such liquid dosage forms may contain, for example, suitable solvents, preservatives, emulsifying agents, suspending agents, diluents, sweeteners, thickeners, and melting agents. Oral dosage forms optionally contain flavorants and coloring agents. Parenteral and intravenous forms may also include minerals and other materials to make them compatible with the type of injection or delivery system chosen. Techniques and compositions for making dosage forms useful in the present invention are described in the following references: 7 Modern Pharmaceutics, Chapters 9 and 10 (Banker & Rhodes, Editors, 1979) Pharmaceutical Dosage Forms: Tablets (Lieberman et al., 1981); Ansel, Introduction to Pharmaceutical Dosage Forms 2nd Edition (1976); Remington's Pharmaceutical Sciences, 17th ed. (Mack Publishing Company, Easton, Pa., 1985); Advances in Pharmaceutical Sciences (David Ganderton, Trevor Jones, Eds., 1992); Advances in Pharmaceutical Sciences Vol. 7. (David Ganderton, Trevor Jones, James McGinity, Eds., 1995); Aqueous Polymeric Coatings for Pharmaceutical Dosage Forms (Drugs and the Pharmaceutical Sciences, Series 36 (James McGinity, Ed., 1909); Pharmaceutical Particulate Carriers: Therapeutic Applications: Drugs and the Pharmaceutical Sciences, Vol 61 (Alain Rolland, Ed., 1993); Drug Delivery to the Gastrointestinal Tract (Ellis Horwood Books in the Biological Sciences. Series in Pharmaceutical Technology; J. G. Hardy, S. S. Davis, Clive G. Wilson, Eds.); Modem Pharmaceutics Drugs and the Pharmaceutical Sciences, Vol 40 (Gilbert S. Banker, Christopher T. Rhodes, Eds.). All of the aforementioned publications are incorporated by reference herein. Tablets may contain suitable hinders, lubricants, disintegrating agents, coloring agents, flavoring agents, flow-inducing agents, and melting agents. For instance, for oral administration in the dosage unit form of a tablet or capsule, the active drug component can be combined with an oral, non-toxic, pharmaceutically acceptable, inert carrier such as lactose, gelatin, agar, starch, sucrose, glucose, methyl cellulose, magnesium stearate, dicalcium phosphate, calcium sulfate, mannitol, sorbitol and the like. Suitable binders include starch, gelatin, natural sugars such as glucose or beta-lactose, corn sweeteners, natural and synthetic gums such as acacia, tragacanth, or sodium alginate, carboxymethylcellulose, polyethylene glycol, waxes, and the like. Lubricants used in these dosage forms include sodium oleate, sodium stearate, magnesium stearate, sodium benzoate, sodium acetate, sodium chloride, and the like. Disintegrators include, without limitation, starch, methyl cellulose, agar, bentonite, xanthan gum, and the like. The compounds used in the method of the present; invention may also be administered in the form of liposome delivery systems, such as small unilamellar vesicles, large unilamellar vesicles, and multilamellar vesicles. Liposomes can be formed from a variety of phospholipids such as lecithin, sphingomyelin, proteolipids, protein-encapsulated vesicles or from cholesterol, stearylamine, or phosphatidylcholines. The compounds may be administered as components of tissue-targeted emulsions. The compounds used in the method of the present invention may also be coupled to soluble polymers as targetable drug carriers or as a prodrug. Such polymers include polyvinylpyrrolidone, pyran copolymer, polyhydroxylpropylmethacrylamide-phenol, polyhydroxyethylasparta-midephenol, or polyethyleneoxide-polylysine substituted with palmitoyl residues. Furthermore, the compounds may be coupled to a class of biodegradable polymers useful in achieving controlled release of a drug, for example, polylactic acid, polyglycolic acid, copolymers of polylactic and polyglycolic acid, polyepsilon caprolactone, polyhydroxy butyric acid, polyorthoesters, polyacetals, polydihydropyrans, polycyanoacylates, and crosslinked or amphipathic block copolymers of hydrogels. Gelatin capsules may contain the active ingredient compounds and powdered carriers, such as lactose, starch, cellulose derivatives, magnesium stearate, stearic acid, and the like. Similar diluents can be used to make compressed tablets. Both tablets and capsules can be manufactured as immediate release products or as sustained release products to provide for continuous release of medication over a period of hours. Compressed tablets can be sugar-coated or film-coated to mask any unpleasant taste and protect the tablet from the atmosphere, or enteric coated for selective disintegration in the gastrointestinal tract. For oral administration in liquid dosage form, the oral drug components are combined with any oral, non-toxic, pharmaceutically acceptable inert carrier such as ethanol, glycerol, water, and the like. Examples of suitable liquid dosage forms include solutions or suspensions in water, pharmaceutically acceptable fats and oils, alcohols or other organic solvents, including esters, emulsions, syrups or elixirs, suspensions, solutions and/or suspensions reconstituted from non-effervescent granules and effervescent preparations reconstituted from effervescent granules. Such dosage forms may contain, for example, suitable solvents, preservatives, emulsifying agents, suspending agents, diluents, sweeteners, thickeners, and melting agents. Liquid dosage forms for oral administration can contain coloring and flavoring to increase patient acceptance. In general, water, asuitable oil, saline, aqueous dextrose (glucose), and related sugar solutions and glycols such as propylene glycol or polyethylene glycols are suitable carriers for parenteral solutions. Solutions for parenteral administration preferably contain a water-soluble salt of the active ingredient, suitable stabilizing agents, and if necessary, buffer substances. Antioxidizing agents such as sodium bisulfite, sodium sulfite, or ascorbic acid, either alone or combined, are suitable stabilizing agents. Also used are citric acid and its salts and sodium EDTA. In addition, parenteral solutions can contain preservatives, such as benzalkonium chloride, methyl- or propyl-paraben, and chlorobactene. Suitable pharmaceutical carriers are described in Remington's Pharmaceutical Sciences, Mack Publishing Company, a standard reference text in this field. The compounds used in the method of the present invention may also be administered in intranasal form via use of suitable intranasal vehicles, or via transdermal routes, using those forms of transdermal skin patches well known to those of ordinary skill in that art. To be administered in the form of a transdermal delivery system, the dosage administration will generally be continuous rather than intermittent throughout the dosage regimen. Parenteral and intravenous forms may also include minerals and other materials such as solutol and/or ethanol to make them compatible with the type of injection or delivery system chosen. The compounds and compositions of the present invention can be administered in oral dosage forms as tablets, capsules, pills, powders, granules, elixirs, tinctures, suspensions, syrups, and emulsions. The compounds may also be administered in intravenous (bolus or infusion), intraperitoneal, subcutaneous, or intramuscular form, or introduced directly, e.g. by topical administration, injection or other methods, to the afflicted area, such as a wound, including ulcers of the skin, ail using dosage forms well known to those of ordinary skill in the pharmaceutical arts. Specific examples of pharmaceutically acceptable carriers and excipients that may be used to formulate oral dosage forms of the present invention are described in U.S. Pat. No. 3,903,297 to Robert, issued Sep. 2, 1975. Techniques and compositions for making dosage forms useful in the present invention are described-in the following references: 7 Modern Pharmaceutics, Chapters 9 and 10 (Banker & Rhodes, Editors, 1979); Pharmaceutical Dosage Forms: Tablets (Lieberman et al., 1931); Ansel, introduction to Pharmaceutical Dosage Forms 2nd Edition (1976); Remington's Pharmaceutical Sciences, 17th ed. (Mack Publishing Company, Easton, Pa., 1985); Advances in Pharmaceutical Sciences (David Ganderton, Trevor Jones, Eds., 1992); Advances in Pharmaceutical Sciences Vol 7. (David Ganderton, Trevor Jones, James McGinity, Eds., 1995); Aqueous Polymeric Coatings for Pharmaceutical Dosage Forms (Drugs and the Pharmaceutical Sciences, Series 36 (James McGinity, Ed., 1989) Pharmaceutical Particulate Carriers: Therapeutic Applications: Drugs and the Pharmaceutical Sciences, Vol 61 (Alain Rolland, Ed., 1993); Drug Delivery to the Gastrointestinal Tract (Ellis Horwood Books in the Biological Sciences. Series in Pharmaceutical Technology; J. G. Hardy, S. S. Davis, Clive G. Wilson, Eds.); Modem Pharmaceutics Drugs and the Pharmaceutical Sciences, Vol 40 (Gilbert S. Banker, Christopher T. Rhodes, Eds.). All of the aforementioned publications are incorporated by reference herein. The active ingredient can be administered orally in solid dosage forms, such as capsules, tablets, powders, and chewing gum; or in liquid dosage forms, such as elixirs, syrups, and suspensions, including, but not limited to, mouthwash and toothpaste. It can also be administered parentally, in sterile liquid dosage forms. Solid dosage forms, such as capsules and tablets, may be enteric-coated to prevent release of the active ingredient compounds before they reach the small intestine. Materials that may be used as enteric coatings include, but are not limited to, sugars, fatty acids, proteinaceous substances such as gelatin, waxes, shellac, cellulose acetate phthalate (CAP), methyl acrylate-methacrylic acid copolymers, cellulose acetate succinate, hydroxy propyl methyl cellulose phthalate, hydroxy propyl methyl cellulose acetate succinate (hypromellose acetate succinate), polyvinyl acetate phthalate (PVAP), and methyl methacrylate-methacrylic acid copolymers. The compounds and compositions of the invention can be coated onto stents for temporary or permanent implantation into the cardiovascular system of a subject. Variations on those general synthetic methods will be readily apparent to those of ordinary skill in the art and are deemed to be within the scope of the present invention. Each embodiment disclosed herein is contemplated as being applicable to each of the other disclosed embodiments. Thus, all combinations of the various elements described herein are within the scope of the invention. This invention will be better understood by reference to the Experimental Details which follow, but those skilled in the art will readily appreciate that the specific experiments detailed are only illustrative of the invention as described more fully in the claims which follow thereafter. Experimental Details The following materials and methods are used to test the compounds of the present invention. Strains, Media and Reagents A series of fungal clinical isolates and reference strains were used in this study. This includesCryptococcus neoformans, Cryptococcus gattii, Candida albicans, Candida krusei, Candida glabrata, Candida parapsilosis, Candida guilliermondii, Aspergillus fumigatus, Rhizopus oryzae, Blastomyces dermatitis, Histoplasma capsulatum, Coccidioidesspp.Paecilomyces variotii, Pneumocystis murina, and,Pneumocystis jiroveci. Escherichia coliDH5-α andPseudomonas aeruginosawere also used. Yeast Peptone Dextrose (YPD), Yeast Nitrogen Base (YNB), Luria Bertani (LB), Roswell Park Memorial Institute (RPMI) or Dulbecco Modified Eagle Medium (DMEM) were purchased from invitrogen Life Technologies and used as described. Fluconazole, Amphotericin B, Dexamethasone, Cyclophosphamide, Tunicamycin were purchased from Sigma-Aldrich, St Louis, MO. Caspofungin. and Posaconazole were obtained from Merck, Rahway, NJ, Voriconazole was obtained from Pfizer, Rey Brook, NY. In Viva Labeling with Tritiated Palmitate (3H palmitate) Labeling fungal cells.C. neoformanscells were grown in YNB (pH 7.4) at in presence of 5% CO2for 16 hrs. Cells were centrifuged for 10 min. at 3,000 rpm at room temperature. Supernatant was removed and the cell pellet was suspended and counted. Next, 900 μL, containing 5×108C. neoformanscells were placed into a 15 ml round bottom Corning centrifuge tube. Then, 100 μL of different concentrations of compound diluted in YNB containing 0.1% DMSO was added resulting in final concentrations of 0.25, 1 and 4 μg/ml, or 0.075, 0.3, 1.2 μg/ml, respectively. Tubes were incubated at in shaker incubator at 225 rpm at 37° C. in the presence of 5% CO2for 4 hours. Then, 30 μCi/ml of3H palmitate (PerkinElmer Waltham, MA) was added to the culture and incubated for additional 2 hours. Cells without the drug were included as negative control. The cells were then pelleted and washed once with distilled sterile water and suspended in 1.5 ml of Mandala lipid extraction buffer. The lipids were extracted by the methods of Mandala, (Mandala, S. M, et al. 1997) and Bligh and Dyer followed by methanolic based-hydrolysis as previously described (Bligh, E. G. & Dyer, W. J. 1959). The tube was flushed with nitrogen gas and the samples dried in a SPD210 SpeedVac system (Thermofisher Scientific, Waltham, MA. The dried lipids were resuspended in 30 μL of 1:1 methanol:chloroform and loaded on thin layered chromatography (TLC) silica gel 60 (EDM Millipore, Billerica, MA), Glucosylceramide (GlcCer) standard from soybean (Avanti Polar Lipids, Alabaster, AL) was added in a separate lane as control. The sample was resolved in a tank containing a chloroform:methanol:water (65:25:4) as the mobile phase. The TLC plates were then dried, exposed to iodine fume for the identification of the GlcCer standard band, which was marked. The TLC plate was then enhanced by spraying with ENHENCER (PerkinElmer) exposed to X-Ray film at −80° C. for 72 hours and the film was developed. Labeling mammalian cells. The murine macrophage cell line J774.16 was maintained in Dulbecco Minimum. Eagle Medium (DMEM) containing 10% Fetal. Bovine Serum (PBS) and 1% Pen-strep by regular seeding. Cell at a density of 5×106cells/mi of passage 8 were cultured in a 6 well culture plate for 14 hours to achieve adherence. Compound at the same concentrations used for fungal cells (see above) were added to the plate for 4 hours. Then, 30 μCi/mL of3H palmitic acid was added and the plate was further incubated for 2 hrs. Labeled J774.16 but untreated cells were included as control. The cells were harvested by the addition of 0.05% trypsin-EDTA and scraping with cell scrapper and washed once with PBS and dissolved in 2 ml methanol and 1 ml chloroform. Lipids were extracted by the method of Bligh and Dyer followed by base hydrolysis. The samples were flushed with nitrogen and dried in SpeedVac. Dried lipids were suspended in 30 μL of 1:1 methanol:chloroform and loaded on a TLC plate with GlcCer as standard. In Vitro Susceptibility Testing Minimal inhibitory concentration (MIC) was determined following the methods of the Clinical Laboratory Standards Institutes (CLSI) with modifications. MIC studies used either RPMI or YNB medium (pH 7.0, 0.2% glucose) buffered with HEPES. HEPES was used instead of MOPS because MOPS totally inhibits the activity of the compound. The compound was serially diluted from 32 to 0.03 μg/ml or 19 to 0.02 μg/ml respectively in a 96 well plate with the respective medium. The yeast inoculum was prepared as described in the CLSI protocol M27-A3 guidelines. Plates were incubated at 37° C. and in the presence of 5% CO2for 24-96 hours. Against all fungal isolates used in the initial susceptibility screen, the MICs were determined as the lowest concentration of the drug that inhibited 50% of growth compared to the control. MIC80 and MIC100, whose drug concentrations inhibited 30% and 100% growth compared to the control respectively, were also determined. For antibacterial activity,E. coliDH5α andP. aeruginosaPA14 were grown overnight in Luria Bertani (LB) broth at 30° C. The cells were washed with PBS and counted. Then, 300 μL from 2×108cells/mL was spreaded onto LB agar plate using a hockey stick glass spreader. The plate was dried, and wells were punched out using a cut tip. Fifty microliters of different drug concentration was added to the well. The plate was then incubated at 30° C. for 24 hours. In Vitro Testing againstP. murinaandP. jiroveci Cryopreserved and characterizedP. cariniiisolated from rat lung tissue (Pc 08-4 #45) was distributed into triplicate wells of 48-well plates with a final volume of 500 μL and a final concentration of 5×107nuclei/ml. Control dilutions were added and incubated at 37° C. At 24, 48, and 72 hours, 10% of the well volume was removed and the ATP content was measured using Perkin Elmer ATP-liteM luciferin-luciferase assay. The luminescence generated by the ATP content of the samples was measured by a spectrophotometer (PolarStar Optima BMG, Ortenberg, Germany). A sample of each group was examined microscopically on the final assay day of the assay to rule out the presence of bacteria contamination. In Vitro Killing Assay From an overnight culture,C. neoformanscells were washed in PBS, resuspended in YNB buffered with HEPES at pH 7.4. Cells were counted and 2×104cells were incubated with either 1, 2 or 4 μg/ml of compound in a final volume of 10 ml. Tubes were then incubated at 37° C. in the presence of 5% CO2on a rotary shaker at 200 rpm. At the illustrated time points, aliquots were taken and diluted and 100 μL was plated onto yeast peptone dextrose (YPD) plates. YPD plates were incubated in a 30° C. incubator and, after 72 hours, colony forming units (CFU) were counted and recorded. Intracellular Effect To assess whether the compound will be effective against intracellularC. neoformans, we first incubated J774.16 macrophages withC. neoformanscells at a 1:20 ratio in presence of opsonins (complement and antibody mAb 18B7 against the cryptococcal capsular antigen). After 2 hours of incubation, about 60-80% of macrophages have at least oneC. neoformanscell internalized. At this time, wells were washed to remove extracellular fungal cells and fresh DMEM medium without serum and without mAb 18B7 but containing different concentrations of compound was added. Plates were incubated at 37° C. and 5% CO2. At selected time points, 0, 6, 12 and 24 hours, extracellular cells were collected by washing and plated onto YPD for CFU counting of extracellular cells. Then, macrophages containingC. neoformanse lysed, collected and serial dilutions were plated onto YPD for CPU counting of intracellular fungal cells. Synergistic Assay Synergistic activity was assayed by calculating the fractional inhibitory index (FIC) as previously described (Del Poeta, M. et al. 2000). Briefly, in a 96 well plate, the compound was serially diluted from 16 to 0.015 μg/ml (11 dilutions) whereas drug B (e.g., either Fluconazole, Amphotericin B, Caspofungin, or Tunicamycin) was serially diluted from 12 to 0.19 μg/ml, 5 to 0.078 μg/ml, 70 to 1.09 μg/ml, and 6 to 0.09 μg/ml (7 dilutions), respectively. The FIC was defined as: [MIC combined/MIC Drug A alone]+[MIC combined/MIC Drug B alone]. Resistance Assay To see whether incubation with the drugs will induce resistance,C. neoformanscells were passaged daily in sub-MIC drug concentrations. Briefly, from an overnight culture,C. neoformanscells were washed with PBS, resuspended in YNB buttered with HEPES at pH 7.4 and counted. Then, 106cells were incubated with 0.5, 0.25 or 0.125 μg/ml of compound or 0.15, 0.075 and 0.037 μg/ml of compound in 1 ml final volume. Tubes without the drug served as negative control. Tubes with Fluconazole (0.5, 1 and 2 μg/ml) served as positive control. The cells were grown at 37° C. in the presence on 5% CO2on a rotary shaker at 200 rpm. Every 24 hours, the cells were pelleted by centrifugation, washed with PBS, and resuspended in YNB, and 106cells were transferred into a fresh drug tube and incubated as above. These daily passages were continued for 15 days. Cell aliquots were collected on day 0 (before any drug exposure), 5, 10, 15, and MIC was determined using the microbroth dilution assay as described above. Animal Studies for Cryptococcosis For survival studies, 4-week old CBA/J female mice (Jackson Laboratory, Bar Harbor, ME) were used. Ten mice per treatment or control group were used. Mice were infected by nasal inoculation of 20 μL containing 5×105cells ofC. neoformansH99 strain. Treated mice received an intraperitoneal injection of 1.2 mg/kg/day of compound in 100 μL final volume of PBS containing 0.4% DMSO. Untreated mice, received 100 μL of PBS/0.4% DMSO. Mice were feed ad-libitum and monitored closely for sign of discomfort and meningitis. Nice showing abnormal gait, lethargic, tremor, significant loss of body weight or inability to reach water r food were sacrificed and survival counted from that day. At the end of the survival study, tissue burden culture was performed iii mice that survived the infection. Mice were sacrificed, and their organs were extracted, and homogenized in 10 ml sterile PBS using a homogenizer (Stomacher80, Cole-Farmer, Vernon Hills, IL). Organ homogenates were serially diluted 1:10 in PBS and 100 μL was plated on YPD agar plates and incubated at 30° C. for 72 hours for CFU count. For histopathology, extracted organs were fixed in 10% formalin before paraffin sectioning and staining with either Hematoxylin-Eosin or Mucicarmine. Images were taken 40× in a Zeiss Axle Observer in brightfield mode. Animal Studies for Pneumocystosis For survival studies, C3H/HeN mice ordered from the National Cancer Institute (Bethesda, MD) were used. Mice were infected withP. murinapneumonia through exposure to mice with a fulminantP. murinainfection (seed mice). These mice were immune suppressed by the addition of dexamethasone at 4 mg/liter to the drinking water. Sulfuric acid at 1 ml/liter was also added to the drinking water for disinfection. The seed mice are rotated within the cages for 2 weeks and then removed. After the mice had developed a moderate infection level (approximately 5 weeks), they were divided into a negative control group (control steroid), positive control group (trimethoprim/sulfamethoxazole) and treatment groups (compound). Twelve mice were used in each group. Compound was administered intraperitoneally or by oral gavage on a mg/kg/day basis for up to 3 weeks. The dose, route, and frequency of administration varied depending on the agent being tested. At the end of the treatment, mice were sacrificed and processed for analysis. Slides were made from the lung homogenates at different dilutions and stained with Diff-Quik to quantify the trophic forms and Cresyl Echt violet to quantify the asci. Additional group of mice were selectively depleted of their CD4+ lymphocytes by antibody treatment with 300 μg of GK 1.5 antibody (Biovest International, Minneapolis, MN) administered intraperitoneally 3 times on days 1, 3, and 7. After this initial treatment, the mice were infected by exposureP. murinainfected mice. Mice then were treated with 100 μg of GK 1.5 antibody intraperitoneally once a week for 6 weeks. Mice were then treated with 1.25 or 12.5 mg/kg/day 1 for 14 days while continuing the GK1.5 treatment. Control mice received vehicle. Animal Studies for Candidiasis For survival studies, 8-week old CBA/J female mice (Jackson Laboratory) were used. Eight mice per treatment or control group were used. Mice were infected by intravenous inoculation of 100 μL containing 1×105cells ofCandida albicansSC-5314 strain. Treated mice received an intraperitoneal injection of 1.2 mg/kg/day of compound in 100 μL final volume of PBS containing 0.4% DMSO. Untreated mice, received. 100 μL of PBS/0.4% DMSO. Mice were feed ad-libitum and monitored closely for sign of discomfort. At the end of the survival study, tissue burden culture was performed in mice that survived the infection. Mice were sacrificed and their organs were extracted and homogenized in 10 ml sterile PBS using homogenizer. Organ homogenates were diluted 10 times in PBS, and 100 μL was plated on YPD agar and incubated at 30° C. for 72 hours for CPU count. Toxicity In vitro. The murine macrophage cell line J774.16 was maintained in DMEM containing 10% FBS and 1% Pen-strep. At passage #7, 105cells/well in DMEM containing 10% FBS was transferred into 96 well plates and cultured for 14 hours for the cells to adhere to the wells. The compound was added to the cells at concentration ranging from 0.1 to 100 μg/ml. The wells without the drug served as control. The plate was incubated at 37° C. the presence of 5% CO2. After 12 or 24 hours, the supernatant was removed and 50 μL of 5 mg/ml of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) solution in PBS was added to each well and plates incubated for 4 additional 4 hours. The formazan crystal formed inside the cell was dissolved by adding 50 μL of isopropanol containing 0.1N HCL. The optical density was measured at 570 nm. To determine whether the compound's toxicity was enhanced by corticosteroids, a separate set of J774.16 cells were incubated with 10 or 100 μg/ml of Dexamethasone alone or combined with either 1, 5 and 10 μg/ml of compound. After 24 hours, the MIT assay was performed as described above. In vivo. Mice toxicity studies were performed using 4-week old CBA/J female mice from. Jackson Laboratory. Five mice received 1.2 mg/kg/day of compound for 60 days. Three control mice received a solvent injection per day. At 60-day, blood was collect in two tubes: one with K2EDTA and the other without K2EDTA to allow blood clotting. The blood clot was then centrifuged at 1500 rpm for 10 min, serum was collected and analyzed for liver and kidney blood tests. The non-coagulated blood was used for hematocrit and blood cells analysis. These tests were done using MASCOT™ HEMAVET 950FS (Drew Scientific Group, Dusseldorf, Germany). Lipid Mass Spectrometry For lipid analysis by mass spectrometry, fungal cells (C. neoformansorC. albicans) were grown in YNB, and incubated with compound as explained for the in vivo labeling (except that tritiated palmitate was not added), for 6 hrs. Samples without drug were included as control. Before lipid extraction, lipid internal standards (C17 ceramide and C17 sphingosine) were added. Lipids were then extracted following the methods of Mandala and Bligh and Dyer and one fourth the sample was aliquoted for determination of the inorganic phosphate. The remainder of the sample was subjected to base hydrolysis and then analyzed using LC/MS. Results were normalized with the inorganic phosphate levels. In Vitro Activity of Gcs1 For the in vitro Gcs1 assay,C. neoformanswild-type (WT) or the Δgcs1 cells were grown in YPD broth overnight at 30° C. in a shaker incubator. Cells were washed with sterile water and then lysed by bead beating in presence of glass bead and protease cocktail inhibitor, as described (Liberto, C. et al. 2001). Next, 800 μg of cell lysate was incubated with 0.3 mM C16 ceramide (C16-R—OH) and in the presence or absence of compound. The mixture was subjected to 3 cycles of sonication (20 sec) and vortexing (5 sec). Next, 8 μM of radiolabelled UDP-14C-Glucose (American Radiolabeled Chemical) was added and, after brief vortexing, the tubes were incubated at 37° C. for 45 min. The reaction was stopped by adding 0.9 ml of 0.45% NaCl solution containing chloroform:methanol 2:1. The organic phase was collected in a glass tube and flushed with nitrogen. The sample was dried and resuspended in chloroform:methanol 1:1. Sample was then loaded on a TLC plate using by chloroform:methanol:water as the mobile phase. Yeast Library Screening Variomics Library: The screening of theSaccharomyces cerevisiaegenome-wide variomics libraries for potential compound resistant clones was performed as described previously (Huang, S. et al. 2013) but with slight modifications. About 6×107haploid cells was plated on solid SC-Ura medium buffered with HEPES at pH 7.0, which contained compound at a concentration of 20 μM (˜7 μg/ml) and incubated at 30° C. for 3 days. HIP-HOP Library: The yeast deletion collection used here comprises of approximately 5900 individually barcoded heterozygous diploid strains (HaploInsufficiency Prolifing) and ˜4800 homozygous diploid strains (HOmozygous deletion Profiling) (Pierce, S. E. et al. 2007). Pools of approximately equal strain abundance were generated by robotically pinning (S and P Robotics, Ontario, Canada) each strain (from frozen stocks) onto YPD agar plates as arrays of 384 strains/plate. After two days of growth at 30° C., colonies were collected from plates by flooding with YPD and aliquoted at optical density of 2 (at 600 nm). The fitness of each strain in each experimental pool was assessed as described (Pierce, S. E. et al. 2007). The dose of compound that resulted in 15% growth inhibition in BY4733 (the parent strain of the yeast deletion collection) was determined by performing a dose response over the course of 16 h of growth at 30° C. Screens of the homozygous deletion collection were performed for 5 generations of growth in compound, and screens of the Heterozygous deletion collection were collected following 20 generations of growth. Cells were processed as described (Proctor, M. et al. 2011). Briefly genomic DNA was extracted from each sample, subjected to PCR to amplify the unique barcode identifiers and the abundance of each barcode was determined by quantifying the microarray signal as described. A ranked list of all genes in the genome was generated for each experiment and then compared using gene set enrichment analysis or GSEA according to Lee (Lee, A Y et al. 2014). C6-NBD-Ceramide Staining The Golgi apparatus ofC. neoformansandC. albicanswas stained with C6-NBD-ceramide using a previously described protocol (Kmetzsch, L. et al. 2011), based on the property that this fluorescent lipid accumulates at the Golgi of either living or fixed cells (Pagano R. E. et al. 1989). Control or compound-treated (4 μg/ml) yeast cells were fixed with 4% paraformaldehyde in PBS. Cell suspensions were then washed with the same buffer and incubated with C6-NBD-ceramide (20 mM) for 16 h at 4° C. The cells were then incubated with bovine serum albumin (BSA, 1%) at 4° C. for 1 h to remove the excess of C6-NBD-ceramide. After washing with PBS, the cells were incubated with 10 μg/ml DAPI (Sigma-Aldrich, St. Louis, USA) for 30 min at room temperature. The cells were washed again with PBS and stained cell suspensions were mounted over glass slides as described above and analyzed under an Axioplan 2 (Zeiss, Germany). Statistical Analysis Statistical analysis for survival studies was performed using Student-Newman-Keels t test for multiple comparisons using INSTAT. Statistical analysis for tissue burden and for trophic form and asci counts was performed using the analysis of variance (ANOVA). Additional statistic was performed using Student t test. Comparison Studies For survival studies, 4-week old CBA/J female mice (Jackson Laboratory, Bar Harbor, ME) were used. Total of forty mice were infected by tail vein injection of 200 μL containing 105cells ofC. neoformansH99 and were randomly separated into 5 groups (8 mice per group). Treatment started within 2 hours of infection. The treated mice received an intraperitoneal injection of 1.2 mg/kg/day of compound and amphotermcin B or 10 mg/kg/day of fluconazole in 100 μL final volume of PBS containing 0.4% DMSO. Untreated mice, received 100 μL of PBS/0.4% DMSO. Mice were fed ad-libitum and monitored closely for sign of discomfort and meningitis. Mice showing abnormal gait, lethargy, tremor, significant loss of body weight, or inability to reach water or food were sacrificed and survival was counted until that day. Sample Preparation for Transmission Electron Microscopy (TEM) Sample preparation for Transmission electron Microscopy (TEM) was performed similar to the methods of Heung (Heung et al. 2005) with minor modifications. Briefly,C. neoformans(H99) were grown in YNB (pH=7.4) at 37° C. and 5% CO2and treated for 6 hours with compound (4 μg/mL), non-treated cells were also included as control. The cells were pelleted at 3000 rpm (1700 g) and fixed with 2% EM glutaraldehyde in PBS solution for 1 hour. Samples were then washed in PBS, placed in 1% osmium tetroxide in 0.1M PBS, dehydrated in a graded series of ethyl alcohol and embedded in Embed812 resin. Ultrathin sections of 80 nm were cut with a Leica EM UC7 ultramicrotome (Leica Microsystems Inc., Buffalo Grove, IL) and placed on uncoated mesh copper grids. Sections were then counterstained with uranyl acetate and lead citrate and viewed with a FEI Tecnail2 BioTwinG2 electron microscope (FEI, Hillsboro, Oregon) Transmission Electron Microscope (TEM). Digital images were acquired with an AMT XR-60 CCD Digital Camera system. Pre-Screening For the compound revertant screen, the drug-sensitive RYO0622 haploid strain was used (Suzuki, Y., et al. 2011). To determine the IC100dose of compound (at which yeast cell growth is inhibited at 100% upon drug exposure), 20 ul of RYO0622 cells (at OD6001−4) were plated on solid synthetic complete (SC) media alone, with DMSO, or with a range of compound doses (0.2, 0.4, 0.8, 1.6 and 3.2 mM) in a 46-well plate. The plate was incubated for 2 days at 30° C. in the dark. Revertant Screening Assay RYO622 cells were cultured to mid-log phase (˜OD6000.5) in liquid SC media before adjusting the cell density to 1×106cells/ml (equivalent to OD600˜0.1). One ml of cells was plated on solid SC media containing DMSO solvent control (0.26% v/v) or compound (at 0.4 mM IC100 dose) and incubated at 30° C. in the dark. A lawn of cells grew on the solvent control, while only a single compound-resistant colony was identified after 9 days. Longer incubation did not result in the appearance of further resistant clones. To confirm compound resistance, single colonies isolated from the compound containing SC media were plated onto fresh solid SC medium containing 0.4 mM compound and incubated for 2 days at 30° C. in the dark. Robust compound-resistant cells wore seen. Yeast Genomic DNA Preparation Genomic DNA was extracted from RYO0622 and compound-resistant cells using the Puregene kit (Qiagen), according to the manufacturer's instructions. Next-Generation Sequencing of Compound-Resistant RYO0622 Genomic DNA was quantified using Qubit fluorometry (Life Technologies) and diluted for sequencing library preparation using Nextera XT library preparation kit according to the manufacturer's instructions (Illumina). Libraries were pooled and sequenced on a single MiSeq lane, generating paired-end 150 bp reads. Mapping & Variant Calling Raw FASTQ paired-end reads for the parent (RYO0622) and the revertant were independently aligned to NCBI sacCer3 (genbank/genomes/Eukaryotes/fungi/Saccharomy ces_cerevisiae/SacCer_Apr2011) reference genome using bwa mem v0.7.4-r385 with the -M flag to mark shorter split hits as secondary for compatibility with Picard (Li, H. & Durbin, H. 2009). Resultant SAM files were converted to BAM format using samtools v1.1 and sorted by coordinate using Picard v1.96 (SortSam) (http://picard.sourceforge.net). PCR duplicate reads were filtered out using Picard MarkDuplicates (10.24% estimated duplication) and indexed using Picard BuildBamIndex. To call single nucleotide variants (SNVs), we ran the GATK Unified Genotyper v2.1-8 (McKenna, A., et al. 2010) with the NCBI sacCer3 reference genome, stand_call_conf=30, and stand_emit_conf=10 (DePristo, M. A., et al. 2011). The ploidy parameter was set to 1 since the parent and revertant are in haploid state. Since a database of known indels and known SNPs was not available, we did not perform re-alignment around known indels and quality score recalibration. TEM. Sample preparation for Transmission electron Microscopy (TEM) was performed similar to the methods of Hueng et al. with minor modifications (Heung, L. J. et al 2005). Briefly,C. neoformans(H99) were grown in YNB (pH-7.4) at 37° C. and 5% CO2and treated for 6 hours with compound (4 μg/mL), non-treated cells were also included as control. The cells were pelleted at 3000 rpm. (1700 g) and fixed with 2% EM glutaraldehyde in PBS solution for 1 hour. Samples were then washed in PBS, placed in 1% osmium tetroxide in 0.1M PBS, dehydrated in a graded series of ethyl alcohol and embedded in Embed812 resin. Ultrathin sections of 80 nm were cut with a Leica EM UC7 ultramicrotome (Leica Microsystems Inc., Buffalo Grove, IL) and placed on uncoated mesh copper grids. Sections were then counterstained with uranyl acetate and lead citrate and viewed with a FEI Tecnail2 BioTwinG2 electron microscope (FBI, Hillsboro, Oregon) Transmission Electron Microscope (TEM). Digital images were acquired with an AMT XR-60 CCD Digital Camera system. Generation of compound-resistant strains. For the generation of compound-resistant strains, the drug-sensitiveS. cerevisiae RYO0622 haploid strain was used (Suzuki, Y. et al. 2011). Prescreening studies were performed to determine the IC100dose of compound for this strain (the 100% inhibitory concentration. [IC100] at which 100% yeast LL growth is inhibited upon drug exposure). For this screening, 20 μl of RYO0622 cells (at an OD600of 10−4) were plated on solid synthetic complete (SC) medium alone or with DMSO or with various compound concentrations (67, 133, 266, 533, and 1,066 μg/ml) in a 48-well plate. The plates were incubated for 2 days at 30° C. in the dark. These studies revealed an IC100dose of 133 μg/ml. Screening for the compound-resistant mutants was performed by growing the RYO0622 cells to mid-log phase (OD600of ˜0.5) in liquid SC medium before adjusting the cell density to 1×106cells/ma (equivalent to an OD600of ˜0.1). One milliliter of cells was plated on solid SC medium containing DMSO solvent control (0.26% [vol/vol]) or compound (133 μg/ml IC100dose) and incubated at 30° C. in the dark. A lawn of cells grew on the solvent control, while seven compound-resistant colonies were identified after 9 days. Longer incubation did not result in the appearance of further resistant colonies. To confirm compound resistance, single colonies isolated from the compound-containing SC medium were plated onto fresh solid SC medium containing 133 μg/ml compound and incubated for 2 days at 30° C. in the dark. Robust compound-resistant cells were seen. Next-generation sequencing of compound-resistant strains. Genomic DNA was extracted from RYO0622 and compound-resistant cells using a standard yeast DNA extraction protocol (Hoffman, C. S. et al. 1987). Genomic DNA samples were quantified using Qubit fluorometry (Life Technologies) and diluted for sequencing library preparation using a Nextera XT library preparation kit according to the manufacturer's instructions (Illumina San Diego, CA). For the initial round of sequencing, individual sequencing libraries were prepared for the parent and a single compound-resistant clone. These libraries were pooled and sequenced on a single MiSeq lane (Illumina), generating paired-end 150-bp reads. Further compound-resistant colonies were obtained in a second screen, and their DNAs were pooled at equal concentrations before preparation of a single sequencing library for the pool. This pool was sequenced alongside a new library for the parent strain on a single HiSeq 2500 lane (Illumina), generating paired-end 100-bp reads. Mapping and variant calling. Raw FASTQ paired-end reads for the parent (RYO0622) and the compound-resistant pool were independently aligned to the NCBI sacCer3 reference genome using bwa mem v0.7.4-r385 (Li, R., Yu, C. et al. 2009) with the -M flag to mark shorter split hits as secondary for compatibility with Picard. Resultant SAM files were converted to BAN format using samtools v1.1 and sorted by coordinate using Picard v1.96 (SortSam). PCR duplicate reads were filtered out using Picard MarkDuplicates and indexed using Picard BuildBamIndex. To call single nucleotide variants (SNVs), the GATK Unified Genotyper v2.1-8 (McKenna, A. et al. 2010) was ran with the NCBI sacCer3 reference genome, stand_call_conf=30, and stand_emit_conf=10 (DePristo, M. A. et al. 2011). The ploidy parameter was set at 1, since the parent and resistant strains are in haploid state. Realignment around known indels and quality score recalibration was not performed, since a database of known indels and known single nucleotide polymorphisms (SNPs) is not available. Validation of compound-resistant yeast mutants. Four yeast genes (ALP5, COS111, MKK1, and STE2) were selected based on the high-quality variant calls present in the compound-resistant pool. To confirm compound resistance, the individual haploid Δap15, Δcos111, Δmkk1 and Δste2 deletion mutants were assayed for growth fitness after treatment with compound. Unrelated drug controls, including methyl methane sulfonate (MMS) (cytotoxic) and fluconazole (antifungal) were assayed in parallel. Strains were cultured to mid-log phase (OD600of ˜0.5) in liquid YPD medium before adjusting the cell density to an OD600of 0.0625 with YPD medium. The cells were transferred to 96-well plates containing 100 μl of YPD with DMSO solvent control (2% [vol/vol]), compound (6 to 733 μg/ml), MMS (10 μg/ml to 625 μg/ml), or fluconazole (2 to 306 μg/ml) and incubated at 30° C. for 24 h. The fitness of individual strains was measured, using a spectrophotometer plate reader (Tecan GENios, Chapel Hill, NC) to read OD600over 24 h as a proxy for cell growth. Relative growth inhibition was calculated by the average rate after normalizing the OD600values in drug wells against the DMSO control wells on each assay plate. Example 1 Synthesis General Synthesis of Compounds The benzaldehyde (1 mmol, 2 ml ethanol) and the benzohydrazide (1 mmol in 2 ml hot ethano) were combined. The product generally crystallize within seconds. After 30 minutes at room temperature the product was collected by filtration (Yield: 80 to 95%). Homogeneity of the product was confirmed by thin layer chromatography (TLC) on silicagel F254(Merck KGaA, Darmstadt, Germany) in two different solvent systems benzene/acetic acid 9:1 v/v and hexane/ethylacetate 1:3 v/v. If impurities were present the product was recrystallized from ethanol. Alternatively, the reaction proceeds for 24 h at 4° C. and the solvent was completely evaporated and the product crystallized from ethyl acetate. Products were analyzed by TLC as described above. Synthesis of 1 To a solution of 2-methylbenzoic hydrazide (0.66 mmol), 2-hydroxy-5-bromobenzaldehyde (0.72 mmol) in methanol (3 mL) was added 3 drops of glacial acetic acid. The reaction mixture was stirred at room temperature overnight. Addition of water to the reaction mixture resulted in precipitation of the product, which was filtered, washed with water and dried to give pure product as white solid. (95% yield);1H NMR (500 MHz, DMSO-d6) δ 2.38 (s, 3H), 6.90 (d, 1H, J=8.8 Hz), 7.28-7.32 (m, 3H), 7.37-7.43 (m, 2H), 7.47 (d, 1H, J=7.5 Hz), 7.78 (s, 1H), 8.47 (s, 1H), 11.19 (s, 1H), 12.05 (s, 1H). Compound 2, 13 and 17 were synthesized by an analogous method using the appropriate starting materials for each. Example 2 PK/PD: Killing Curve Versus MIC KappCoefficient Analysis CompoundMICKapp*A549SIMIC110.024323220.25−0.1426464130.06−0.428>1284266.6170.50.0771632*Kapp= K0− Ki(C − Ci) Example 3 Kill Characteristics of 1 and 2 Compound 1 killedC. neoformansin a concentration dependent manner (seeFIG.1A). Compound 2 also killedC. neoformansin a time dependent manner (seeFIG.1B). Example 4 Fungicidal Data TABLE 1IC80Killing assaySI-A549/SI-HepG2/Structure(μg/mL)48 H (μg/mL)A549HepG2MICMIC0.25Fungistatic32321281280.250.516166464113216321610.5323232320.250.254816320.251646425625610.572327232*Units are μg/ml for A549, HepG2, SI-A549/MIC and SI-HepG2/MIC. TABLE 2IC80Killing assaySI-A549/SI-HepG2/Structure(μg/mL)48 H (μg/mL)A549HepG2MICMIC0.250.12593223610.5>6464128640.50.25323264640.120.516>32133.3533.30.250.253216128640.50.25>329128180.060.12>32>6410662133.3*Units are μg/ml for A549, HepG2, SI-A549/MIC and SI-HepG2/MIC. TABLE 3IC80Killing assaySI-A549/SI-HepG2/Structure(μg/mL)48 H (μg/mL)A549HepG2MICMIC0.50.25161632320.06Fungistatic1632266.6533.30.120.253216266.6133.30.06Fungistatic3232533.3533.30.120.12>3259533.3491.660.251163264128*Units are μg/ml for A549, HepG2, SI-A549/MIC and SI-HepG2/MIC. Example 5 Administration of the Compound An amount of the compound of the present invention is administered to a subject afflicted with a fungal infection. The amount of the compound is effective to treat the subject. An amount of the compound of the present invention is administered to a subject afflicted with a fungal infection. The amount of the compound is effective to treat the subject by inhibiting sphingolipid synthesis in the fungus without substantially inhibiting sphingolipid synthesis in the subject. An amount of the compound of the present invention in combination with an anti-fungal agent are administered to a subject afflicted with a fungal infection. The amount of the compound and the agent are effective to treat the subject. Example 6 Assessment of Efficacy of Compound as Add-On Therapy to Anti-Fungal Agents The add-on therapy provides a synergistic effect, and allows for lower doses with reduced side effects and resistance. Periodic administration of the compound of the present invention as an add-on therapy for a subject afflicted with a fungal infection who is already receiving treatment with an anti-fungal agent provides a clinically meaningful advantage and is more effective (provides at least an additive effect or more than an additive effect) in treating the subject than when the anti-fungal agent is administered alone (at the same dose). Periodic administration an anti-fungal agent as an add-on therapy for a human patient afflicted with a fungal infection who is already receiving a compound of the present invention provides a clinically meaningful advantage and is more effective (provides at least an additive effect or more than an additive effect) in treating the subject than when the compound is administered alone (at the same dose). The add-on therapies also provide efficacy (provides at least an additive effect or more than an additive effect) in treating the subject without undue adverse side effects or affecting the safety of the treatment. As compared to when each agent is administered alone: 1. The add-on therapy is more effective (provides an additive effect or more than an additive effect) in killing the fungus; and/or 2. The add-on therapy is more effective (provides an additive effect or more than an additive effect) in slowing the growth of the fungus. Example 7 Synthesis and Characterization Chemical Synthesis and Characterization of Aromatic Acylhydrazones of this Invention 4-Bromo-N′-(2-hydroxy-5-trifluoromethoxybenzylidene)benzohydrazide (A1) To a solution of 4-bromobenzoic hydrazide (100 mg, 0.47 mmol), 5-trifluoromethoxysalicylaldehyde (102 mg, 0.49 mmol) in methanol (2 mL) was added 3 drops of glacial acetic acid. The reaction mixture was stirred at room temperature overnight. Addition of water to the reaction mixture resulted in precipitation of the product, which was filtered, washed with water and dried, to give pure product as white solid (93% yield); m.p. 213-214° C.; 1H NMR (500 MHz DMSO-d6) δ 7.02 (d, 1H, J=9 Hz), 7.30 (dd, 1H, J=8.9, 2.6 Hz), 7.64 (s, 1H), 7.77 (d, 2H, J=8.5 Hz), 7.89 (d, 2H, J=8.5 Hz), 8.67 (s, 1H), 11.25 (s, 1H), 12.23 (s, 1H);13C NMR (125 MHz DMSO-d6) δ 117.73, 119.19, 120.21, 120.37, 121.22, 123.25, 124.34, 125.83, 129.77, 131.60, 131.07, 140.67, 145.61, 156.06, 162.06;19F NMR (376 MHz DMSO-d6) δ 57.30 (s, 3F); HRMS (ESI) m/z calcd for C15H10BrF3N2O3H+: 402.99, Found: 402.991 (Δ=−2.47 ppm). The same procedure was followed for the rest of the compounds. 4-Bromo-N′-(5-fluoro-2-hydroxybenzylidene)benzohydrazide (A2) White solid (88% yield); m.p.>220° C.;1H NMR (500 MHz DMSO-d6) δ 6.92-6.94 (m, 1H), 7.15 (td, 1H, J=8.6, 3.2 Hz), 7.44 (dd, 1H, J=9.4 3.1 Hz), 7.76 (d, 2H, J=8.5 Hz), 7.09 (d, 2H, J=0.5 Hz), 8.63 (s, 1H), 10.94 (s, 1H), 12.20 (s, 1H);13C NMR (125 MHz DMSO-d6) δ 113.61, 113.80, 117.58, 117.64, 118.01, 119.74, 119.80, 125.80, 129.74, 131.58, 131.86, 146.34, 153.57, 154.39, 156.26, 161.97;19F NMR (376 MHz DMSO-dd 3-125.06 (s, 1F); HRMS (ESI) m/z calcd for C14H10BrFN2O2H+: 336.9982, Found: 336.9996 (Δ=−3.95 ppm). 2,4-Dibromo-N′-(2-hydroxy-5-trifluoromethoxybenzylidene)benzohydrazide (A3) White solid (99% yield); m.p. 170-172° C.;1H NMR (500 MHz DMSO-d6) δ 6.91 (d, 1H, 40%, J=8.8 Hz), 7.01 (d, 1H, 60%, J=8.9 Hz), 7.16-7.17 (m, 1H, 50%), 7.19-7.20 (1H, m, 20%), 7.30 (dd, 1H, 60%, J=9, 2.8 Hz), 7.40 (d, 1H, 40%, J=8.2 Hz), 7.54 (d, 1H, 60%, J=8.2 Hz), 7.64 (s, 1H, 60%), 7.69 (dd, 1H, 40%, J=8.2, 1.8 Hz), 7.74 (dd, 1H, 60%, J=8.2, 1.8 Hz), 7.97 (s, 1H, 35%), 8.02 (s, 1H, 40%), 8.50 (s, 1H, 60%), 10.28 (s, 1H, 40%), 11.03 (s, 1H, 60%), 12.18 (s, 1H, 63%), 12.20 (s, 1H, 34%);13C NMR (125 MHz DMSO-d6) δ 117.54, 117.73, 113.54, 119.06, 119.17, 119.86, 119.94, 120.19, 120.61, 120.63, 121.09, 121.21, 123.78, 123.86, 124.56, 130.15, 130.57, 130.80, 130.87, 134.01, 134.84, 136.08, 137.20, 140.69, 140.70, 140.85, 145.36, 155.16, 155.96, 162.52, 168.45;19F NMR (376 MHz DMSO-d6) δ −57.31, −57.40; HRMS (ESI) m/z calcd for C15H9Br2F3N2O3+: 480.9005, Found: 480.9013 (Δ=−1.74 ppm). 2,4-Dibromo-N′(5-fluoro-2-hydroxybenzylidene)benzohydrazide (A4) White solid (96% yield); m.p. 182-183° C.;1H NMR (500 MHz DMSO-d6) δ 6.83 (dd, 1H, 40%, J=9, 4.7 Hz), 6.94 (dd, 1H, 60%, J=9, 4.7 Hz), 6.98 (dd, 1H, 40%, J=9.4, 3.2 Hz), 7.06 (td, 1H, 40%, J=8.5, 3.3 Hz), 7.16 (td, 1H, 60%, J=8.5, 3.3 Hz), 7.41 (d, 1H, 40%, J=8.2 Hz), 7.44 (dd, 1H, 60%, J=9.4, 3.2), 7.54 (d, 1H, 60%, J=8.2 Hz), 7.70 (dd, 1H, 40%, J=8.2, 1.9 Hz), 7.74 (dd, 1H, 60%, J=8.2, 1.9 Hz), 8.00 (s, 1H, 35%), 8.02 (s, 1H, 55%), 8.27 (s, 1H, 40%), 8.47 (s, 1H, 60%), 9.90 (s, 1H, 40%), 10.71 (s, 1H, 60%), 12.15 (s, 1H, 66%), 12.17 (s, 1H, 33%);13C NMR (125 MHz DMSO-d6) δ 111.98, 112.18, 113.20, 113.39, 117.44, 117.50, 117.58, 117.65, 117.78, 117.97, 118.25, 118.43, 119.75, 119.81, 120.18, 120.24, 120.63, 122.66, 123.76, 130.16, 130.66, 130.78, 130.86, 134.13, 134.82, 136.08, 137.16, 141.81, 146.09, 152.80, 153.48, 154.32, 154.41, 156.18, 156.27, 162.45, 168.29;19F NMR (376 MHz DMSO-d6) δ −124.76 (s, 1F), −124.91 (s, 1F); HRMS (ESI) m/z calcd for C14H9Br2FN2O2H+: 414.9088, Found: 414.9095 (Δ=−1.7 ppm). 3-Difluoromethoxy-N′-(5-bromo-2-hydroxybenzylidene)benzohydrazide (A5) Yellow solid (90% yield); m.p. 166-168° C.;1H NMR (500 MHz DMSO-d6) δ 6.91 (d, 1H, 90%, J=8.8 Hz), 6.95 (d, 1H, 10%, J=8.8 Hz), 7.18 (s, 1H, 25%), 7.33 (s, 1H, 50%), 7.42-7.44 (m, 2H, 90%), 7.48 (s, 1H, 25%), 7.54-7.56 (m, 2H, 10%), 7.61 (t, 1H, 100%, J=8 Hz), 7.72 (s, 1H, 90%), 7.81-7.83 (m, 2H, 100%, 90%), 7.90 (s, 1H, 10%), 8.63 (s, 1H, 90%), 8.93 (s, 1H, 10%), 11.13 (s, 1H, 10%), 11.20 (s, 1H, 90%), 12.22 (s, 1H, 90%);13C NMR (125 MHz DMSO-d6) δ 110.48, 110.56, 114.26, 117.94, 118.36, 118.68, 118.91, 120.57, 121.33, 122.26, 124.45, 130.23, 130.41, 131.57, 133.70, 134.65, 135.49, 145.84, 150.94, 150.96, 156.41, 157.66, 160.76, 161.83;19F NMR (376 MHz DMSO-d6) δ −82.16 (s, 2F); HRMS (ESI) m/z calcd for C15H11BrF2N2O3H+: 384.9994, Found: 384.9996 (Δ=−0.49 ppm). 3-Difluoromethoxy-N′-(3,5-dibromo-2-hydroxybenzylidene)benzohydrazide (A6) Yellow solid (99% yield); m.p. 143-147° C.;1H NMR (500 MHz DMSO-d6) δ 7.19 (s, 1H, 25%), 7.34 (s, 1H, 50%), 7.46 (d, 1H, 90%, J=8 Hz), 7.49 (s, 1H, 25%), 7.63 (t, 1H, 100%, J=8 Hz), 7.73 (s, 1H, 100%), 7.83-7.96 (m, 3H, 100%), 8.54 (s, 1H, 90%), 9.06 (s, 1H, 10%), 10.08 (s, 1H, 5%), 11.99 (s, 1H, 10%), 12.60 (s, 1H, 90%), 12.64 (s, 1H, 95%);13C NMR (125 MHz DMSO-d6) δ 110.44, 110.80, 111.25, 111.64, 114.22, 116.28, 118.05, 118.34, 120.35, 120.92, 122.55, 124.53, 130.50, 132.14, 133.47, 134.02, 135.69, 137.77, 147.49, 150.90, 151.00, 153.65, 154.71, 161.94, 163.98;19F NMS. (376 MHz DMSO-d6) δ −82.22 (s, 2F); HRMS (ESI) m/z calcd for C15H10Br2F2N2O3H+: 462.9099, Found: 462.91 (Δ=−0.2 ppm). 4-Trifluoromethoxy-N′-(5-bromo-2-hydroxybenzylidene)benzohydrazide (A7) Beige solid (88% yield); m.p. 199-201° C.;1H NMR (500 MHz DMSO-d6) δ 6.91 (d, 1H, J=8.8 Hz), 7.42-7.44 (m, 1H), 7.54 (d, 2H, J=8.3 Hz), 7.81 (s, 1H), 8.07 (d, 2H, J=8.3 Hz), 3.61 (s, 1H), 11.21 (s, 1H), 12.25 (s, 1H);13C NMR (125 MHz DMSO-d6) δ 110.47, 116.88, 118.68, 118.92, 120.83, 120.97, 121.31, 123.02, 130.10, 130.28, 131.88, 133.69, 145.81, 150.74, 156.42, 161.77;19F NMR (376 MHz DMSO-d6) δ −56.64; HRMS (ESI) m/z calcd for C15H10BrF3N2O3H+: 402.99, Found: 402.9902 (Δ=−0.63 ppm). 2-Fluoro-4-trifluoromethyl-N′-(5-bromo-2-hydroxybenzylidene)benzohydrazide (A8) Yellow solid (61% yield); m.p. 179-182° C.;1H NMR (400 MHz DMSO-d6) δ 6.80 (d, 1H, 30%, J=8.6 Hz), 6.90 (d, 1H, J=8.7 Hz), 7.29-7.31 (m, 2H, 25%), 7.33-7.34 (m, 1H, 17%), 7.44 (dd, 1H, 80%, J=8.8, 2.6 Hz), 7.72-7.76 (m, 2H, 75%), 7.81-7.93 (m, 2H, 100%), 8.29 (s, 1H, 33%), 8.51 (s, 1H, 77%), 10.26 (s, 1H, 30%), 11.00 (s, 1H, 70%), 12.25 (s, 1H, 30%), 12.27 (s, 1H, 70%);13C NMR (100 MHz DMSO-d6) δ 110.55, 113.87, 114.12, 118.46, 118.68, 121.24, 121.64, 123.87, 126.70, 128.19, 129.99, 131.54, 133.52, 133.96, 140.99, 145.93, 155.63, 156.38, 157.70, 159.21, 160.21, 165.61;19F NMR (376 MHz DMSO-d6) 3-61.33 (s, 3F), −61.46 (s, 3F), −111.26 (s, 1F), −111.49 (s, 1F); HRMS (ESI) m/z calcd for C15H9BrF4N2O2H+: 404.9856, Found: 404.9864 (Δ=−1.84 ppm). 2-Fluoro-4-trifluoromethyl-N′-(3,5-dibromo-2-hydroxybenzylidene)benzohydrazide (A9) Yellow solid (74% yield); m.p. 192-195° C.;1H NMR (400 MHz DMSO-d6) δ 7.52 (s, 1H, 15%), 7.74 7.97 (m, 1H, 85%, 4H, 100%), 8.27 (s, 1H, 20%), 8.46 (s, 1H, 80%), 10.2 (s, 1H, 25%), 12.34 (s, 1H, 75%), 12.53 (s, 1H, 15%), 12.67 (s, 1H, 80%);13C NMR (100 MHz DMSO-d6) δ 110.57, 171.17, 111.92, 113.96, 114.21, 120.89, 121.58, 121.69, 121.73, 122.27, 126.01, 126.17, 130.49, 130.65, 131.66, 131.69, 132.84, 132.92, 133.16, 133.25, 135.68, 135.96, 143.57, 148.06, 152.33, 153.62, 157.78, 159.35, 160.29, 165.41;19F NMR (376 MHz DMSO-d6) δ −61.34 (s, 3F), −61.50 (s, 3F), −111.16 (s, 1F), −111-93 (s, 1F); HRMS (ESI) m/z calcd for C15H8Br2F4N2O2H+: 482.8961, Found: 482.8958 (Δ=0.69 ppm). N′-(3,5-dibromo-2-hydroxybenzylidene)quinolinylhydrazide (A10) Beige solid (99% yield); m.p.>215° C.;1H NMR (700 MHz DMSO-d6) δ 7.33 (t, 1H, J=7.9 Hz), 7.85 (dd, 2H, J=13.4, 2.4 Hz), 7.91 (t, J=7.7 Hz), 8.12 (d, 1H, J=8.5 Hz), 8.16 (d, 1H, J=7.8 Hz), 8.57 (s, 1H), 8.95 (s, 1H), 9.34 (s, 1H), 12.63 (s, 1H), 12.85 (s, 1H);13C NMR (175 MHz DMSO-d6) δ 110.50, 111.33, 120.96, 125.11, 126.36, 127.72, 128.86, 129.29, 131.80, 132.19, 135.77, 136.54, 147.50, 148.79, 153.70, 161.75. 4-Cyano-N′-(3,5-dibromo-2-hydroxybenzylidene)benzohydrazide (A11) White solid (47% yield); m.p.>215° C.;1H NMR (500 MHz DMSO-d6) δ 7.83 (s, 2H), 8.05 (d, 2H, J=8.6 Hz), 8.09 (d, 2H, J=8.6 Hz), 8.53 (s, 1H), 12.64 (s, 2H);13C NMR (125 MHz DMSO-d6) δ 110.47, 111.32, 114.50, 118.17, 120.90, 128.62, 132.20, 132.65, 135.82, 136.20, 147.89, 153.70, 161.76; HRMS (ESI) m/z calcd for C15H9Br2N3O2H+: 421.9134, Found: 421.915 (Δ=−3.67 ppm). 2-Fluoro-4-trifluoromethoxy-N′-(5-bromo-2-hydroxybenzylidene)benzohydrazide (A12) Yellow solid (57% yield); m.p. 151-152° C.;1H NMR (500 MHz DMSO-d6) δ 6.62 (d, 1H, 30%, J=8.8 Hz), 6.39 (d, 1H, 73%, J=3.8 Hz), 7.31-7.33 (m, 2H, 52%), 7.35 (d, 1H, 30%, J=8.8 Hz), 7.38-7.40 (m, 1H, 70%), 7.43 (dd, 1H, 67%, J=8.8, 2.6 Hz), 7.52-7.54 (m, 1H, 30%), 7.57-7.60 (m, 1H, 70%), 7.67 (t, 1H, 30%, J=8 Hz), 7.30 (s, 1H, 70%), 7.84 (t, 1H, 70%, J=8.2 Hz), 8.27 (s, 1H, 28%), 8.49 (s, 1 C, 72%), 10.27 (s, 1H, 30%), 11.03 (s, 1H, 70%), 12.15 (s, 1H, 35%), 12.19 (s, 1H, 65%);13C NMR (125 MHz DMSO-d6) δ 109.89, 110.10, 110.53, 117.17, 118.68, 121.25, 121.99, 122.01, 122.13, 128.17, 130.08, 131.01, 131.05, 131.92, 131.95, 133.45, 133.89, 140.53, 145.79, 150.32, 150.41, 155.60, 156.38, 158.48, 159.29, 160.49, 165.78;19F NMR (376 MHz DMSO-d6) δ −56.95 (s, 3F), −57.01 (s, 3F), −109.09 (s, 1F), 109.47 (s, 11F); HRMS (ESI) m/z calcd for C15H9BrF4N2O3H+: 420.9805, Found: 420.982 (Δ=−3.47 ppm). 2-Fluoro-4-trifluoromethoxy-N′-(3,5-dibromo-2-hydroxybenzylidene)-benzohydrazide (A13) Yellow solid (62% yield); m.p. 206-207° C.;1H NMR (500 MHz DMSO-d6) δ 7.41 (d, 1H, J=8.6 Hz), 7.61 (d, 1H, J=8.8 Hz), 7.83 (dd, 2H, J=7.3, 2.4 Hz), 7.87 (t, 1H, J=8.3 Hz), 8.45 (s, 1H), 12.39 (s, 1H), 12.57 (s, 1H);13C NMR (125 MHz DMSO-d6) δ 109.92, 110.13, 110.52, 111.10, 111.32, 111.84, 117.18, 117.42, 118.77, 120.88, 121.31, 121.43, 122.21, 122.88, 130.60, 130.93, 132.07, 132.10, 132.19, 135.60, 135.87, 143.31, 147.78, 150.58, 150.67, 153.62, 158.57, 159.41, 160.59; 165.56;19F NMR (376 MHz DMSO-d6) δ −56.94 (s, 3F), −57.02 (s, 3F), −109.09 (s, 1F), −109.94 (s, 1F); HRMS (ESI) m/z calcd for C15H8Br2F4N2O3H+: 498.8911, Found: 498.8923 (Δ=−2.57 ppm). 3-Bromo-N′-(2-hydroxy-5-trifluoromethylbenzylidene)benzohydrazide (A14) White solid (92% yield); m.p. 175-176° C.;1H NMR (400 MHz DMSO-d6) δ 7.10 (d, 1H, 90%, J=8.6 Hz), 7.15 (d, 1H, 10%, J=8.5 Hz), 7.51 (t, 1H, 100%, J=7.9 Hz), 7.62 (dd, 1H, 90%, J=8.6, 1.5 Hz), 7.73 (m, 1H, 10%), 7.81 (d, 1H, 100%, J=7.8 Hz), 7.93 (d, 1H, 100%, J=7.9 Hz), 8.00 (s, 1H, 95%), 8.09 (s, 1H, 5%), 8.12 (s, 1H, 100%), 8.71 (s, 1H, 90%), 9.06 (s, 1H, 10%), 11.64 (s, 1H, 10%), 11.71 (s, 1H, 90%), 12.27 (s, 1H, 90%);13C NMR (100 MHz DMSO-d6) δ 117.19, 119.69, 119.92, 120.24, 120.57, 121.77, 123.06, 125.24, 125.75, 126.93, 128.02, 130.18, 130.82, 134.74, 134.94, 145.73, 160.00, 161.52;19F NMR (376 MHz DMSO-d6) δ −56.92 (s, 3F), −60.12 (s, 3F); HRMS (ESI) m/z calcd for C15H10F3N2O2H+: 386.9951, Found: 386.9957 (Δ=−1.78 ppm). 4-Methoxymethyl-N′-(3,5-dibromo-2-hydroxybenzylidene)benzohydrazide (A15) Yellow solid (84% yield); m.p.>215° C.1H NMR (500 MHz DMSO-d6) δ 3.31 (s, 1H), 3.32 (s, 2H), 4.49 (s, 2H), 7.48 (d, 2H, J=8.1 Hz), 7.81 (d, 2H, J=5.3 Hz), 7.94 (d, 2H, J=8.1 Hz), 8.52 (s, 1H), 12.52 (s, 1H), 12.74 (s, 1H);13C NMR (125 MHz DMSO-d6) δ 57.77, 72.95, 110.36, 111.19, 120.96, 127.25, 127.82, 131.07, 132.11, 135.52, 142.97, 146.97, 153.65, 162.75; HRMS (ESI) m/z calcd for C16H14Br2N2O3H+: 440.9444, Found: 440.9448 (Δ=−0.88 ppm). 4-Dimethylamino-N′-(4-dibromo-2-hydroxybenzylidene)benzohydrazide (A16) Yellow solid (93% yield); m.p. 195-196° C.;1H NMR (400 MHz DMSO-d6) δ 2.99 (s, 6H), 6.75 (d, 2H, J=9 Hz), 7.09 (dd, 1H, J=8.24, 1.8 Hz), 7.12 (s, 1 h), 7.47 (d, 1H, J=8.3 Hz), 7.81 (d, 2H, J=9 Hz), 8.55 (s, 1H), 11.76 (s, 1H), 11.85 (s, 1H);13C NMR (100 MHz DMSO-d6) δ 110.84, 118.55, 119.04, 122.27, 123.38, 129.14, 130.65, 145.41, 152.62, 158.03, 162.57; HRMS (ESI) m/z calcd for C16H16BrN3O2H+: 362.0499, Found: 362.0504 (Δ=−1.37 ppm). 3,5-Dibromo-2-hydroxy-N′-(5-methyl-2-hydroxyphenylmethylidene)benzohydrazide (A17) Yellow solid (88% Yield), m.p 148-153° C.;1H NMR (700 MHz. DMSO-d) δ 2.23 (s, 3H), 6.83 (d, 1H, J=8.3 Hz), 7.12 (dd, 1H, J=8.3, 1.9 Hz), 7.43 (s, 1H), 8.01 (s, 1H), 8.19 (s, 1H), 8.67 (s, 1H), (s, 1H), 12.37 (s, 1H), 13.09 (s, 1H);13C NMR (175 MHz DMSO-d6) δ 19.96, 109.81, 112.41, 116.32, 116.57, 118.35, 128.08, 128.48, 129.119, 132.84, 138.74, 149.52, 155.39, 156.82, 164.17; MS (ESI) m/z 426.9 (M+1)+ 3,5-Dibromo-2-hydroxy-N′-(4-bromo-2-hydroxybenzylidene)benzohydrazide (A18) Yellow solid (95% Yield); m.p>230° C.;1H NMR (700 MHz DMSO-d6) δ 7.10 (dd, 1H, J=8.3, 1.8 Hz), 7.12 (s, 1H), 7.62 (d, 1H, J=8.3 Hz), 8.00 (s, 1H), 8.17 (s, 1H), 8.68 (s, 1H), 11.17 (s, 1H), 12.41 (s, 1H);13C NMR (175 MHz DMSO-d6) δ 109.79, 112.46, 116.61, 118.59, 119.07, 122.61, 124.62, 129.22, 129.54, 138.76, 147.78, 156.83, 158.06, 164.24; MS (ESI) m/z 488.7 (M−1)− 3,5-Difluoro-N′-(4-bromo-2-hydroxybenzylidene)benzohydrazide (A19) White solid (87% yield); m.p. 222-228° C.;1H NMR (400 MHz DMSO-d6) δ 6.97 (d, 1H, 25%, J=8.3 Hz), 7.03 (s, 1H, 25%), 7.11 (d, 1H, 75%, 8.3 Hz), 7.19 (d, 1H, 25%, J=8.4 Hz), 7.30-7.37 (m, 2H, 25%, 100%), 7.49-7.51 (m, 1H, 75%), 7.58 (d, 1H, 75%, J=8.3 Hz), 7.60-7.66 (m, 2H, 100%, 75%), 8.30 (s, 1H, 26%), 8.52 (s, 1H, 74%), 10.41 (s, 1H, 30%), 11.22 (s, 1H, 70%), 12.16 (s, 1H, 100%);13C NMR (100 MHz DMSO-d6) δ 118.55, 118.80, 118.88, 119.05, 119.17, 119.87, 120.04, 122.52, 123.69, 124.23, 124.59, 124.81, 124.93, 125.27, 125.31, 127.94, 129.95, 141.79, 145.94, 146.09, 149.39, 148.52, 148.58, 150.97, 157.19, 157.96, 159.07, 165.38;19F NMR. (376 MHz DMSO-d6) δ −137.95 (d, 1F, J=23 Hz), −138.74 (d, 1F, J=23 Hz), −139.00 (d, 1F, 23 Hz), −139.94 (d, 1F, J=23 Hz); MS (ESI) m/z 352.9 (M−1)− 3,5-Difluoro-N′-(5-chloro-2-hydroxybenzylidene)benzohydrazide (A20) Brown solid (56% yield); m.p. 171-173° C.;1H NMR (400 MHz DMSO-d6) δ 6.85 (D, 1H, 25%, J=8.6 HZ), 6.94 (D, 1H, 75%, J=8.8 HZ), 7.20 (S, 1H, 15%), 7.21 (s, 1H, 40%), 7.30-7.37 (m, 3H, 100%, 25%, 60%), 7.48-7.52 (m, 1H, 75%), 7.55-7.58 (m, 1H, 15%), 7.60-7.64 (m, 1H, 85%), 7.67 (s, 1H, 85%), 8.29 (s, 1H, 25%), 8.51 (s, 1H, 75%), 10.25 (s, 1H, 20%), 11.01 (s, 1H, 80%), 12.22 (s, 1H, 100%);13C NMR (100 MHz DMSO-d6) δ 118.06, 118.24, 118.94, 119.12, 119.91, 120.08, 121.35, 123.03, 123.07, 124.64, 124.79, 124.90, 125.28, 125.38, 127.20, 130.68, 131.11, 141.07, 146.05, 155.25, 155.99, 159.16, 159.18;19F NMR (376 MHz DMSO-d6) δ −137.95 (d, 1F, J=23 Hz), −138.73 (d, 1F, J=23 Hz), −139.07 (d, 1F, J=23 Hz), −139.92 (d, 1F, J=23 Hz); MS (ESI) m/z 309.0 (M−1)− 4-Difluoromethoxy-N′-(4-bromo-2-hydroxybenzylidene)benzohydrazide (A21) Yellow solid (96% yield); m.p. 195-200° C.;1H NMR (400 MHz DMSO-d6) δ 7.10-7.14 (m, 2H, 100%), 7.20 (s, 1H, 25%), 7.33 (d, 2H, J=0.5 Hz), 7.39, (s, 1H, 50%), 7.56 (d, 2H, 25%, 100%, J=7.4 Hz), 8.01 (d, 2H, 100% J=8.5 Hz), 8.62 (s, 1H, 100%), 11.49 (s, 1H, 100%), 12.14 (s, 1H, 100%);13C NMR (100 MHz, DMSO-d6) δ 113.46, 116.02, 118.07, 110.56, 118.59, 119.07, 122.43, 123.92, 129.31, 129.86, 130.31, 146.51, 158.03, 161.84;19F NMR (376 MHz DMSO-d6) δ −82.94 (s, 1F); HRMS (ESI) m/z calcd for C10H11BrF2N2O3H−: 384.9994, Found: 385.0007 (Δ=−3.49 ppm). 4-Difluoromethoxy-N′-(5-bromo-2-hydroxybenzylidene)benzohydrazide (A22) Beige solid (94% yield); m.p. 194-196° C.;1H NMR (400 MHz DMSO 6) δ 6.90 (d, 1H, 100%, J==8.8 Hz), 7.20 (s, 1H, 25%), 7.33 (d, 2H, 100%, J=8.6), 7.39 (s, 1H, 50%), 7.43 (dd, 1H, 100%, J=8.8, 2.2 Hz), 7.57 (s, 1H, 25%), 7.80 (s, 1H, 100%), 8.01 (d, 2H, 100%, J=8.6 Hz), 8.61 (s, 1H, 100%), 11.26 (s, 1H, 100%), 12.19 (s, 1H, 100%);13C NMR (100 MHz, DMSO-d6) δ 110.45, 113.46, 116.03, 118.07, 110.60, 118.68, 121.32, 129.28, 129.90, 130.36, 133.60, 145.62, 153.68, 156.41, 161.94;19F NMR (376 MHz DMSO-d6) δ −82.94 (s, 1F) HRMS (ESI) m/z calcd for C15H11BrF2N2O3H+: 384.9994, Found: 305.0019 (Δ=−6.65 ppm). 4-Difluoromethoxy-N′-(3,5-dibromo-2-hydroxybenzylidene)benzohydrazide (A23) Beige solid (89% yield); m.p.>220° C.;1H NMR (400 MHz DMSO-d6) δ 7.21 (s, 1H, 25%), 7.35 (d, 2H, 100%, J=8.6 Hz), 7.40 (s, 1H, 50%), 7.58 (s, 1H, 25%), 7.83 (s, 2H, 100%), 8.03 (d, 2H, 100% J=8.7 Hz), 8.53 (s, 1H, 100%), 12.56 (s, 1H, 100%), 12.70 (s, 1H, 100%);13C NMR (100 MHz, DMSO-d6) δ 110.38, 111.21, 113.42, 115.99, 118.09, 120.95, 128.65, 130.04, 132.12, 135.58, 147.09, 153.66, 162.02;19F NMR (376 MHz DMSO-d6) δ −83.03 (s, 1F); HRMS (ESI) m/z calcd for C15H10Br2F2N2O3H+: 462.9099, Found: 462.9103 (Δ=−0.92 ppm). 3-Trifluoromethyl-N′-(3-chloro-2-hydroxybenzylidene)benzohydrazide (A24) White solid (68% yield);1H NMR (500 MHz, DMSO-d6) δ 6.98 (t, J=7.8 Hz, 1H), 7.51 (m, 1H), 7.82 (t, J=7.0 Hz, 1H), 8.01 (d, J=7.0 Hz, 1H), 8.26 (d, J=7.9 Hz, 1H), 8.29 (s, 1H), 12.28 (s, 1H), 12.55 (s, 1H).13C NMR (125 MHz, DMSO-d6) δ 119.6, 120.1, 120.4, 124.2, 128.7, 129.2, 129.5, 130.0, 131.5, 131.9, 133.3, 149.2, 153.3, 161.5.19F NMR (376 MHz, DMSO-d6) δ −61.14 (s, 3H). MP>220° C. HRMS [M+H]+calcd for C15H11ClF3N2O2+: 343.0456, found: 343.0459 (Δ=−0.9 ppm). 3-Trifluoromethyl-N′-(3-bromo-2-hydroxybenzylidene)benzohydrazide (A25) White solid (72% yield);1H NMR (400 MHz, DMSO-d6) δ 6.93 (t, J=7.8 Hz, 1H), 7.55 (dd, J=7.7 Hz, J=1.4 Hz, 1H), 7.65 (dd, J=7.9 Hz, J=1.4 Hz, 1H), 7.82 (t, J=7.9 Hz, 1H), 8.02 (d, J=7.9 Hz, 1H), 8.26 (d, J=8.0 Hz, 1H), 8.29 (s, 1H), 8.60 (s, 1H), 12.49 (br s, 1H), 12.55 (br s, 1H).13C NMR (125 MHz, DMSO-d6) δ 110.0, 119.3, 120.6, 124.3, 125.3, 128.8, 130.0, 130.4, 132.0, 133.3, 134.5, 149.3, 154.2, 161.5.19F NMR (376 MHz, DMSO-d6) δ −61.14 (s, 3H). MP>220° C. HRMS [M+H]+calcd for C15H11BrF3N2O2+: 386.9951, found: 386.9946 (Δ=1.3 ppm). 3-Trifluoromethyl-N′-(4-bromo-2-hydroxybenzylidene)benzohydrazide (A26) White solid (73% yield);1H NMR (400 MHz, DMSO-d6) δ 7.13 (m, 2H), 7.60 (d, J=8.3 Hz, 1H), 7.80 (t, J=7.7 Hz, 1H), 7.99 (d, J=7.7 Hz, 1H), 8.24 (d, J=8.0 Hz, 1H), 8.28 (s, 1H), 8.66 (s, 1H), 11.37 (s, 1H), 12.28 (s, 1H).13C NMR (125 MHz, DMSO-d6) δ 110.6, 119.1, 122.5, 124.1, 120.5, 129.1, 129.9, 130.0, 131.9, 133.7, 146.7, 158.0, 161.4.19F NMR (376 MHz, DMSO-d6) δ −61.12 (s, 3H). MP>220° C. HRMS [M+H]+calcd for C15H11BrF3N2O2+: 386.9951, found: 306.9957 (Δ=−1.6 ppm). 3-Fluoro-N′-(3-bromo-2-hydroxybenzylidene)benzohydrazide (A27) White solid (73% yield);1H NMR (700 MHz, DMSO-d6) δ 6.92 (t, 1H, 75%, J=7.8 Hz), 6.99 (t, 1H, 25%, J=7.8 Hz), 7.50 (td, 1H, 75%, J=8.5 Hz, J=2.2 Hz), 7.54 (d, 1H, 75%, J=7.6 Hz), 7.61-7.65 (m, 2H, 75%, 100%), 7.75-7.77 (m, 2H, 25%, 75%), 7.81 (d, 1H, 75%, J=7.7 Hz), 8.58 (s, 1H, 75%), 9.13 (s, 1H, 25%), 12.08 (br s, 1H, 25%), 12.45 (br s, 1H, 75%), 12.50 (s, 1H, 100%).13C NMR (175 MHz, DMSO-d6) δ 110.1, 110.1, 114.5, 114.6, 118.8, 119.1, 119.3, 119.3, 120.6, 121.1, 124.0, 124.0, 130.5, 130.9, 132.1, 134.5, 134.6, 134.7, 136.4, 149.1, 154.2, 155.3, 161.3, 161.6, 162.7, 165.1.19F NMR (376 MHz, DMSO-d6) δ −112.26 (td, J=5.6 Hz, J=, 9.2 Hz, 1F). MP=192-193° C. HRMS [M+H]+calcd for C14H11BrFN2O2+: 386.9982, found: 386.9986 (Δ=−0.9 ppm). 3-Fluoro-N′-(4-bromo-2-hydroxybenzylidene)benzohydrazide (A28) White solid (61% yield);1H NMR (700 MHz, DMSO-d6) δ 7.12 (d, 1H, 78%, J=7.8 Hz), 7.14-7.17 (m, 2H, 78%, 24%), 7.19 (s, 1H, 19%), 7.47 (td, 1H, 79%, J=2.0 Hz, J=8.5 Hz), 7.58-7.62 (m, 2H, 100%, 78%), 7.67 (d, 1H, 20%, J=8.3 Hz), 7.74 (d, 1H, 79%, J=9.7 Hz), 7.79 (d, 1H, 79%, J=7.7 Hz), 8.63 (s, 1H, 81%), 9.0 (s, 1H, 21%), 11.42 (s, 1H, 100%), 12.17 (s, 1H, 100%).13C NMR (175 MHz, DMSO-d6) δ 114.4, 114.5, 118.0, 118.6, 118.9, 119.0, 119.1, 119.3, 122.5, 121.8, 123.9, 123.9, 124.1, 126.1, 130.2, 130.8, 131.5, 135.1, 135.1, 136.7, 158.0, 159.2, 161.3, 161.3, 161.6, 162.6.19F NMR (376 MHz, DMSO-d6) δ −112.41 (td, J=6.0 Hz, J=9.4 Hz, 1F). MP=201-202° C. HRMS [M+H]+calcd for C14H11BrFN2O2+: 386.9982, found: 386.9985 (Δ=−0.8 ppm). 3,4-Dibromo-N′-(3,5-dibromo-2-hydroxybenzylidene)benzohydrazide (A29) Yellow solid (78% yield); m.p. 225-230° C.;1H NMR (400 MHz, DMSO-d6) δ 7.91-7.85 (m, 3H, 100%), 7.93-7.95 (m, 2H, 100%, 20%), 8.27 (s, 1H, 80%), 8.50 (s, 1H, 80%), 9.03 (s, 1H, 20%), 12.53 (s, 2H, 100%, 50%);13C NMR (100 MHz, DMSO-d6) δ 110.48, 110.76, 111.30, 111.68, 120.37, 120.91, 124.28, 128.58, 132.53, 133.45, 135.77, 137.77, 147.64, 153.65, 154.75, 160.86, 163.95; HRMS (ESI) m/z calcd for C14H8Br4N2O2: 552.7391, Found: 552.7392 (Δ=0.18 ppm). 3,4-Dibromo-N′-(3,5-dichloro-2-hydroxybenzylidene)benzohydrazide (A30) Yellow solid (64% yield); m.p. 210-215° C.;1H NMR (400 MHz, DMSO-d6) δ 7.63 (d, 1H) 7.69 (d, 1H) 7.84 (dd, 1H) 7.97 (d, 1H) 8.29 (s, 1H) 8.55 (s, 1H) 12.35 (d, 2H)13C NMR (125 MHz, DMSO-d6) δ 120.77, 121.99, 123.03, 124.29, 128.36, 128.58, 130.47, 133.05, 134.16, 147.48, 152.24, 160.86, 163.54; HRMS (ESI) m/z calcd for C14H8Br2Cl2N2O2: 464.8404, Found: 464.8402 (Δ=−0.32 ppm). 3,4-Dibromo-N′-(5-chloro-2-hydroxybenzylidene)benzohydrazide (A31) Light yellow solid (35% yield); m.p.>230° C.;1H NMR (400 MHz, DMSO-d6) δ 6.95 (d, 1H, 60%, J=8.8 Hz), 7.00 (d, 1H, 40%, J=8.8 Hz), 7.32 (dd, 1H, 60%, J=8.8, 2.6 Hz), 7.41 (dd, 1H, J=8.8, 2.6 Hz), 7.68 (d, 1H, 60%, J=2.5 Hz), 7.77 (d, 1H, 40%, J=2.6 Hz), 7.85 (dd, 1H, 65%, J=8.3, 1.7 Hz), 7.95 (d, 1H, 60%, J=8.3 Hz), 8.29 (s, 1H, 65%), 8.62 (s, 1H, 60%), 8.94 (s, 1H, 40%), 11.13 (s, 1H, 100%), 12.25 (s, 1H, 60%);13C NMR (125 MHz, DMSO-d6) δ 118.21, 118.47, 119.94, 120.70, 123.11, 124.19, 127.22, 128.01, 128.51, 131.00, 132.44, 133.59, 134.06, 146.06, 155.98, 157.24, 160.83; HRMS (ESI) m/z calcd for C14H9Br2ClN2O2: 430.8812, Found: 430.8792 (Δ=−4.51 ppm). 3,4-Dibromo-N′-(2-hydroxy-1-naphthylidene)benzohydrazide (A32) Dark yellow solid (66% yield); m.p.>230° C.;1H NMR (400 MHz, DMSO-d6) δ 7.22 (d, 1H, 85%, J=9 Hz), 7.7.27 (d, 1H, 15%, J=9 Hz), 7.40 (t, 1H, 100%, J=7.5 Hz), 7.60 (t, 1H, 100%, J=7.6 Hz), 7.87-7.89 (m, 2H, 85%, 85%), 7.93 (d, 1H, 100%, J=9 Hz), 7.98 (d, 1H, 85%, J=8.3 Hz), 8.02 (d, 1H, 15%, J=8.3 Hz), 8.28 (d, 1H, 85%, J=8.6 Hz), 8.32 (s, 1H, 85%), 8.63 (d, 1H, 15%, J=8.6 Hz), 9.44 (s, 1H, 85%), 9.97 (s, 1H, 15%), 12.28 (s, 1H, 85%), 12.55 (s, 1H, 85%), 12.86 (s, 1H, 10%);13C NMR (100 MHz, DMSO-d6) δ 108.55, 118.85, 120.91, 123.64, 124.33, 127.89, 128.12, 129.01, 131.60, 132.39, 133.05, 134.23, 147.57, 158.12, 160.35; HRMS (ESI) m/z calcd for C18H11Br2N2O2: 446.934, Found: 446.9338 (Δ=−0.46 ppm). 3,4-Dibromo-N′-(5-bromo-2-hydroxybenzylidene)benzohydrazide (A33) Light yellow, cream solid (53% yield); m.p.>230° C.;1H NMR (400 MHz, DMSO-d6) δ 6.89 (d, 1H, 65%, J=8.8 Hz), 6.94 (d, 1H, 35%, J=8.8 Hz), 7.42 (dd, 1H, 65%, J=8.7, 2.3 Hz), 7.52 (dd, 1H, 35%, J=8.8, 2.4 Hz), 7.80 (s, 1H, 65%), 7.83 (d, 1H, 70%, J=8.3 Hz), 7.88 (s, 1H, 35%), 7.94 (d, 1H, 70%, J=8.3 Hz), 8.28 (s, 1H, 70%), 8.60 (s, 1H, 65%), 8.92 (s, 1H, 35%), 11.13 (s, 1H, 100%), 12.23 (s, 1H, 60%);13C NMR (100 MHz, DMSO-d6) δ 110.38, 118.73, 121.15, 124.02, 128.35, 129.91, 132.28, 133.44, 133.61, 145.72, 156.23, 157.48, 160.56; HRMS (ESI) m/z calcd for C14H9Br3N2O2: 474.8288, Found: 474.8287 (Δ=−0.19 ppm). 3,4-Dibromo-N′-(2-hydroxy-5-methylbenzylidene)benzohydrazide (A34) White solid (94% yield); m.p. 212-216° C.;1H NMR (400 MHz DMSO-d6) δ 2.24 (s, 3H), 6.82 (d, 1H, 55%, J=8.3 Hz), 6.86 (d, 1H, J=8.3 Hz), 7.10 (d, 1H, 55%, J=8.2 Hz), 7.19 (d, 1H, 45%, J=8.3 Hz), 7.36 (s, 1H, 55%), 7.47 (s, 1H, 45%), 7.83 (d, 1H, 60%, J=8.3 Hz), 7.94 (d, 2H, 30%, 30%, J=8.3 Hz), 8.27 (s, 1H, 60%), 8.58 (s, 1H, 55%), 8.91 (s, 1H, 45%), 10.84 (s, 1H, 60%), 10.90 (s, 1H, 40%), 12.15 (s, 1H, 50%);13C NMR (100 MHz, DMSO-d6) δ 116.38, 118.36, 124.19, 128.14, 128.49, 132.42, 148.46, 155.28, 156.49, 160.54, 162.47; HRMS (ESI) m/z calcd C15H11Br2N2O2: 410.9343, Found: 410,9338 (Δ=−1.25 ppm). 3,4-Dibromo-N′-(4-bromo-2-hydroxybenzylidene)benzohydrazide (A35) Off-white solid (63% yield); m.p.>230° C.;1H NMR (400 MHz, DMSO-d6) δ 7.08-7.18 (m, 2H, 100%, 100%), 7.57 (d, 1H, 80%, J=8.3 Hz), 7.65 (d, 2H, 20%, 20%, J=8.3 Hz), 7.83 (dd, 1H, 80%, J=8.3, 1.9 Hz), 7.94 (d, 1H, 80%, J=8.3 Hz), 8.27 (s, 1H, 80%), 8.61 (s, 1H, 75%), 8.94 (s, 1H, 25%), 11.33 9 s, 1H, 100%), 12.18 (s, 1H, 75%);13C NMR (100 MHz, DMSO-d6) δ 118.60, 122.49, 124.11, 126.08, 128.48, 130.02, 132.42, 146.74, 157.99, 160.61; HRMS (ESI) m/z calcd for C14Br4N2O2: 474.8286, Found: 474.8287 (Δ=0.16 ppm). 3,5-Dibromo-N′-(5-bromo-2-hydroxybenzylidene)benzohydrazide (A36) White solid (58% yield); m.p.>230° C.;1H NMR (400 MHz, DMSO-d6) δ 6.90 (d, 1H, J=8.8 Hz), 7.43 (dd, 1H, J=8.8, 2.6 Hz), 7.82 (d, 1H, J=2.5 Hz), 8.11 (s, 3H), 8.61 (s, 1H), 11.10 (s, 1H), 12.25 (s, 1H);13C NMR (100 MHz, DMSO-d6) δ 110.52, 118.67, 121.33, 122.72, 129.60, 129.95, 136.40, 136.59, 145.99, 156.39; HRMS (ESI) m/z calcd for C14H9Br3N2O2: 474.8288, Found: 474.8287 (Δ=−0.32 ppm). 3,5-Dibromo-N′-(2-hydroxy-1-naphthylidene)benzohydrazide (A37) Yellow solid (42% yield); m.p.>230° C.;1H NMR (700 MHz, DMSO-d6) δ 7.24 (d, 1H, J=8.9 Hz), 7.42 (t, 1H, J=7.4 Hz), 7.62 (t, 1H, J=7.6 Hz), 7.90 (d, 1H, J=8 Hz), 7.95 (d, 1H, J=8.9 Hz), 8.14 (s, 1H), 8.16 (s, 2H), 8.32 (d, 1H, J=8.6 Hz), 9.44 (s, 1H), 12.31 (s, 1H), 12.50 (s, 1H);13C NMR (175 MHz, DMSO-d6) δ 108.54, 118.82, 120.99, 122.85, 123.63, 127.86, 127.90, 129.00, 129.56, 131.58, 133.12, 136.84, 136.69, 147.79, 158.15, 159.66; HRMS (ESI) m/z calcd for C14H9Br3N2O2: 446.934, Found: 446.9338 (Δ=−0.34 ppm). 3,5-Dibromo-N′-(3,5-dichloro-2-hydroxybenzylidene)benzohydrazide (A38) Tan solid (Quantitative yield); m.p.>230° C.;1H NMR (400 MHz, DMSO-d6) δ 7.63 (s, 1H), 7.69 (s, 2H), 8.11 (s, 2H), 8.12 (s, 1H), 8.56 (s, 1H), 12.25 (s, 1H), 12.61 (s, 1H);13C NMR (100 MHz, DMSO-d6) δ 120.78, 121.62, 122.81, 123.08, 128.34, 129.70, 130.55, 135.85, 136.91, 147.67, 152.23, 160.24; HRMS (ESI) m/z calcd for C14H8Br2Cl2N2O2: 446.9339, Found: 446.9338 (Δ=−0.19 ppm). 3,5-Dibromo-N′-(4-bromo-2-hydroxybenzylidene)benzohydrazide (A39) White solid (84% yield); m.p.>230° C.;1H NMR (700 MHz, DMSO-d6) δ 7.15 (d, 1H, J=8.3 Hz), 7.14 (s, 1H), 7.59 (d, 1H, J=8.3 Hz), 8.10 (s, 3H), 8.62 (s, 1H), 11.30 (s, 1H), 12.20 (s, 1H);13C NMR (175 MHz, DMSO-d6) δ 118.64, 119.06, 122.53, 122.76, 124.21, 129.60, 129.89, 136.46, 136.60, 146.81, 157.99, 159.98; HRMS (ESI) m/z calcd for C14H9Br3N2O2: 474.8289, Found: 474.8287 (Δ=−0.42 ppm). 3,5-Dibromo-N′-(5-chloro-2-hydroxybenzylidene)benzohydrazide (A40) White solid (92% yield); m.p.>230° C.;1H NMR (700 MHz, DMSO-d6) δ 6.95 (d, 1H, J=8.8 Hz), 7.33 (dd, 1H, J=8.8, 2.7 Hz), 7.69 (s, 1H), 8.11 (s, 3H), 8.62 (s, 1H), 11.09 (s, 1H), 12.25 (s, 1H);13C NMR (175 MHz, DMSO-d6) δ 118.24, 120.74, 122.76, 127.09, 129.62, 131.09, 136.41, 146.15, 156.00, 160.09; HRMS (ESI) calcd for C14H9Br2ClN2O2: 430.8902, Found: 430.8792 (Δ=−2.34 ppm). 3,5-Dibromo-N′-(2-hydroxy-5-methylbenzylidene)benzohydrazide (A41) White solid (92% yield); m.p.>230° C.;1H NMR (400 KHz, DMSO-d6) δ 2.25 (s, 3H), 6.82 (d, 1H, J=8.2 Hz), 7.10 (dd, 1H, J=8.3, 1.8 Hz), 7.38 (s, 1H), 8.09 (s, 3H), 8.91 (s, 1H), 10.78 (s, 1H), 12.15 (s, 1H);13C NMR (175 MHz, DMSO-d6) δ 19.96, 116.29, 116.41, 117.88, 122.76, 128.00, 128.87, 129.64, 130.45, 131.22, 132.45, 133.95, 136.55, 148.56, 155.30, 156.52, 159.90, 162.50; HRMS (ESI) m/z calcd for C15H12Br2N2O2: 410.9345, Found: 410.9338 (Δ=−1.65 ppm). 2,3-Dibromo-N′-(3,5-dibromo-2-hydroxybenzylidene)benzohydrazide (A42) White solid (98% yield); m.p. 227-230° C.;1H NMR (400 MHz, DMSO-d6) δ 7.42-7.46 (m, 2H, 30%, 100%), 7.56-7.58 (m, 2H, 70%, 30%), 7.74 (s, 1H, 25%), 7.82 (s, 1H, 75%), 7.84 (s, 1H, 70%), 7.88 (d, 1H, 20%), 7.90 (dd, 1H, 80%, J=7.9, 1.4 Hz), 8.21 (s, 1H, 25%), 8.38 (s, 1H, 75%), 10.30 (s, 1H, 25%), 12.32 (s, 1H, 75%), 12.47 (s, 1H, 35%), 12.60 (s, 1H, 65%);13C, NMR (175 MHz, DMSO-d6) δ 110.57, 111.54, 120.77, 120.93, 121.54, 121.83, 125.15, 125.45, 127.18, 128.14, 129.52, 129.74, 131.33, 132.14, 134.45, 135.17, 135.68, 135.93, 139.15, 139.70, 144.00, 147.75, 152.57, 153.63, 163.06, 168.31; HRMS (ESI) m/z calcd for C15H8Br4N2O2: 552.7393, Found: 552.7392 (Δ=−0.19 ppm). 2,3-Dibromo-N′-(3,5-dichloro-2-hydroxybenzylidene)benzohydrazide (A43) Product washed with water and ˜1 mL ethyl acetate, filtered, and washed with DCM and hexanes. Tan solid. (43% yield); m.p. 227-2301H NMR (500 MHz DMSO-d6) δ 7.37 (d, 1H, 30%, 2.6 Hz), 7.42-7.46 (m, 3H, 30%, 70%, 30%), 7.53 (d, 1H, 30%, J=2.6 Hz), 7.57 (dd, 1H, 70%, J=7.6, 1.5 Hz), 7.64 (d, 1H, J=2.6 Hz), 7.68 (d, 1H, 70%, J=2.6 Hz), 7.89 (dd, 1H, 40%, J=6.7, 2.9 Hz), 7.91 (dd, 1H, 60%, J=8. 1.5 Hz), 8.25 (s, 1H, 30%), 8.42 (s, 1H, 70%), 10.27 (s, 1H, 30%), 12.08 (s, 1H, 70%), 12.45 (s, 1H, 30%), 12.56 (s, 70%);13C NMR (125 MHz, DMSO-d6) δ 120.84, 121.80, 123.15, 123.41, 125.03, 127.15, 128.28, 129.51, 130.61, 134.32, 135.07, 139.19, 139.87, 143.35, 147.30, 151.07, 152.16, 163.00, 168.35; MS (ESI) m/z 462.8 (M−1)− 4-Fluromethyl-N′-(3,5-dibromo-2-hydroxybenzylidene)benzohydrazide (A44) White solid (46% yield); m.p.>230° C.;1H NMR (400 MHz DMSO-d6) δ 5.46 (s, 1H), 5.58 (s, 1H), 7.57 (d, 2H, J=7.6 Hz), 7.80-7.82 (m, 2H), 7.99 (d, 2H, J=7.9 Hz), 8.53 (s, 1H), 12.56 (s, 1H), 12.71 (s, 1H);13C NMR (100 MHz, DMSO-d6) δ 82.71, 84.33, 110.39, 111.21, 120.95, 127.27, 127.33, 128.05, 132.13, 135.58, 140.40, 140.57, 147.17, 153.66, 162.61;19F NMR (376 MHz DMSO-d6) δ 209.61 (t, 1F, J=47.2 Hz); MS (ESI) m/z 428.9 (M+1)+ 4-Azido-N′-(5-dibromo-2-hydroxybenzylidene)benzohydrazide (A45) White solid (64% yield); m.p. 193-197° C.;1H NMR (400 MHz DMSO-d6) δ 7.28 (d, 2H, J=8.6 Hz), 7.79-7.81 (m, 2H), 8.00 (d, 2H, J=8.6 Hz), 8.51 (s, 1H), 12.53 (s, 1H), 12.71 (s, 1H);13C NMR (100 MHz, DMSO-d6). δ 110.39, 111.21, 119.26, 120.98, 128.45, 129.74, 132.11, 135.55, 143.53, 146.99, 153.65, 162.05. 4-Ethynyl-N′-(3,5-dibromo-2-hydroxybenzylidene)benzohydrazide (A46) Yellow solid (55% yield); m.p.>230° C.;1H NMR (300 MHz DMSO-d6) δ 4.46 (s, 1H), 7.39 (d, 1H, J=7.9 Hz), 7.65 (d, 1H, J=8.4 Hz), 7.80-7.96 (m, 4H), 8.52 (s, 1H), 12.48-12.66 (m, 2H) MS (ESI) m/z 418.9 (M−1)− 4-Ethynyl-N′-(3,5-dibromo-2-hydroxybenzylidene)benzohydrazide (A47) Yellow solid (75% yield); m.p.>230° C.;1H NMR (300 MHz DMSO-d6) δ 4.44 (s, 1H), 6.89 (d, 1H, J=3.7 Hz), 7.35-7.44 (m, 2H), 7.63 (d, 1H, J=8 Hz), 7.78-7.95 (m, 2H), 8.60 (s, 1H), 11.23-11.32)m, 1H), 12.13-12.24 (m, 1H); MS (ESI) m/z 340.9 (M−1− Chemical Synthesis and Characterization of Heteroaromatic Acylhydrazones of this Invention 5-Bromo-N′-(3,5-dibromo-2-hydroxybenzylidene)pyrimidine-2-carbohydrazide (H1) To a solution of 5-bromopyrimidine-2-carbohydrazide (50 mg, 0.23 mmol), 3,5-dibromo-2-hydroxybenzaldehyde (67 mg, 0.24 mmol) in methanol (5 mL) was added 1 drop of glacial acetic acid. The reaction mixture was stirred at room temperature overnight. Addition of water to the reaction mixture resulted in precipitation of the product, which was filtered, washed with water and dried under vacuum, to give pure product as white solid (95 mg, 86% yield:1H NMR (700 MHz, DMSO-d6) δ 7.73 (d, J=8.3, 2.2 Hz, 1H), 7.84 (t, J=3.1 Hz, 1H), 8.73 (s, 1H), 9.23 (s, 2H), 12.63 (br s, 1H), 13.06 (s, 1H).13C NMR (175 MHz, DMSO-d6) δ 110.5, 110.7, 111.3, 111.7, 120.4, 120.9, 122.9, 132.2, 133.4, 135.9, 137.8, 149.0, 153.8, 154.8, 154.9, 158.4, 158.5, 164.0. MP>220° C. HRMS [M+H]+calcd for C12H8Br3N4O2+476.8192, found 476.8183 (Δ=1.9 ppm). The procedure detailed in the example above can be used for the synthesis of the following compounds. 5-Bromo-N′-(5-bromo-2-hydroxybenzylidene)thiophene-2-carbohydrazide (H2) White solid (85% yield);1H NMR (500 MHz, DMSO-d6) δ 6.90 (d, J=8.8 Hz, 1H), 7.43 (dd, J=8.8 Hz, J=2.4 Hz, 1H), 7.69 (d, J=1.1 Hz, 1H), 7.80 (d, J=2.4 Hz, 1H), 8.31 (d, J=1.1 Hz, 1H), 8.57 (s, 1H), 11.15 (s, 1H), 12.01 (s, 1H).13C NMR (125 MHz, DMSO-d6) δ 110.5, 112.5, 118.6, 121.4, 129.4, 130.1, 132.6, 133.6, 135.8, 145.2, 156.3, 157.2. MP: 210-211° C. HRMS [M+H]+calcd for C12H9Br2N2O2S+402.8746, found 402.0755 (Δ=−2.1 ppm). 5-Bromo-N′-(4-bromo-2-hydroxybenzylidene)thiophene-2-carbohydrazide (H3) White solid. (89 yield);1H NMR (400 MHz, DMSO-d6) δ 7.11 (m, 2H), 7.57 (d, J=8.2 Hz, 1H), 7.68 (d, J=1.2 Hz, 1H), 8.30 J=1.2 Hz, 1H), 8.58 (s, 1H), 11.35 (s, 1H), 11.95 (s, 1H).13C NMR (100 MHz, DMSO-d6) δ 112.5, 118.6, 119.0, 122.4, 123.9, 129.4, 130.0, 132.5, 135.8, 146.1, 157.2, 157.9. MP: 217-219° C. HRMS [M+H]+calcd for C12H9Br2N2O2S+402.8746, found 402.8757 (Δ=−2.9 ppm). 5-Bromo-N′-(3,5-dibromo-2-hydroxybenzylidene)thiophene-2-carbohydrazide (H4) White solid (91% yield);1H NMR (500 MHz, DMSO-d6) δ 7.69 (d, J=1.2 Hz, 1H), 7.83 (s, 2H), 8.34 (d, J=1.4 Hz, 1H), 8.48 (s, 1H), 12.40 (s, 1H), 12.56 (s, 1H).13C NMR (125 MHz, DMSO-d6) δ 110.4, 111.2, 112.8, 121.0, 129.4, 132.1, 133.2, 135.1, 135.6, 146.9, 153.6, 157.3. MP>220° C. HRMS [M+H]+calcd for. C12H8Br3N2S+480.7851, found 480.7856 (Δ=−1.0 ppm). 5-Bromo-N′-((2-hydroxynaphthalen-1-yl)methylene)thiophene-2-carbohydrazide (H5) White solid (78% yield);1H NMR (700 MHz, DMSO-d6) δ 7.23 (d, J=8.9 Hz, 1H), 7.41 (t, J=7.4 Hz, 1H), 7.61 (t, J=7.5 Hz, 1H), 7.71 (d, J=1.5 Hz, 1H), 7.90 (d, J=8.0 Hz, 1H), 7.94 (d, J=9.0 Hz, 1H), 8.28 (d, J=8.6 Hz, 1H), 8.33 (d, J=1.4 Hz, 1H), 9.40 (s, 1H), 12.07 (s, 1H), 12.57 (s, 1H).13C NMR (125 MHz, DMSO-d6) δ 108.6, 112.8, 118.9, 120.9, 123.6, 127.9, 129.0, 129.3, 131.6, 132.6, 132.9, 135.7, 146.7, 156.9, 158.0. MP: 197-198° C. HRMS [M+H]+calcd for C16H12BrN2O2S+374.9797, found 374.9809 (Δ=−3.2 ppm). 5-Bromo-N′-(4-bromo-2-hydroxybenzylidene) nicotinohydrazide (H6) White solid (83% yield);1H NMR (700 MHz, DMSO-d6) δ 7.12 (dd, J=8.3 Hz, J=1.8 Hz, 1H), 7.14 (d, J=1.8 Hz, 1H), 7.61 (d, J=8.3 Hz, 1H), 8.51 (t, J=2.1 Hz, 1H), 8.62 (S, 1H), 8.92 (d, J=2.2 Hz, 1H), 9.04 (d, J=1.8 Hz, 1H), 11.28 (s, 1H), 12.27 (s, 1H).13C NMR (175 MHz, DMSO-d6) δ 118.6, 119.1, 120.1, 122.5, 124.3, 129.8, 130.3, 137.7, 146.8, 147.3, 153.1, 158.0, 160.0. MP>220° C. HRMS [M+H]+calcd for C13H10Br2N3O2+397.9134, found 397.9147 (Δ=−3.3 ppm). 4,5-Dibromo-N′-(5-bromo-2-hydroxybenzylidene) furan-2-carbohydrazide (H7) White solid (67 yield);1H NMR (700 MHz, DMSO-d6) δ 6.89 (d, J=8.8 Hz, 1H), 7.43 (dd, J=8.7 Hz, J=2.4 Hz, 1H), 7.56 (s, 1H), 8.79 (d, J=2.2 Hz, 1H), 8.61 (s, 1H), 11.01 (s, 1H), 12.23 (s, 1H).13C NMR (175 MHz, DMSO-d6) δ 103.6, 110.5, 118.7, 119.2, 121.4, 127.2, 129.8, 133.8, 145.8, 148.1, 152.4, 156.3. MP>220° C. HRMS [M+H]+calcd for C12H8Br3N2O3+464.8080, found 464.8092 (Δ=−2.6 ppm). 4,5-Dibromo-N′-(4-bromo-2-hydroxybenzylidene)furan-2-carbohydrazide (H8) White solid 73% yield);1H NMR (400 MHz, DMSO-d6) δ 7.10 (dd, J=8.2 Hz, J=1.8 Hz, 1H), 7.12 (d, J=1.7 Hz, 1H), 7.55 (s, 1H), 7.57 (d, J=8.3 Hz, 1H), 3.62 (s, 1H), 11.21 (s, 1H), 12.18 (s, 1H).13C NMR (100 MHz, DMSO-d6) δ 103.6, 118.7, 119.0, 119.1, 122.5, 124.1, 127.0, 129.7, 146.6, 148.1, 152.3, 157.9. MP>220° C. HRMS [M+H]+calcd for C12H8Br3N2O3+464.8080, found 464.8073 (Δ=1.5 ppm). 4,5-Dibromo-N′-(3,5-dibromo-2-hydroxybenzylidene)furan-2-carbohydrazide (H9) White solid (79% yield);1H NMR (700 MHz, DMSO-d6) δ 7.60 (s, 1H), 7.81 (d, J=2.3 Hz, 1H), 7.84 (d, J=2.3 Hz, 1H), 8.53 (s, 1H), 12.38 (s, 1H), 12.66 (s, 1H).13C NMR (125 MHz, DMSO-d6) δ 103.8, 110.5, 111.4, 119.8, 121.0, 127.6, 132.0, 135.8, 147.6, 147.8, 152.4, 153.5, MP>220° C. HRMS [M+H]+calcd for C12H7Br4N2O3+542.7185, found 542.7190 (Δ=−0.9 ppm). 4,5-Dibromo-N′-(2-hydroxynaphthalen-1-yl)methylenefuran-2-carbohydrazide (H10) White solid (77% yield);1H NMR (400 MHz, DMSO-d6) δ 7.23 (d, J=9.0 Hz, 1H), 7.41 (t, J=7.4 Hz, 1H), 7.59 (s, 1H), 7.61 (t, J=7.3 Hz, 1H), 7.90 (d, J=8.0 Hz, 1H), 7.94 (d, J=8.9 Hz, 1H), 8.29 (d, J=8.6 Hz, 1H), 9.48 (s, 1H), 12.30 (s, 1H), 12.41 (s, 1H).13C NMR (100 MHz, DMSO-d6) δ 103.9, 108.6, 118.8, 119.3, 121.0, 123.6, 127.0, 127.8, 128.9, 131.6, 133.1, 147.9, 148.1, 152.0, 158.0. MP>220° C. HRMS [M+H]+calcd for C16H11Br2N2O3+436.9131, found 436.9148 (Δ=−3.9 ppm). 4-Bromo-N′-(5-bromo-2-hydroxybenzylidene)furan-2-carbohydrazide (H11) White solid. (67 yield);1H NMR (700 MHz, DMSO-d6) δ 6.90 (d, J=8.8 Hz, 1H), 7.43 (dd, J=8.7 Hz, J=2.1 Hz, 1H), 7.48 (s, 1H), 7.78 (s, 1H), 8.23 (s, 1H), 8.61 (s, 1H), 11.05 (s, 1H), 12.21 (s, 1H).13C NMR (175 MHz, DMSO-d6) δ 100.6, 110.5, 117.3, 118.6, 121.4, 130.0, 133.7, 144.4, 145.7, 146.9, 153.1, 156.3. MP: 203-205° C. HRMS [M+H]+calcd for C22H9Br2O3+386.8974, found 386.8977 (Δ=−0.8 ppm). 4-Bromo-N′-(4-bromo-2-hydroxybenzylidene)furan-2-carbohydrazide (H12) White solid (69% yield);1H NMR (500 MHz, DMSO-d6) δ 7.11 (m, 2H), 7.47 (s, 1H), 7.57 (d, J=8.3 Hz, 1H), 8.23 (d, J=0.6 Hz, 1H), 8.62 (s, 1H), 11.26 (s, 1H), 12.17 (s, 1H).13C NMR (125 MHz, DMSO-d6) δ 100.7, 117.3, 118.7, 119.0, 122.5, 124.1, 129.9, 144.4, 146.5, 146.9, 153.1, 157.9. MP>220° C. HRMS [M+H]+calcd for C12H9Br2N2O3+386.8974, found 386.8975 (Δ=−0.2 ppm). 4-bromo-N′-(3,5-dibromo-2-hydroxybenzylidene) furan-2-carbohydrazide (H13) White solid (72% yield);1H NMR (700 MHz, DMSO-d6) δ 7.52 (s, H), 7.81 (d, J=2.0 Hz, 1H), 7.84 (d, J=2.4 Hz, 1H), 8.27 (s, 1H), 8.53 (s, 1H), 12.44 (s, 1H), 12.63 (s, 1H).13C NMR (175 MHz, DMSO-d6) δ 100.9, 110.5, 111.3, 118.0, 121.0, 132.1, 135.7, 144.8, 146.5, 147.6, 153.2, 153.6. MP=214-215° C. HRMS [M+H]+calcd for C12H8Br3N2O3+464.8080, found 463.8086 (Δ=−1.3 ppm). N′-(4-bromo-2-hydroxybenzylidene)furan-3-carbohydrazide (H14) White solid. (82% yield);1H NMR (700 MHz, DMSO-d6) δ 7.11 (dd, J=8.2 Hz, J=1.6 Hz, 1H), 7.14 (d, J=1.7 Hz, 1H), 7.56 (d, J=8.3 Hz, 1H), 7.60 (dd, J=5.0 Hz, J=1.0 Hz, 1H), 7.68 (dd, J=5.0 Hz, J=3.0 Hz, 1H), 8.32 (d, J=1.8 Hz, 1H), 8.59 (s, 1H), 11.48 (s, 1H), 11.97 (s, 1H).13C NMR (175 MHz, DMSO-d6) δ 118.6, 119.0, 122.4, 123.8, 126.8, 127.3, 130.2, 135.5, 145.8, 157.9, 158.4. MP>220° C. HRMS [M+H]+calcd for C12H10BrN2O3+308.9869, found 308.9871 (Δ=−0.6 ppm). N′-(3,5-dibromo-2-hydroxybenzylidene)tetrahydro-2H-pyran-4-carbohydrazide (H15) White solid (67% yield);1H NMR (500 MHz, DMSO-d6) δ 1.68 (s, 3H), 2.00 (s, 2H), 2.19 (s, 1H), 2.50 (s, 1H), 3.32-3.36 (m, 3H), 3.89 (d, 1H, J=2.2), 7.74-7.79 (m, 2H), 8.16-8.29 (m, 1H), 12.02 (s, 1H), 12.58 (d, 1H, J=3.97).13C NMR (125 MHz, DMSO-d6) δ 21.19, 28.49, 66.21, 111.03, 122.90, 132.04, 135.29, 140.97, 145.73, 153.47, 165.79, 171.45. MP>220° C. HRMS [M+H]+calcd for C13H15Br2N2O3+404.9444, found 404.9443 (Δ=0.2 ppm). Example 8 In Vitro Activities (MIC80and K100of Acylhydrazones In Vitro Susceptibility (MIC80) Assay MICs was determined following the methods of the Clinical and Laboratory Standards Institutes (CLSI) with modifications. Yeast Nitrogen Base (YNB) medium (pH 7.0, 0.2% glucose) buffered with HEPES was used for MIC studies. HEPES was used instead of morpholinepropanesulfonic acid (MOPS), because MOPS was found to inhibit the activity of this kind of compounds. The compound was serially diluted from 16 to 0.03 μg/ml, in a 96-well plate. The inoculum was prepared as described in the CLSI protocol M27A3 guidelines. The plates were incubated at 37° C. with 5% CO2 for 24 to 72 h and the optical density was measure at 450 nm. The MICs was determined as the lowest concentration of the compound that inhibited. 80% of growth compared to the control. In Vitro Killing Activity (K100) Assay C. neoformanscells from a culture grown overnight were washed in PBS and resuspended in YNB buffered with HEPES at pH 7.4. The cells were counted, and 2×104cells were incubated with different concentration of compounds in a final volume of 10 ml with a final concentration of 0.5% DMSO. The tubes were then incubated at 37° C. with 5% CO2on a rotary shaker at 200 rpm. Aliquots were taken at time points and diluted, and 100-1 portions were plated onto Yeast Extract-Peptone-Dextrose (YPD) plates. YPD plates were incubated in a 30° C. incubator and after 48 h, the numbers of CPU were counted and recorded. TABLE 4MIC80and killing activity (K100) of aromatic acylhydrazones.CompoundMIC80(μg/mL)K100* (μg/mL)A10.25>1A21>4A30.252A41>4A50.12FungistaticA60.120.5A70.5>4A80.51A90.120.5A100.25FungistaticA110.06>1A120.50.5A130.060.5A140.5>2A150.0070.03A160.25>1A170.250.25A180.250.25A190.50.25A2010.5A210.12—A220.25—A230.12—A2414A2512A260.51A2712A280.5>2A290.06>0.5A30<0.03>0.025A310.06>0.5A320.12>1A330.252A340.12>1A350.06>5A360.06>5A370.250.5A380.50.5A3911A400.121A410.51A420.50.5A4311A440.50.5A450.06—A460.12FungistaticA470.120.12*The minimum concentration of a compound that kills 100% ofC.neoformanscells in 48 h. TABLE 5MIC80and killing activity (K100) of heteroaromatic acylhydrazones.CompoundMIC80(μg/mL)K100* (μg/mL)H10.25>2H20.12>0.5H30.12>0.5H40.06>0.25H50.12>0.5H61>4H70.25>1H80.06>0.25H90.12>0.5H100.12>0.5H110.25>1H120.5>2H130.06>0.25H140.5>1H150.5>2*The minimum concentration of a compound that kills 100% ofC.neoformanscells in 48 h. Example 9 In Vivo Efficacy Evaluation (Survival Study) of Compound A15 in an Animal Model For survival study, 4-week old CBA/J (Envigo) le mice were used. They were divided as ten mice for each treatment or control group. Mice were infected intranasally with 20 μl of a suspension containing 5×105C. neoformanscells and subsequently treated orally with 20 mg/kg/day of compound A15 and fluconazole as drug control in a final volume of 100 μl of PEG30% in a saline buffer. The untreated control group mice received 100 μl of PEG30% in a saline buffer. Gavage was used as route of administration. At the end of the experiment, 80% of the mice treated with compound A15 survived whereas, only 30% of the mice treated with fluconazole survived. Mice were fed ad libitum and monitored every day for discomfort and meningitis signs. Mice showing weight loss, lethargy, tremor or inability to reach food or water were sacrificed and survival was counted until that day (seeFIG.2). Discussion The compounds described herein potent killing activity with low or no toxicity that can be used alone or in combination of current antifungal agents to treat superficial or invasive fungal infections. A particular challenge with the discovery of antifungal drugs is toxicity due to the similarities between the fungal and human eukaryotic genomes. In exploring potential therapeutic targets, it became apparent that fungal sphingolipid pathways are quite distinct from human sphingolipid pathways. In addition, it is well established that the sphingolipid pathway is involved in the virulence of clinically important pathogenic fungi includingCryptococcus neoformans(Cn). Work from our lab and others showed that fungal sphingolipid complex, glucosylceramide (GlcCer), has increased expression on the fungal membrane in a lung infection model, GlcCer is critical in maintaining fungal cell membrane integrity and represents an attractive therapeutic target. In addition, it is well-established that gene deletion of glucosylceramide synthase (Gcs1) results in the creation of aC. neoformansstrain, Δgcs1, that does not cause morbidity or mortality in a mouse model of CM. Moreover, Δgcs1 fungi exhibit deficient growth in vitro at a pH of >7, a similar pH to that found in the extracellular alveolar space in the lung where Cn thrives 10 and is the predominant first site of infection. There is a major clinical need for new drugs due to a dramatic increase of morbidity and mortality by invasive fungal infections. Without being limited by a particular theory, the compounds contained herein decrease the synthesis of fungal but not mammalian GlcCer. This action seems to be specific to the transport of fungal ceramide species. The compounds are active in vitro against fungi, especiallyC. neoformans, P. murina, P. jiroveci, R. oryzae, and dimorphic fungi. The compounds appear to be effective in vivo against cryptococcosis, candidiasis and also against pneumocystosis. The compounds do not induce resistance in vitro and they are synergistic with existing antifungals. C. albicansis resistant in vitro but not in vivo. Studies performed in this fungus have suggested that GlcCer is important for virulence but through a mechanism other than facilitating growth at neutral/alkaline pH, which is the pH used to screen our ChemBridge library. Hence, inhibition of GlcCer inC. albicansdoes not block fungal growth in vitro. However, because the compound still decreases GlcCer synthesis, which is required forCandidavirulence, the treatment is effective in partially protecting mice from invasive candidiasis. These findings support previous studies suggesting that the effect of GlcCer in vivo duringCandidainfection goes beyond the regulation of fungal alkaline tolerance. The compounds disclosed herein inhibit GlcCer synthesis; however, this lipid is most likely not the only target of these compounds. In fact, the blockage of fungal growth in alkaline pH due to the loss of GlcCer (Δgcs1 mutant) can be restored if Δgcs1 cells are shifted to an acidic environment (Singh A. et al. 2012). This can occur even after the cells are left in cell cycle arrest for 72 hours. This means that the lack of GlcCer has a “static” effect on cell growth. However, the compounds disclosed herein kill fungal cells. One explanation for this effect is that treatment with the compound acutely leads to the accumulation of sphingosines, which is highly toxic to fungal cells (Chung, N. et al, 2001; Chung, N. et al. 2000). The accumulation of sphingosine species is not present when Gsc1 is deleted (Rittershaus, P. C. 2006) or in mammalian cells treated with compound. Thus, the effect seems to go beyond the inhibition of GlcCer and this may account for the fungal killing effect exerted by the compounds and not by the absence of GlcCer. In summary, molecules were identified that target the synthesis of fungal but not mammalian GlcCer. These hydrazycins have potent antifungal in vitro and in vivo against a variety of clinically important fungi. They also displayed synergistic action with current antifungals, low toxicity, favorable PK parameters, and fungal specific mechanisms of action. REFERENCES Aerts A M, et al. 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11858881 | MODE OF CARRYING OUT THE INVENTION The method for purifying a nitrile solvent of the present invention includes performing contact treatment A, contact treatment B, and contact treatment C in this order. A preferred method for purifying a nitrile solvent of the present invention further includes performing contact treatment D and/or distillation treatment. The nitrile solvent as a subject of the purification method of the present invention is an organic solvent having a cyano group (—CN) in the molecule and contains impurities. The nitrile solvent that is used in the present invention is preferably hydrophobic. Here, the term “hydrophobic” means that the solvent is separated into an aqueous phase and a nitrile solvent phase when left to stand at ordinary temperature. As the nitrile solvent, a saturated aliphatic nitrile, such as propionitrile, butyronitrile, isobutyronitrile, or valeronitrile, an aromatic nitrile, such as benzonitrile, o-tolunitrile, m-tolunitrile, or p-tolunitrile, or the like may be exemplified. Among these nitrile solvents, a saturated aliphatic nitrile and an aromatic nitrile are preferable. The purification method of the present invention may be preferably applied to a nitrile solvent containing an imine as an impurity and may be more preferably applied to a nitrile solvent containing an imine and a conjugated diene, a carbonyl compound, and/or a high-boiling material as impurities. As the imine that is an impurity contained in the nitrile solvent, for example, a compound of formula (I) may be exemplified. In the formula (I), R1to R3each represent a hydrogen atom or an organic group. As the conjugated diene that is an impurity contained in the nitrile solvent, for example, a compound of formula (II) may be exemplified. In the formula (II), R4to R9each represent a hydrogen atom or an organic group, and R5and R6may be linked to form a ring. As the carbonyl compound that is an impurity contained in the nitrile solvent, a ketone and an aldehyde may be exemplified. The high-boiling material that is an impurity contained in the nitrile solvent is a material other than the above-mentioned imine, conjugated diene, and carbonyl compound and having a boiling point higher than the boiling point of the nitrile solvent. (Contact Treatment A) As the acidic aqueous solution that is used in the contact treatment A, for example, an aqueous solution of a mineral acid, such as hydrochloric acid (aqueous hydrogen chloride solution), an aqueous sulfuric acid solution, or an aqueous nitric acid solution, may be exemplified. Among these acidic aqueous solutions, hydrochloric acid is preferable. The pH (20° C.) of the acidic aqueous solution is usually 3 or less, and preferably a pH of, for example, 2.9 or less, 2.8 or less, 2.7 or less, 2.6 or less, 2.5 or less, 2.4 or less, 2.3 or less, 2.2 or less, 2.1 or less, 2.0 or less, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, or 1.5 or less may be selected. The amount of the acidic aqueous solution to be brought into contact is not particularly limited, but an amount of, for example, 1 to 500 wt %, 1 to 400 wt %, 1 to 300 wt %, 1 to 200 wt %, or 1 to 100 wt % with respect to the total weight of the nitrile solvent may be selected. The method for bringing a nitrile solvent into contact with an acidic aqueous solution is not particularly limited. For example, a method in which a nitrile solvent and an acidic aqueous solution are placed in a batch extractor and stirred or a method in which a nitrile solvent and an acidic aqueous solution are brought into counterflow contact with each other in a continuous extractor may be exemplified. The temperature when a nitrile solvent is brought into contact with an acidic aqueous solution is not particularly limited, but a temperature of, for example, 0° C. to 100° C., 0° C. to 90° C., 0° C. to 80° C., 0° C. to 70° C., 0° C. to 60° C., or 0° C. to 50° C. may be selected. The imine that is an impurity contained in a nitrile solvent is decomposed into corresponding carbonyl compound and primary amine by the contact treatment with an acidic aqueous solution. The primary amine is more soluble in the acidic aqueous solution phase than in the nitrile solvent phase. Therefore, the primary amine can be removed from the nitrile solvent by separating the acidic aqueous solution phase from the nitrile solvent phase. Consequently, the carbonyl compound remains as an impurity in the nitrile solvent subjected to the contact treatment A. (Contact Treatment B) The aqueous sodium hydrogen sulfite solution that is used in the contact treatment B is not particularly limited by the concentration thereof, but a concentration of, for example, 1 wt % to solubility, 5 wt % to solubility, wt % to solubility, 15 wt % to solubility, 20 wt % to solubility, 25 wt % to solubility, 30 wt % to solubility, or wt % to 35 wt % may be selected. Incidentally, the solubility of sodium hydrogen sulfite (NaHSO3) in water at 25° C. is about 43 to 44 wt %, and the pH of an aqueous sodium hydrogen sulfite solution at 20° C. is preferably higher than 3.0 and more preferably 3.5 to 5.0. The amount of the aqueous sodium hydrogen sulfite solution to be brought into contact is not particularly limited, but an amount of, for example, 1 to 500 wt %, 1 to 400 wt %, 1 to 300 wt %, 1 to 200 wt %, or 1 to 100 wt % with respect to the total weight of the nitrile solvent may be selected. The method for bringing a nitrile solvent into contact with an aqueous sodium hydrogen sulfite solution is not particularly limited. For example, a method in which a nitrile solvent and an aqueous sodium hydrogen sulfite solution are placed in a batch extractor and stirred or a method in which a nitrile solvent and an aqueous sodium hydrogen sulfite solution are brought into counterflow contact with each other in a continuous extractor may be exemplified. The temperature when a nitrile solvent and an aqueous sodium hydrogen sulfite solution are brought into contact with each other is not particularly limited, but a temperature of, for example, 0° C. to 100° C., 0° C. to 90° C., 0° C. to 80° C., 0° C. to 70° C., 0° C. to 60° C., or 0° C. to 50° C. may be selected. The carbonyl compound that is an impurity contained in the nitrile solvent is converted into corresponding α-hydroxysulfonic acid compound by the contact treatment with an aqueous sodium hydrogen sulfite solution. The α-hydroxysulfonic acid compound is more soluble in the aqueous sodium hydrogen sulfite solution phase than in the nitrile solvent phase. Therefore, the α-hydroxysulfonic acid compound (i.e., carbonyl compound) can be removed from the nitrile solvent by separating the aqueous sodium hydrogen sulfite solution phase from the nitrile solvent phase. Thus, an imine being an impurity can be removed. Instead of the contact treatment B, known treatment for removing a carbonyl compound, such as aldehyde, from a nitrile compound may be performed. For example, a treatment method including removal of aldehyde or the like being impurities in nitrile with an ion exchange resin (see, for example, Japanese unexamined Patent Application Publication Nos. 2000-16978, 58-134063, 10-7638, and 54-151915 and International Publication No. WO 2006/121081 A) or a treatment method including addition of acetylacetone and dimethylaminoethanol to acrylonitrile, heating at 50° C., subsequent addition of an aqueous ferric chloride solution, subsequent cooling to ordinary temperature, and rectification (see, for example, Japanese unexamined Patent Application Publication No. 52-68118) may be exemplified. (Contact Treatment C) As the alkaline aqueous solution that is used in the contact treatment C, an aqueous alkali metal hydroxide solution, such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, an aqueous alkaline-earth metal hydroxide solution, such as an aqueous calcium hydroxide solution or an aqueous strontium hydroxide solution, aqueous ammonia, an aqueous methylamine solution, or the like may be exemplified. Among these alkaline aqueous solutions, an aqueous sodium hydroxide solution is preferable. The concentration of the alkaline aqueous solution is not particularly limited, but a concentration of, for example, 1 wt % to solubility, wt % to solubility, 10 wt % to solubility, 15 wt % to solubility, 20 wt % to solubility, 25 wt % to solubility, 30 wt % to solubility, or 30 wt % to 35 wt % may be selected. Incidentally, the solubility of sodium hydroxide in water at 20° C. is about 109 g/100 mL, and the solubility of potassium hydroxide in water at 25° C. is about 110 g/100 mL. The amount of the alkaline aqueous solution to be brought into contact is not particularly limited, but an amount of, for example, 1 to 500 wt %, 1 to 400 wt %, 1 to 300 wt %, 1 to 200 wt %, or 1 to 100 wt % with respect to the total weight of the nitrile solvent may be selected. The method for bringing a nitrile solvent into contact with an alkaline aqueous solution is not particularly limited. For example, a method in which a nitrile solvent and an alkaline aqueous solution are placed in a batch extractor and stirred or a method in which a nitrile solvent and an alkaline aqueous solution are brought into counterflow contact with each other in a continuous extractor may be exemplified. The temperature when a nitrile solvent and an alkaline aqueous solution are brought into contact with each other is not particularly limited, but a temperature of, for example, 0° C. to 100° C., 0° C. to 90° C., 0° C. to 80° C., 0° C. to 70° C., 0° C. to 60° C., or 0° C. to 50° C. may be selected. The contact with an alkaline aqueous solution neutralizes the acidic material that is an impurity contained in the nitrile solvent and the acidic materials added in the contact treatment A and B to convert them into corresponding salts. The salts are more soluble in the alkaline aqueous solution phase than in the nitrile solvent phase. Therefore, the salts (i.e., acidic materials) can be removed from the nitrile solvent by separating the alkaline aqueous solution phase from the nitrile solvent phase. (Contact Treatment D) As the oxidizing agent that is used in the contact treatment D, for example, an aqueous sodium hypochlorite solution (antiformin), hydrogen peroxide, oxygen, air, or ozone may be exemplified. Among these oxidizing agents, oxygen and air are preferable because of ease of handling. The contact treatment D may be subjected to a nitrile solvent containing impurities before being subjected to the contact treatment A, a nitrile solvent having been contacted with an acidic aqueous solution and before being subjected to the contact treatment B, a nitrile solvent having been contacted with an aqueous sodium hydrogen sulfite solution and before being subjected to the contact treatment C, or a nitrile solvent having been contacted with an alkaline aqueous solution by being subjected to the contact treatment C. The method for bringing a nitrile solvent into contact with an oxidizing agent is not particularly limited. For example, a method in which a gaseous oxidizing agent, such as oxygen, air, or ozone, is bubbled through a nitrile solvent, a method in which a gaseous oxidizing agent and a nitrile solvent are brought into counterflow contact with each other in a gas absorption column, a method in which a liquid oxidizing agent, such as an aqueous sodium hypochlorite solution (antiformin) or hydrogen peroxide, is added to a nitrile solvent and the mixture is stirred, or a method in which a nitrile solvent is added to a liquid oxidizing agent and the mixture is stirred may be exemplified. A conjugated diene or the like being an impurity contained in a nitrile solvent is oxidized by bringing the nitrile solvent into contact with an oxidizing agent. From the viewpoint of accelerating the oxidation of the conjugated diene, it is preferable to perform the contact treatment D using a gaseous oxidizing agent in the presence of an aqueous sodium hydrogen sulfite solution. The product obtained by oxidation of a conjugated diene can be removed from the nitrile solvent by the contact treatment with an acidic aqueous solution, the contact treatment with an aqueous sodium hydrogen sulfite solution, or the contact treatment with an alkaline aqueous solution, or the distillation treatment described below. (Distillation Treatment) The distillation treatment is preferably performed after the contact treatment C or the contact treatment D. The distillation treatment may be performed by a known method. In the distillation treatment, the nitrile solvent is evaporated, and high-boiling materials, such as N-isobutylformamide, can be separated as a residue. EXAMPLES Subsequently, the present invention will be more specifically described by showing an Example, but the technical scope of the present invention is not limited to the example. Example 1 Crude isobutyronitrile containing, as impurities, 2454 ppm of N-isobutyl-2-methylpropane-1-imine, 37 ppm of isobutyl aldehyde, 8 ppm of 2,5-dimethylhexa-2,4-diene, and 220 ppm of N-isobutylformamide was prepared. To a 5-L four-necked flask, 2567 mL of the crude isobutyronitrile and 513 mL of water were added. The pH of the aqueous phase thereof was adjusted to 1.9 with 35% hydrochloric acid. Then, the mixture was stirred at 23° C. for 0.5 hours. The liquid was then left to stand for separating into an isobutyronitrile phase and an aqueous phase, and the aqueous phase was removed (contact treatment A). To the isobutyronitrile phase prepared by the contact treatment A, 488 mL of water and 57.24 g of a 35 wt % aqueous sodium hydrogen sulfite solution were added, followed by stirring at 24° C. for 1 hour. Subsequently, the liquid was left to stand for separating into an isobutyronitrile phase and an aqueous phase, and the aqueous phase was removed (contact treatment B). To the isobutyronitrile phase prepared by the contact treatment B, 488 mL of water, 34.34 g of a 35% aqueous sodium hydrogen sulfite solution, and 11.36 g of 35% hydrochloric acid were added. The mixture was heated up to 60° C. while blowing air into the gas phase at 10 mL/min and was left to stand at the same temperature for 1.5 hours. Then, cooling down to 24° C. and leaving to stand were performed for separating into an isobutyronitrile phase and an aqueous phase, and the aqueous phase was removed (contact treatment D). To the isobutyronitrile phase prepared by the contact treatment D, 257 mL of water and a 25 wt % aqueous sodium hydroxide solution were added to adjust the pH to 11.1, followed by stirring at 24° C. for 0.5 hours. The liquid was left to stand for separating into an isobutyronitrile phase and an aqueous phase, and the aqueous phase was removed (contact treatment C). To the isobutyronitrile phase prepared by the contact treatment C, 257 mL of water was added, followed by stirring at 24° C. for 0.5 hours. Subsequently, the liquid was left to stand for separating into an isobutyronitrile phase and an aqueous phase, and the aqueous phase was removed (water washing treatment). The isobutyronitrile phase prepared by the water washing treatment was heat-refluxed for Dean-Stark dehydration. Subsequently, distillation was performed at the boiling point of isobutyronitrile (internal temperature: 108° C. or less) (distillation treatment). The impurities contained in the isobutyronitrile phase prepared by the distillation treatment were less than 2 ppm of N-isobutyl-2-methylpropane-1-imine, less than 2 ppm of isobutyl aldehyde, less than 2 ppm of 2,5-dimethylhexa-2,4-diene, and less than 2 ppm of N-isobutylformamide. | 15,708 |
11858882 | DETAILED DESCRIPTION OF THE INVENTION When describing the invention, the terms used are to be construed in accordance with the following definitions, unless a context dictates otherwise. Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention, and form different embodiments, as would be understood by those in the art. As used in the specification and the appended claims, the singular forms “a”, “an,” and “the” include plural referents unless the context clearly dictates otherwise. By way of example, “a flow” means one flow or more than one flow. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art. All publications referenced herein are incorporated by reference thereto. Throughout this application, the term “about” is used to indicate that a value includes the standard deviation of error for the device or method being employed to determine the value. The recitation of numerical ranges by endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g. 1 to 5 can include 1, 2, 3, 4 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when referring to, for example, measurements). The recitation of end points also includes the end point values themselves (e.g. from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein. The present inventors have now surprisingly found that one or more of these objects can be obtained by diluting a urea solution obtained from the urea reaction process, with at least some amount of partially purified water, generated in the downstream purification process of the urea reaction process. More in particular, it has been found that using at least part of the first partially purified flow that leaves the first desorption column to dilute the first aqueous urea solution and/or the concentrated second aqueous urea solution obtained after the separation of the crude urea mixture provides in a more efficient urea production process, particularly a more energy efficient urea production process. In a first aspect, the invention provides a method for providing a target aqueous urea composition with a target concentration urea, comprising the steps of:a) reacting CO2and NH3in a synthesis section to form a crude urea mixture;b) separating the crude urea mixture in an first aqueous urea solution and a process condensate using a separating section;c) passing the process condensate through a first desorption column to provide a first partially purified flow;d) passing at least part of the first partially purified flow through a hydrolyser to provide a second partially purified flow;e) passing the second partially purified flow through a second desorption column to provide a purified water flow;f) optionally concentrating the first aqueous urea solution in a pre-evaporator to provide a concentrated second aqueous urea solution;g) mixing the first aqueous urea solution and/or the concentrated second aqueous urea solution with at least part of the first partially purified flow and at least part of the purified water flow in such a ratio to provide a target aqueous urea composition with the target concentration urea. Such a method is especially advantageous when a liquid urea solution is desired instead of a dried or prilled form of urea. By “a target aqueous urea composition with a target urea concentration” may be meant a urea solution with a predetermined urea concentration, which concentration may be specific for a certain usage. A typical example of such a solution is known as AdBlue® or Diesel Exhaust Fluid (DEF) which is added in diesel exhausts. AdBlue® or Diesel Exhaust Fluid (DEF) is an aqueous urea solution comprising between 30.0% by weight and 35.0% by weight urea and between 65.0% by weight and 70.0% by weight clean water, in particular 32.5% by weight urea and 67.5% by weight clean water. Alternatively, such solutions may comprise between 50.0% by weight and 52.0% by weight. The method removes at least a part of unreacted starting materials, or contaminants such as CO2and NH3from the urea composition. Because at least some first partially purified flow is used in step g) to make the target aqueous urea composition, the fraction of first partially purified flow used does not need to pass through the hydrolyser thereby lowering the amounts of energy required that need to be added to the hydrolyser, e. g, in the form of medium pressure steam. Furthermore, the fraction of first partially purified flow is not converted into second partially purified flow, hence less second partially purified flow needs to go through the second desorption column thereby lowering the amounts of energy required for the second desorption column e. g, in the form of low pressure steam. Hence, the more first partially purified flow used in step g) the larger the energy saving. The method further reduces the flow through the hydrolyser and the second desorption column thereby creating unused capacity, allowing more flexibility in the urea production process. This may also result in a higher amount of urea produced in a certain production plant, as a possible bottleneck formed by the hydrolyser and second desorption column is at least partially relieved. The term “crude urea mixture” as used herein, refers to a urea mixture that is obtained after the urea formation reaction and/or carbamate decomposition reaction. It is a solution of urea ((NH2)2CO) in water and it may comprises contaminants such as carbon dioxide (CO2), ammonia (NH3), biuret (H2N—C═O—NH—(C═O)—NH2) and optionally ammonium carbamate (H4N′O—(C═O)—NH2), here also referred to as “carbamate”. In some cases, the crude urea mixture has not yet undergone a purification step. In particular embodiments, the crude urea mixture comprises at least 10.0% by weight urea, in particular at least 15.0% by weight urea, more in particular at least 20.0% by weight urea, even more particular at least 24.0% by weight urea, compared to the total weight of the crude urea mixture. In particular embodiments, the crude urea mixture comprises at most 55.0% by weight urea, in particular at most 40.0% by weight urea, more in particular at most 35.0% by weight urea, even more particular at most 32.0% by weight urea, compared to the total weight of the crude urea mixture. In particular embodiments, the crude urea mixture comprises at least 10.0% by weight to at most 55.0% by weight urea, in particular at least 15.0% by weight to at most 40.0% by weight urea, more in particular at least 20.0% by weight to at most 35.0% by weight urea, even more particular at least 24.0% by weight to at most 32.0% by weight urea, compared to the total weight of the crude urea mixture. In some embodiments, the crude urea mixture may comprise at least 5.0% by weight urea, in particular at least 7.5% by weight urea, more in particular at least 10.0% by weight urea, compared to the total weight of the crude urea mixture. In some embodiments, the crude urea mixture may comprise at least 5.0% by weight CO2, in particular at least 7.5% by weight CO2, more in particular at least 10.0% by weight CO2, compared to the total weight of the crude urea mixture. The term “process condensate” as used herein, refers to an aqueous solution that comprises higher amounts of urea then the crude urea mixture. In particular embodiments, the comprises at least 50.0% by weight urea, in particular at least 55.0% by weight urea, more in particular at least 60.0% by weight urea, even more particular at least 65.0% by weight urea, compared to the total weight of the crude urea mixture. In particular, the process condensate comprises less urea than the crude urea mixture. In particular, the process condensate comprises less than 5.0% by weight urea, in particular less than 4.0% by weight urea, more particular less than 3.0% by weight urea, even more particular less than 2.0% by weight urea, yet even more particular less than 1.0% by weight urea, the % by weight being expressed compared to the total weight of the process condensate. In some embodiments, the process condensate may comprise higher concentrations CO2than the first aqueous urea solution, particular at least 5 times higher, more particular at least 7 times higher, even more particular at least 10 times higher, yet more particular at least 15 times higher, still more particular at least 20 times higher. The process condensate may comprise at least 1.0% by weight CO2, in particular at least 2.0% by weight CO2, more particular at least 4.0% by weight CO2, even more particular at least 6.0% by weight CO2, yet even more particular at least 8.0% by weight CO2, the % by weight being expressed compared to the total weight of the process condensate. In some embodiments, the process condensate may comprise higher concentrations NH3than the first aqueous urea solution, particular at least 2 times higher, more particular at least 4 times higher, even more particular at least 6 times higher, yet more particular at least 7 times higher, still more particular at least 8 times higher. The process condensate may comprise at least 2.0% by weight NH3, in particular at least 4.0% by weight NH3, more particular at least 5.0% by weight NH3, even more particular at least 6.0% by weight NH3, yet even more particular at least 8.0% by weight NH3, the % by weight being expressed compared to the total weight of the process condensate. The term “desorption column” as used herein, refers to a column for removing at least part of the CO2in an aqueous composition such as the process condensate and/or the second partially purified flow. In some embodiments, steam is added to the desorption column, in particular low pressure (LP) steam, typically steam at least 3.0 barg to at most 10.0 barg, in particular at least 4.0 barg to at most 8.0 barg, more in particular at least 5.0 barg to at most 6.5 barg, typically at saturation temperature, like 160-170° C. In some embodiments, the desorption column(s) consume about 7 to 14 t/h LP steam. In particular, the steam and aqueous composition are contacted in the desorption column in counter current. In particular, the pressure in the desorption column is at least 1.0 barg, to at most 5.0 barg, in particular at least 1.5 barg, to at most 4.0 barg, more in particular at least 2.0 barg, to at most 3.0 barg. In some embodiments, the temperature in the bottom liquid outlet is about 146° C. while the temperature of the vapours in the top outlet is about 116° C. The term “first partially purified flow” as used herein, refers to an aqueous flow derived from the process condensate, typically comprising lower amounts of NH3and/or lower amounts of CO2as compared to the process condensate. In particular, the amount of NH3in the first partially purified flow is reduced at least 5 times as compared to the process condensate, more in particular at least 7 times, even more in particular at least 10 times, yet even more in particular at least 13 times and still more in particular at least 15 times. Typically, the first partially purified flow comprises at most 2.0% by weight NH3, in particular at most 1.5% by weight NH3, more particular at most 1.0% by weight NH3, even more particular at most 0.7% by weight NH3, yet even more particular at most 0.5% by weight NH3, the % by weight being expressed compared to the total weight of the first partially purified flow. In particular, the amount of CO2is reduced in the first partially purified flow at least 10 times as compared to the process condensate, more in particular at least 30 times, even more in particular at least 50 times, yet even more in particular at least 75 times and still more in particular at least 90 times. Typically, the first partially purified flow comprises at most 1.0% by weight CO2, in particular at most 0.5% by weight CO2, more particular at most 0.2% by weight NH3, even more particular at most 0.1% by weight CO2, yet even more particular at most 0.5% by weight CO2, the % by weight being expressed compared to the total weight of the first partially purified flow. The term “second partially purified flow” as used herein, refers to an aqueous flow derived from the first partially purified flow, typically comprising lower amounts of NH3and/or lower amounts of CO2as compared to the first partially purified flow. In particular, the amount of NH3in the second partially purified flow is reduced at least 1.1 times as compared to the first partially purified flow, more in particular at least 1.2 times and even more in particular at least 1.3 times. Typically, the second partially purified flow comprises at most 1.0% by weight NH3, in particular at most 0.8% by weight NH3, more particular at most 0.6% by weight NH3, even more particular at most 0.5% by weight NH3, yet even more particular at most 0.4% by weight NH3, the % by weight being expressed compared to the total weight of the second partially purified flow. The term “purified water flow” as used herein, refers to an aqueous flow derived from the second partially purified flow, typically comprising lower amounts of NH3and/or lower amounts of CO2as compared to the second partially purified flow. In particular, the purified water flow comprises 0.0% by weight CO2and 0.0% by weight NH3; the % by weight being expressed compared to the total weight of the purified water flow. The term “hydrolyser” as used herein, refers to a device wherein urea present in an aqueous flow is hydrolysed, i.e. converted into NH3and CO2. In some embodiments, steam, in particular medium pressure (MP) steam is added to the hydrolyser, typically steam at least 10.0 barg to at most 27.0 barg, in particular at least 15.0 barg to at most 25.0 barg, more in particular at least 18.0 barg to at most 21 barg, typically at saturation temperature, like 210-217° C. In particular, the steam and aqueous flow are contacted in the hydrolyser in counter current. In particular embodiments, the hydrolyser consumes 2.5 to 3.5 t/h of MP steam. In particular embodiments, at least part of the first partially flow is provided to the hydrolyser in the top region of the hydrolyser. In particular embodiments, medium pressures steam is provided in the bottom region of the hydrolyser. In some embodiments, the first aqueous urea solution is concentrated in a pre-evaporator to provide a concentrated second aqueous urea solution. In some embodiments, the pre evaporator is an evaporate, however, the prefix “pre-” may refer to the place of the evaporator, which is comparable to the place of a pre-evaporator in layouts for producing dried forms of urea. In some embodiments, the first aqueous urea solution may comprise at least 40.0% by weight urea, in particular at least 45.0% by weight urea, more particular at least 55.0% by weight urea, even more particular at least 60.0% by weight urea, yet even more particular at least 65.0% by weight urea, the % by weight being expressed compared to the total weight of the first aqueous urea solution. The term “concentrated second aqueous urea solution” as used herein, refers to an aqueous urea composition with a higher concentration of urea than the first aqueous urea solution. In particular is the concentration of urea in the concentrated second aqueous urea solution at least 1.05 times, more in particular at least 1.10 times, even more in particular at least 1.15 times yet more in particular at least 1.17 times the concentration of urea in the second partially purified flow. In some embodiments, the concentrated second aqueous urea solution may comprise at least 60.0% by weight urea, in particular at least 65.0% by weight urea, more particular at least 70.0% by weight urea, even more particular at least 75.0% by weight urea, yet even more particular at least 80.0% by weight urea, the % by weight being expressed compared to the total weight of the concentrated second aqueous urea solution. In some embodiments, the concentration NH3in the concentrated second aqueous urea solution is at least 5 times less, more in particular at least 7 times less, even more in particular at least 10 times less, yet even more in particular at least 13 times less and still more in particular at least 15 times less than the concentration NH3in the first aqueous urea solution. Typically, the concentrated second aqueous urea solution comprises at most 0.20% by weight NH3, in particular at most 0.17% by weight NH3, more particular at most 0.15% by weight NH3, even more particular at most 0.13% by weight NH3, yet even more particular at most 0.10% by weight NH3, the % by weight being expressed compared to the total weight of the concentrated second aqueous urea solution. In some embodiments, the target aqueous urea composition has at least an upper limit for a first contaminant, the first contaminant being comprised in the first partially purified flow; and, wherein in step g) the amount of first partially purified flow used is such that in the target aqueous urea composition at least 10% to at most 100% of the limit for the first contaminant is reached. In some, embodiments the first contaminant may also be comprised in the first aqueous urea solution and/or the concentrated second aqueous urea solution. In some embodiments, the limit of the first contaminant is expressed as % by weight compared to the total weight of the target aqueous urea composition. In some embodiments, the first contaminant is ammonia (NH3). In some embodiments, the upper limit for the first contaminant is 0.20% by weight, compared to the total weight of the target aqueous urea composition. Such an upper limit results in that the urea composition may be used in selective catalytic reduction (SRC) in exhaust gasses, like diesel exhaust gasses. In some embodiments, the method further comprises the step of determining the concentration of the first contaminant in the first partially purified flow and using the concentration in determining the ratio in step g). The determined concentration of the first contaminant may be used to optimise the amount of first partially purified flow that is used to form the target aqueous urea composition and to minimise the amount of purified water flow. The more first partially purified flow the more energy is saved as less medium pressure steam needs to be added to the hydrolyser and the less low pressure steam needs to be added to the second desorption column. This may also speed up the urea production process as the reaction in the hydrolyser is typical a bottleneck. In some embodiments, the concentration of the first contaminant is derived from measuring the pH, the conductivity and/or a first contaminant specific measurement method. In some embodiment, the concentration of the first contaminant as determined by a measuring device suitable for such concentration determination, is used to control the flow of the first partially purified flow in step g), in particular by controlling a valve downstream from the tapping point. In some embodiments, a measuring devise such as an ion specific electrode may be used. In some embodiments, the method further comprises the step of determining the urea concentration and/or the first contaminant in the first partially purified flow and using the concentration in determining the ratio in step g). Such determination of the relevant concentrations may allow a method that can change the ratios in step g) based on fluctuations in the first partially purified flow. In some embodiments, the method further comprises the step of determining the concentration of urea in the first aqueous urea solution and/or the second aqueous urea solution and using the concentration in determining the ratio in step g). In some embodiments, the method comprises the step of determining the concentration of the first contaminant in the first aqueous urea solution and/or the second aqueous urea solution and using the concentration in determining the ratio in step g). Such determination of the relevant concentrations may allow a method that can change the ratios in step g) based on fluctuations in the first aqueous urea solution and/or the second aqueous urea solution. In some embodiments, the method comprises the step of premixing at least part of the first partially purified flow with at least part of the purified water flow to obtain a premix, before the premix is mixed with the first aqueous urea solution and/or the second concentrated aqueous urea solution. In some embodiments, the urea concentration is determined in the premix before it is mixed with the first aqueous urea solution and/or the second concentrated aqueous urea solution, the urea concentration being used to determine the ratio in step g). This might be an alternative to determining the concentration of the first contaminant in the first partially purified flow. In some embodiments, the concentration of the first contaminant is determined in the premix before the premix is mixed with the first aqueous urea solution and/or the second concentrated aqueous urea solution, the concentration of the first contaminant being used to determine the ratio in step g). In some embodiments, the method comprises the step of determining the urea concentration and/or the first contaminant in the target aqueous urea composition after step g) and using this information to adjust the ratio is step g). In some embodiment, the method step is performed at least weekly, in particular at least daily. In some embodiments, it can be assumed that the concentration of the first contaminant in the first partially purified flow is stable for at least one day, in particular at least three days, in particular at least one week, in particular at least one month, in particular at least one year, in particular forever. In some embodiments, it can be assumed that the concentration of the first contaminant in the first aqueous urea solution and/or the second concentrated aqueous urea solution is stable for at least one day, in particular at least three days, in particular at least one week, in particular at least one month, in particular at least one year, in particular forever. In some embodiments, the first desorption column is placed on top of the second desorption column. In some embodiments, gasses leaving the second desorption column are fed into the first desorption column. In some embodiments, the first desorption column and the second desorption column and share the same low pressure steam inlet, in particular a steam inlet placed in the second desorption column. In some embodiments, the first desorption column and the second desorption column are two sections in a single desorption column divided from each other in a way that vapours can travel from the first desorption column to the second desorption column, in particular, no liquids travel directly form the second desorption column to the first desorption column, but pass though the hydrolyser first. In some embodiments, step b) is performed in a condenser and/or flash vessel. In particular, producing a first aqueous urea solution comprising about 65.0 to 70.0% by weight urea, compared to the total weight of the first aqueous urea solution. In some embodiments, the synthesis section may comprise an urea reactor, a carbamate condenser, a NH3-stripper, a CO2-stripper and/or a carbamate decomposer. In some embodiments, the synthesis section may form a reaction loop, wherein gaseous reagents may circulate. In some embodiments, the ratio of the first partially purified flow over the purified water flow in step g) is at least 0.5, in particular at least 0.7, in particular at least 1.0, in particular at least 1.2, in particular at least 1.3, in particular at least 1.4; the ratio being expressed as weight over weight. In some embodiments, the ratio of the first partially purified flow over the purified water flow in step g) is at least 0.5 to at most 5.5, in particular at least 0.7 to at most 5.0, in particular at least 1.0 to at most 4.0, in particular at least 1.2 to at most 3.0, in particular at least 1.3 to at most 2.5, in particular at least 1.4 to at most 2.0; the ratio being expressed as weight over weight. In some embodiments, the ratio of first aqueous urea solution or the second urea solution over the sum of the first partially purified flow and the purified water flow, in step g) is at least 1.0, in particular at least 1.2, in particular at least 1.3, in particular at least 1.4, in particular at least 1.5, in particular at least 1.6, the ratio being expressed as weight over weight. In some embodiments, the ratio of first aqueous urea solution or the second urea solution over the first partially purified flow the purified water flow in step g) is at least 1.0 to at most 5.5, in particular at least 1.2 to at most 5.0, in particular at least 1.3 to at most 4.0, in particular at least 1.4 to at most 3.5, in particular at least 1.5 to at most 3.0, in particular at least 1.6 to at most 2.6, the ratio being expressed as weight over weight. The invention further foresees in a process condensate treatment plant comprising:a first desorption column, comprising an inlet for the process condensate and an outlet for a first partially purified flow;a hydrolyser comprising an inlet for the first partially purified flow and an outlet for a second partially purified flow;a second desorption column, comprising an inlet for the second partially purified flow and an outlet for a purified water flow. In particular, the invention further foresees a process condensate treatment plant wherein the process condensate treatment plant comprises a tapping point for bypassing at least partially the first partially purified flow from the hydrolyser and the second desorption column. In some embodiments, the tapping point is provided between the outlet from the first desorption column for the first partially purified flow and the inlet to the hydrolyser for the first partially purified flow. In some embodiments, the process condensate treatment plant further comprises a mixing device for mixing a urea solution with the bypassed first partially purified flow and purified water flow. In some embodiments, the process condensate treatment plant comprises a bypass for the hydrolyser, in particular a bypass for sending at least a portion of the first partially purified flow to the second partially purified flow. Further does the invention provide in a urea production plant comprising the process condensate treatment plant according to an embodiment of the invention. The invention will be more readily understood by reference to the following examples, which are included merely for purpose of illustration of certain aspects and embodiments of the present invention and are not intended to limit the invention. EXAMPLES Example 1 FIG.1provides a schematic overview of a lay-out that can be used to implement an embodiment of the invention. InFIG.1, CO21and NH32are provided to a synthesis section3, reaction conditions are applied for the formation of a crude urea mixture4. The crude urea mixture4is split in a condenser, belonging to the separating section23, into a process condensate6and a first aqueous urea solution5, for a typical composition see Table 1. Gaseous effluent20in the separating section23may be fed back to synthesis section3for further reaction. The first aqueous urea solution5may be further concentrated in a pre-evaporator15to yield a concentrated second aqueous urea solution14, for a typical composition see Table 1. The process condensate6is fed into the top of a first desorption column7, which is placed on top of second desorption column8, in a way that the gaseous effluent form the second desorption column8is fed into the bottom of the first desorption column7, but that no liquid can directly travel from the first desorption column7to the second desorption column8. Low pressure steam18is fed into the bottom of the second desorption column8. A first partially purified flow9,13leaves the bottom of the first desorption column7. A large part of the CO2and the NH3present in the process condensate6are removed in the first desorption column7, as indicated in Table 1, and leaves as a gaseous effluent21via the top of the first desorption column7which may be fed back to the synthesis section3or separating section23. The first partially purified flow9,13is then split in the tapping point24. A first part of the first partially purified flow9is fed into the hydrolyser10. The second part of the first partially purified flow13is used to dilute the second concentrated aqueous urea solution14. In the hydrolyser10, medium pressure steam19is supplied at the bottom to decompose the urea in first partially purified flow9into CO2and NH3. A second partially purified flow11leaves the hydrolyser at the bottom and is fed in the top of a second desorption column8. In the second desorption column8, the remaining NH3and CO2are removed, as indicated in Table 1, and a purified water flow12leaves the second desorption column8at the bottom. In mixer16, the purified water flow12, the second part of the first partially purified flow13and the concentrated second aqueous urea solution14are mixed in a ratio as illustrated in Example 1 in Table 1. TABLE 1flow compositionExample 2Flow56 (6a + 6b)111213(or 9)1417Composition61.7 wt % flow 14+22.3 wt % flow 13+16.0 wt % flow 12P, barg1.22.718.74.22.70.40.0T, ° C.105.783.4210.0145.6140.394.520.00wt % Urea69.200.30.000.000.2080.9750.00wt % Biuret0.300.00.000.000.000.330.20wt % CO20.409.90.000.000.130.030.05wt % NH31.109.80.400.000.550.110.19wt % H2O29.0080.099.59100.0099.1318.6049.56 Example 3 FIG.2depicts a practical implementation of and embodiment of a process condensate treatment plant according to the invention. Process condensate6band recovered process condensate6aare provided at the top of a first desorption column7. The first desorption column7is placed on top of a second desorption column8, in a way that the gaseous effluent from the second desorption column8is fed into the bottom of the first desorption column7. Low pressure steam18is fed into the bottom of the second desorption column8, but that no liquid can directly travel from the first desorption column7to the second desorption column8. A first partially purified flow9,13leaves the bottom of the first desorption column7. A large part of the CO2and the NH3present in the process condensate6are removed in the first desorption column7, as indicated in Table 1, and leaves as a gaseous effluent21via the top of the first desorption column7. The gaseous effluent21is fed into a condenser (not shown) to recover process condensate6a. The first partially purified flow9,13is then split in the tapping point24. A first part of the first partially purified flow9is fed into the hydrolyser10. The second part of the first partially purified flow13is used to dilute a second concentrated aqueous urea solution14, as indicated in Table 1, which may be obtained in an urea production process, in particular after a (pre-)evaporation step, like passing the urea solution through a heater with a separator placed on top. In the hydrolyser10, medium pressure steam19is supplied at the bottom to decomposed the urea in first partially purified flow9into CO2and NH3, as indicated in Table 1. A second partially purified flow11leaves the hydrolyser at the bottom and is fed in the top of a second desorption column8. The gaseous effluent25leaving the top of the hydrolyser10is fed into the bottom of the first desorption column7. In the second desorption column8, the remaining NH3and CO2are removed, see Table 1, and a purified water flow12leaves the second desorption column8at the bottom. The purified water flow12and the second part of the first partially purified flow13are cooled via heat exchangers30,31and33respectively, the heat exchangers30and33are being cooled by cool water26. The purified water flow12may be stored in a tank29, wherein a pump35may send it to the mixing device16to product the target aqueous urea composition17. It is to be understood that although particular embodiments and/or materials have been discussed for providing embodiments according to the present invention, various modifications or changes may be made without departing from the scope and spirit of this invention. Example 4 This example provides a relation between the different flows and the urea concentrations. Given that:purified water flow12=“A” (expressed in t/h)first partially purified flow13=“B” (expressed in t/h)flow of second concentrated aqueous urea solution14=“C” (expressed in t/h)flow of the target aqueous urea composition17=“D” (expressed in t/h)weight fraction of urea in second concentrated aqueous urea solution14is “X” (typically 80 wt %, thus a weight fraction of 0.80)weight fraction of urea in target aqueous urea solution17is “Y” (typically 50-52 wt %, thus 0.52)Ratio (Fraction of “A” in the total A+B) between “A” and “B” is “Z” (typically 0.40-0.60) Then: D=C/X*Y(or, of course:C=D/Y*X) A+B=(C*X/Y)*(1−Y)−C*(1−X) Further,A=(A+B)*Z Thereby,B=(A+B)*(1−Z) Example 5 Using the equations of Example 4, a typical example is given below: IfD=100t/h; Y=0.52; and, X=0.80 ThenC=100/0.52*0.80=65t/h AlsoA+B=(65*0.80/0.52)*(1−0.52)−65*(1−0.80)=35t/h And: A=35*0.4=14t/h B=35*(1−0.4)=21t/h Analysis Methods To analyse the composition of the different flows method may be used as listed in Standard Methods for the Examination of Water and Wastewater 20theditions, edited by Lenore S. Clesceri, Arnold E. Greenberg and Andrew D. Eaton. For the determination of the amount of urea in a flow, several options may be used, like for example the use of urease, i.e. enzymatic conversion to NH3and subsequent acidimetric titration; HPLC, i.e. standard chromatographic detection; colorimetric determination after reaction with pDAB; etc. For the determination of the amount of CO2in a flow, distillation into barite solution and titration may be used. For the determination of the amount of NH3in a flow, several options may be used, like the use of Nessler's reagent, Acidimetric titration, distillation into boric acid followed by titration, or Ion chromatography. Especially for continuous on-line measurement for example for process control, an ion specific electrode might be most suitable. As used in herein, the amount of NH3does also include the amount of NH4+dissolved in the flow. Similarly herein, the amount of CO2also includes the amount of H2CO3dissolved in the flow. | 35,561 |
11858883 | DETAILED DESCRIPTION OF THE EMBODIMENTS In order to illustrate the technical effects of the disclosure, the following examples are described. The following embodiments show the practice of the disclosure but are not intended to limit its scope. The raw materials used in the following embodiments are commercially available products unless otherwise specified, the methods used are conventional methods unless otherwise specified, and the material content refers to a mass-volume percentage unless otherwise specified. HPLC and LC-MS analysis shows the content of substances in the detection reaction. In order to provide a generally simple and efficient method for recycling a taurine mother liquor, the inventors have conducted a lot of relevant researches and experiments. After the inventor's experiments, it was found that under certain conditions, alkali metal taurate can be converted into alkali metal hydroxyethyl sulfonate. Under this inspiration, the inventors experimentally confirmed that the alkali metal hydroxyethyl sulfonate can be produced by repeatedly recycling the taurine mother liquor. Therefore, this discovery allows the taurine mother liquor to be further recycled. Based on the above experiments by the inventors, the present disclosure provides a method for producing an alkali metal hydroxyethyl sulfonate by using a taurine mother liquor, including: after converting the taurine mother liquor into the alkali metal hydroxyethyl sulfonate, the content of the alkali metal hydroxyethyl sulfonate is increased, while since the solubility of the alkali metal hydroxyethyl sulfonate is very high, the separation of impurities is realized by adsorptive decolorization at a reduced temperature, and then the alkali metal hydroxyethyl sulfonate is separated by concentration and crystallization to obtain a high content of alkali metal hydroxyethyl sulfonate. The separated alkali metal hydroxyethyl sulfonate can be used as a raw material of taurine. This embodiment realizes the recycling of the taurine mother liquor by converting the mother liquor into alkali metal hydroxyethyl sulfonate, thereby realizing recycling of taurine production. The inventors also found that the mother liquor after extraction of taurine contains a certain amount of taurine. Sodium hydroxyethyl sulfonate and ammonia can be obtained by adding a base into the mother liquor and reacting at a certain temperature for a certain time. Therefore, it is also possible to provide a method of converting the taurine mother liquor into an alkali metal hydroxyethyl sulfonate solution, and use the alkali metal hydroxyethyl sulfonate solution, in combination with the aforementioned method for producing the alkali metal hydroxyethyl sulfonate by using the taurine mother liquor, for achieving the purpose of efficiently producing alkali metal hydroxyethyl sulfonate by recycling of the taurine mother liquor, as shown inFIG.1, this embodiment further includes: step (1): a hydrolysis step, including: an appropriate liquid base is added to the taurine mother liquor, and the obtained mixture is heated to a certain temperature, and subjected to a reaction for a period of time, and the resulting ammonia is continuously discharged and absorbed. Then the solution is appropriately evaporated and concentrated to obtain a sodium hydroxyethyl sulfonate solution having a content of greater than 20%; the above reaction can be carried out under any pressure, generally under atmospheric pressure. After further experiments, the inventors found that the higher the temperature of the hydrolysis reaction within a certain range, the shorter the time required for the reaction and the higher the content of sodium hydroxyethyl sulfonate obtained, which indicates that the higher the temperature, the more conducive to the occurrence of hydrolysis. When the temperature exceeds a certain value, the content of sodium hydroxyethyl sulfonate will have a certain trend of decline, mainly because the temperature is too high, sodium hydroxyethyl sulfonate is unstable to be decomposed. While, if an appropriate alkali metal is added in the hydrolysis process, it will also be beneficial to hydrolysis. Therefore, the hydrolysis is carried out for a period of at least greater than 1 minute, generally 0.5 h-5 h; the hydrolysis is carried out at 20-350° C., preferably 140-280° C. The liquid base can be selected from an alkaline compound, such as alkali metal hydroxide, preferably sodium hydroxide. The amount of the added alkali metal can be preferably selected by a person skilled in the art. There is also a preferable solution, for example, if the alkali metal is added less, hydroxyethyl sulfonic acid will be present, which is unstable and easy to decompose, but the inventors found through the researches that it is preferred that a molar amount of the added alkali metal should be 0.2 times a molar amount of taurine or above. In addition to metal hydroxide, the compounds, such as an alkali metal carbonate compound and an alkali metal sulfite compound, can also be selected. Therefore, the amount of the liquid base is at least 0.2 times the equivalent amount (a molar ratio) of taurine, wherein preferably, a molar ratio of taurine to the liquid base is 1:0.5 to 1.5. The inventors also found that the continuous recycling of ammonia during the hydrolysis reaction facilitates the production of sodium hydroxyethyl sulfonate. According to the chemical equilibrium, the timely transfer of the resulting products is more favorable for the reaction to proceed toward the positive direction. Therefore, in addition to indirect ammonia discharge in the hydrolysis process, ammonia can also be recycled continuously in the reaction process. Step (2): a step of decolorization and removing impurities, including: a decolorizing agent is added into the sodium hydroxyethyl sulfonate solution having the content of greater than 20% for decolorization, and stirred and then filtering is carried out. The decolorizing agent can be ion exchange resin or activated carbon, etc. Further, the decolorization reaction may be performed at a temperature of 10-100° C., wherein the step of decolorization and removing impurities is preferably performed at a temperature of 35° C.-65° C. The stirring is carried out for a period of greater than 1 min, preferably 0.5-5 h. Step (3): a concentrating and crystallizing step, including: the decolorized sodium hydroxyethyl sulfonate solution is concentrated, crystallized, purified, and separated to obtain a solid alkali metal hydroxyethyl sulfonate as well as a mother liquor. As shown inFIG.2andFIG.3, the obtained solid hydroxyethyl sulfonate can be used as a raw material for cyclic production of taurine or as a raw material for other reactions. The mother liquor after concentrating and crystallizing can be crystallized and purified again for recycling, or can be directly returned to the step (1) as the taurine mother liquor for the hydrolysis reaction. Wherein, the concentrating and crystallizing is carried out at 20° C.-150° C., preferably from 50° C.-80° C. The concentrating and crystallizing can be carried out by intermittent or continuous concentration and crystallization such as single-effect, multi-effect, thermal vapor recompression (TVR), and mechanical vapor recompression (MVR). Separation can be carried out by solid-liquid separation equipment, such as centrifugation, and filtration. The inventors further found through research that the conversion of the taurine mother liquor into the alkali metal hydroxyethyl sulfonate solution can be cycled one or more times, that is, after the taurine mother liquor is hydrolyzed into a hydroxyethyl sulfonate solution by adding a base at a certain temperature and ammonia is released, the taurine mother liquor can be hydrolyzed into a hydroxyethyl sulfonate solution again or more times under the same conditions; or the mother liquor after concentrating and crystallizing to extract hydroxyethyl sulfonate is hydrolyzed again to be further converted to the hydroxyethyl sulfonate solution. Thus, in the above embodiment, the step (1) can be repeatedly performed for multiple times to form the hydroxyethyl sulfonate solution. The step (1) can also be combined with the step (2) and the step (3) to produce the alkali metal hydroxyethyl sulfonate, and the taurine mother liquor obtained in the step (3) can be recycled for multiple times. After extensive experiments by the inventors, it was found that a mixture of sodium hydroxyethyl sulfonate and ammonia obtained by the hydrolysis reaction of taurine with sodium hydroxide at 260° C. for 2 hours is a superior choice. Taurine can be subjected to a reverse reaction under a certain condition to produce sodium hydroxyethyl sulfonate and ammonia by hydrolysis. The mother liquor after extraction of taurine contains a certain amount of taurine, sodium hydroxyethyl sulfonate, hydroxyethyl sulfonic acid derivatives, taurine derivatives and so on. Subjecting the mother liquor to a reaction at 260° C. for 2 hours in the present of sodium hydroxide can also obtain sodium hydroxyethyl sulfonate and ammonia. The hydroxyethyl sulfonic acid derivatives and taurine derivatives are hydrolyzed to different degrees to hydroxyethyl sulfonate. Based on the above, this embodiment describes an example of a method for producing alkali metal hydroxyethyl sulfonate by using taurine mother liquor, in which sodium hydroxide is added in the hydrolysis step, as shown inFIGS.1to3, including: step (1): a hydrolysis step, including: an appropriate sodium hydroxide is added to the taurine mother liquor, and the obtained mixture is heated to a certain temperature, and subjected to a reaction for a period of time, and the resulting ammonia is continuously discharged and absorbed. Then the solution is appropriately evaporated and concentrated to obtain a sodium hydroxyethyl sulfonate solution having a content of greater than 20%. Wherein, the hydrolysis is performed at a temperature of 30-350° C. for 0.5 h-50 h, and the amount of sodium hydroxide is at least 0.2 times the equivalent amount of taurine, wherein preferably a molar ratio of taurine in the taurine mother liquor to sodium hydroxide is 1:0.5-1.5. Step (2): a step of decolorization and removing impurities, including: activated carbon is added into the sodium hydroxyethyl sulfonate solution having the content of greater than 20% for decolorization, with continuous stirring during decolorization, and filtering is carried out when the decolorization is completed. Further, the step of decolorization and removing impurities is performed at a temperature of 0-100° C. and the stirring is carried out for 0.5-5 h. Wherein, the step of decolorization and removing impurities is preferably performed at a temperature of 35° C.-65° C. Step (3): a concentration and crystallization step, including: the decolorized sodium hydroxyethyl sulfonate solution is concentrated and crystallized to obtain a solid sodium hydroxyethyl sulfonate, and a mother liquor. The mother liquor after concentration and crystallization can be purified by crystallization after impurity removal to achieve recycling, or can be returned to the step (1) to be hydrolyzed again. Wherein, the concentration and crystallization is carried out at 50° C.-80° C. Further, for other embodiments, the alkali metal hydroxyethyl sulfonate obtained after the hydrolysis of the mother liquor can be used to produce other products such as sodium cocoyl hydroxyethyl sulfonate, sodium lauroyl hydroxyethyl sulfonate, sodium cocoyl methyl taurate, sodium lauroyl methyl taurate, 2-(N-morpholino)ethanesulfonic acid, sodium 2-(N-morpholino)ethanesulfonate, 2-(N-morpholino)ethanesulfonic acid monohydrate, 4-hydroxyethyl piperazinyl ethanesulfonic acid, sodium 4-hydroxyethyl piperazinyl ethanesulfonate, piperazine-N,N′-bis(2-ethanesulfonic acid), dis odium piperazine-N,N′-bis(3-ethanesulfonate), hydroxyethyl sulfonic acid, sodium methyl taurate, methyl taurine, etc., thereby achieving the purpose of the recycling of the taurine mother liquor. As shown inFIG.4, this embodiment introduces the recycling of the taurine mother liquor by the method for producing the alkali metal hydroxyethyl sulfonate by using the taurine mother liquor in a process for production of taurine by an ethylene oxide method, specifically including: S1. reacting ethylene oxide with a bisulfite solution to obtain hydroxyethyl sulfonate; S2. mixing the hydroxyethyl sulfonate obtained in S1 with ammonia in the presence of alkali metal for an ammonolysis reaction; S3. evaporating to remove excess ammonia after the ammonolysis reaction; S4. converting the resulting taurate to taurine; S5. concentrating and crystallizing the obtained taurine solution, and separating crude taurine and a taurine mother liquor; S6. decolorizing, recrystallizing, and separating the crude taurine to obtain a refined taurine product, and drying to obtain a finished taurine product, and returning the refined taurine mother liquor after separating to decolorization or concentrating and crystallizing in S5 for recycling; S7. adding an appropriate base into the mother liquor after extraction of the crude taurine in S5, then heating and hydrolyzing, evaporating to remove ammonia to obtain a hydroxyethyl sulfonate solution; S8. decolorizing and removing impurities from the solution obtained in the step S7; S9. concentrating and crystallizing the solution obtained in the step S8; and S10. carrying out solid-liquid separation on the crystallization solution obtained in S9to obtain solid hydroxyethyl sulfonate, wherein the solid hydroxyethyl sulfonate can be returned to the step S2for recycling, and the mother liquor after solid-liquid separation can be returned to the step S7or S9for recycling. It can be seen that the method for producing the alkali metal hydroxyethyl sulfonate by using the taurine mother liquor of the present disclosure can be used mainly for the recycling of the taurine mother liquor again after concentrating and crystallizing the taurine solution and separating to obtain the crude taurine and the taurine mother liquor in the process of taurine production, which is completed by the above steps S7to S10. Of course, actual mother liquor obtaining is not limited to this, but can also be extended to other taurine production processes, as long as there is a production process in which a taurine mother liquor is produced. The technical effects of the present disclosure are demonstrated below by several different sets of experiments. 1. This embodiment shows an experiment of hydrolysis of taurine in the presence of sodium hydroxide at different temperatures: 62.5 g (0.50 mol) of taurine was added to a 3 L reaction kettle, and dissolved with 1000 ml of purified water, and then 24 g of sodium hydroxide was added. The resulting solution was heated to different temperatures in Table 1, and was subjected to heat preservation while stirring for 2 h. The ammonia gas released during the reaction was absorbed. TABLE 1Molar amount of sodium hydroxyethyl sulfonateafter reaction at different temperaturesTemperatureSodium hydroxyethyl(° C.)sulfonate (mol)1300.301800.352000.402400.462600.472800.46 2. This embodiment shows an experiment of hydrolysis of a taurine mother liquor at different temperatures in the presence of sodium hydroxide: 625 ml of taurine mother liquor which contained 10% of taurine and 15% of sodium hydroxyethyl sulfonate was added to a 3 L reaction kettle, and then dissolved with 1000 ml of purified water, and then 24 g of sodium hydroxide was added. The resulting solution was heated to different temperatures as shown in Table 2, and was subjected to heat preservation while stirring for 2 hours. The ammonia gas released during the reaction was absorbed. TABLE 2Molar amount of sodium hydroxyethyl sulfonateafter reaction at different temperaturesTemperatureSodium hydroxyethyl(° C.)sulfonate (mol)13011801.052001.152401.22601.252801.3 3. This embodiment shows an experiment of hydrolysis of a taurine mother liquor in different alkali metals: 625 ml of taurine mother liquor which contained 10% of taurine and 15% of sodium hydroxyethyl sulfonate was added to a 3 L reaction kettle, and then dissolved with 1000 ml of purified water, and then different alkali metals as shown in Table 3 were added. The resulting solutions were heated to 260° C., and were subjected to heat preservation while stirring for 2 hours. The ammonia gas released during the reaction was absorbed. TABLE 3Molar amount of sodium hydroxyethyl sulfonateafter reaction with different alkali metalsAdded amounts ofSodium hydroxyethylAlkali metalalkali metal (mol)sulfonate (mol)None00.91Sodium hydroxide0.11.11Sodium hydroxide0.251.2Sodium hydroxide0.51.3Sodium hydroxide0.61.4Sodium hydroxide0.751.4Sodium carbonate0.51.21Sodium sulfite0.51.19Potassium hydroxide0.51.22Potassium carbonate0.51.23Potassium sulfite0.51.2Lithium hydroxide0.51.23Lithium carbonate0.51.2 4. This embodiment shows an experiment of the purification and subsequent utilization of sodium hydroxyethyl sulfonate after hydrolysis of a taurine mother liquor: 1250 ml of taurine mother liquor which contained 10% of taurine and 15% of sodium hydroxyethyl sulfonate was added to a 3 L reaction kettle, and then dissolved with 1000 ml of purified water, and then 48 g of sodium hydroxide was added. The resulting solution was subjected to heat preservation while stirring at 260° C. for 2 hours, and the ammonia gas released during the reaction was absorbed. The solution after the reaction was decolorized for impurity removal and then concentrated and crystallized, and extracted once to obtain 235 g of sodium hydroxyethyl sulfonate solid which contains 4.5% of water, 95% of sodium ethyl sulfonate, less than 0.01% of ethylene glycol and less than 0.01% of sulfate ion. Then, the obtained solid was subsequently used to prepare sodium cocoyl hydroxyethyl sulfonate, sodium lauroyl hydroxyethyl sulfonate, sodium cocoyl methyl taurate, sodium lauroyl methyl taurate, 2-(N-morpholino)ethanesulfonic acid, sodium 2-(N-morpholino)ethanesulfonate, 2-(N-morpholine)ethanesulfonic acid monohydrate, 4-hydroxyethyl piperazinyl ethanesulfonic acid, sodium 4-hydroxyethyl piperazinyl ethanesulfonate, piperazine-N,N′-bis(2-ethanesulfonic acid), disodium piperazine-N,N′-bis(3-ethanesulfonate), hydroxyethyl sulfonic acid, sodium methyl taurate, methyl taurine and other products, and the corresponding qualified products can be obtained. Based on the long-term experimental summary of the inventors, the present disclosure provides the method for producing the alkali metal hydroxyethyl sulfonate solution by using the taurine mother liquor, which is capable of converting the taurine mother liquor into the alkali metal hydroxyethyl sulfonate by hydrolysis, thereby performing various flexible applications of the alkali metal hydroxyethyl sulfonate by a person skilled in the art, and realizing the recycling of the taurine mother liquor. In addition, the present disclosure further provides a method to realize the recycling of taurine production, in which the taurine mother liquor is converted into the alkali metal hydroxyethyl sulfonate, thereby increasing the content of the alkali metal hydroxyethyl sulfonate, while since the solubility of the alkali metal hydroxyethyl sulfonate is very large, the separation of impurities can be realized by adsorptive decolorization at a reduced temperature, and then the alkali metal hydroxyethyl sulfonate is separated by concentration and crystallization, which further realizes the separation of impurities, thereby obtaining a high content of alkali metal hydroxyethyl sulfonate. The separated alkali metal hydroxyethyl sulfonate can be used as a raw material of taurine. The recycling process for producing the alkali metal hydroxyethyl sulfonate provided by the present disclosure can be discontinuous, semi-continuous or continuous. In summary, the general method of recycling the taurine mother liquor provided by the present disclosure is an efficient and simple method of separating impurities, very easy to implement industrially, and can effectively recycle the taurine mother liquor. The above are only preferred embodiments of the present disclosure, and it should be noted that for a person of ordinary skill in the art, a number of improvements and variations can be made without departing from the technical principles of the present disclosure, and these improvements and variations should also be regarded as falling into the protection scope of the present disclosure. | 20,720 |
11858884 | DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS In some aspects, the present disclosure provides lipocationic dendrimers which may be used as carriers of nucleic acids. In some embodiments, the dendrimers contain one or more groups which undergoes degradation under physiological conditions. In some embodiments, the dendrimers are formulated into compositions comprising the dendrimers and one or more nucleic acids. These compositions may also further comprise one or more helper lipids such as cholesterol and/or a phospholipid. Finally, in some aspects, the present disclosure also provides methods of treating one or more diseases which may be treated with a nucleic acid therapeutic using the dendrimer compositions. A. CHEMICAL DEFINITIONS When used in the context of a chemical group: “hydrogen” means —H; “hydroxy” means —OH; “oxo” means ═O; “carbonyl” means —C(═O)—; “carboxy” means —C(═O)OH (also written as —COOH or —CO2H); “halo” means independently —F, —Cl, —Br or —I; “amino” means —NH2; “hydroxyamino” means —NHOH; “nitro” means —NO2; imino means ═NH; “cyano” means —CN; “isocyanate” means —N═C═O; “azido” means —N3; in a monovalent context “phosphate” means —OP(O)(OH)2or a deprotonated form thereof; in a divalent context “phosphate” means —OP(O)(OH)O— or a deprotonated form thereof, “mercapto” means —SH; and “thio” means ═S; “sulfonyl” means —S(O)2—; “hydroxysulfonyl” means —S(O)2OH; “sulfonamide” means —S(O)2NH2; and “sulfinyl” means —S(O)—. In the context of chemical formulas, the symbol “—” means a single bond, “═” means a double bond, and “≡” means triple bond. The symbol “” represents an optional bond, which if present is either single or double. The symbol “” represents a single bond or a double bond. Thus, for example, the formula includes And it is understood that no one such ring atom forms part of more than one double bond. Furthermore, it is noted that the covalent bond symbol “—”, when connecting one or two stereogenic atoms, does not indicate any preferred stereochemistry. Instead, it covers all stereoisomers as well as mixtures thereof. The symbol “”, when drawn perpendicularly across a bond (e.g. for methyl) indicates a point of attachment of the group. It is noted that the point of attachment is typically only identified in this manner for larger groups in order to assist the reader in unambiguously identifying a point of attachment. The symbol “” means a single bond where the group attached to the thick end of the wedge is “out of the page.” The symbol “” means a single bond where the group attached to the thick end of the wedge is “into the page”. The symbol “” means a single bond where the geometry around a double bond (e.g., either E or Z) is undefined. Both options, as well as combinations thereof are therefore intended. Any undefined valency on an atom of a structure shown in this application implicitly represents a hydrogen atom bonded to that atom. A bold dot on a carbon atom indicates that the hydrogen attached to that carbon is oriented out of the plane of the paper. When a group “R” is depicted as a “floating group” on a ring system, for example, in the formula: then R may replace any hydrogen atom attached to any of the ring atoms, including a depicted, implied, or expressly defined hydrogen, so long as a stable structure is formed. When a group “R” is depicted as a “floating group” on a fused ring system, as for example in the formula: then R may replace any hydrogen attached to any of the ring atoms of either of the fused rings unless specified otherwise. Replaceable hydrogens include depicted hydrogens (e.g., the hydrogen attached to the nitrogen in the formula above), implied hydrogens (e.g., a hydrogen of the formula above that is not shown but understood to be present), expressly defined hydrogens, and optional hydrogens whose presence depends on the identity of a ring atom (e.g., a hydrogen attached to group X, when X equals —CH—), so long as a stable structure is formed. In the example depicted, R may reside on either the 5-membered or the 6-membered ring of the fused ring system. In the formula above, the subscript letter “y” immediately following the group “R” enclosed in parentheses, represents a numeric variable. Unless specified otherwise, this variable can be 0, 1, 2, or any integer greater than 2, only limited by the maximum number of replaceable hydrogen atoms of the ring or ring system. For the chemical groups and compound classes, the number of carbon atoms in the group or class is as indicated as follows: “Cn” defines the exact number (n) of carbon atoms in the group/class. “C≤n” defines the maximum number (n) of carbon atoms that can be in the group/class, with the minimum number as small as possible for the group/class in question, e.g., it is understood that the minimum number of carbon atoms in the group “alkenyl(C≤8)” or the class “alkene(C≤8)” is two. Compare with “alkoxy(C≤10)”, which designates alkoxy groups having from 1 to 10 carbon atoms. “Cn-n′” defines both the minimum (n) and maximum number (n′) of carbon atoms in the group. Thus, “alkyl(C2-10)” designates those alkyl groups having from 2 to 10 carbon atoms. These carbon number indicators may precede or follow the chemical groups or class it modifies and it may or may not be enclosed in parenthesis, without signifying any change in meaning. Thus, the terms “C5 olefin”, “C5-olefin”, “olefin(C5)”, and “olefinC5” are all synonymous. The term “saturated” when used to modify a compound or chemical group means the compound or chemical group has no carbon-carbon double and no carbon-carbon triple bonds, except as noted below. When the term is used to modify an atom, it means that the atom is not part of any double or triple bond. In the case of substituted versions of saturated groups, one or more carbon oxygen double bond or a carbon nitrogen double bond may be present. And when such a bond is present, then carbon-carbon double bonds that may occur as part of keto-enol tautomerism or imine/enamine tautomerism are not precluded. When the term “saturated” is used to modify a solution of a substance, it means that no more of that substance can dissolve in that solution. The term “aliphatic” when used without the “substituted” modifier signifies that the compound or chemical group so modified is an acyclic or cyclic, but non-aromatic hydrocarbon compound or group. In aliphatic compounds/groups, the carbon atoms can be joined together in straight chains, branched chains, or non-aromatic rings (alicyclic). Aliphatic compounds/groups can be saturated, that is joined by single carbon-carbon bonds (alkanes/alkyl), or unsaturated, with one or more carbon-carbon double bonds (alkenes/alkenyl) or with one or more carbon-carbon triple bonds (alkynes/alkynyl). The term “aromatic” when used to modify a compound or a chemical group atom means the compound or chemical group contains a planar unsaturated ring of atoms that is stabilized by an interaction of the bonds forming the ring. The term “alkyl” when used without the “substituted” modifier refers to a monovalent saturated aliphatic group with a carbon atom as the point of attachment, a linear or branched acyclic structure, and no atoms other than carbon and hydrogen. The groups —CH3(Me), —CH2CH3(Et), —CH2CH2CH3(n-Pr or propyl), —CH(CH3)2(i-Pr,iPr or isopropyl), —CH2CH2CH2CH3(n-Bu), —CH(CH3)CH2CH3(sec-butyl), —CH2CH(CH3)2(isobutyl), —C(CH3)3(tert-butyl, t-butyl, t-Bu ortBu), and —CH2C(CH3)3(neo-pentyl) are non-limiting examples of alkyl groups. The term “alkanediyl” when used without the “substituted” modifier refers to a divalent saturated aliphatic group, with one or two saturated carbon atom(s) as the point(s) of attachment, a linear or branched acyclic structure, no carbon-carbon double or triple bonds, and no atoms other than carbon and hydrogen. The groups —CH2— (methylene), —CH2CH2—, —CH2C(CH3)2CH2—, and —CH2CH2CH2— are non-limiting examples of alkanediyl groups. An “alkane” refers to the class of compounds having the formula H—R, wherein R is alkyl as this term is defined above. When any of these terms is used with the “substituted” modifier one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —NHCH3, —NHCH2CH3, —N(CH3)2, —C(O)NH2, —C(O)NHCH3, —C(O)N(CH3)2, —OC(O)CH3, —NHC(O)CH3, —S(O)2OH, or —S(O)2NH2. The following groups are non-limiting examples of substituted alkyl groups: —CH2OH, —CH2Cl, —CF3, —CH2CN, —CH2C(O)OH, —CH2C(O)OCH3, —CH2C(O)NH2, —CH2C(O)CH3, —CH2OCH3, —CH2OC(O)CH3, —CH2NH2, —CH2N(CH3)2, and —CH2CH2Cl. The term “haloalkyl” is a subset of substituted alkyl, in which the hydrogen atom replacement is limited to halo (i.e. —F, —Cl, —Br, or —I) such that no other atoms aside from carbon, hydrogen and halogen are present. The group, —CH2Cl is a non-limiting example of a haloalkyl. The term “fluoroalkyl” is a subset of substituted alkyl, in which the hydrogen atom replacement is limited to fluoro such that no other atoms aside from carbon, hydrogen and fluorine are present. The groups —CH2F, —CF3, and —CH2CF3are non-limiting examples of fluoroalkyl groups. The term “cycloalkyl” when used without the “substituted” modifier refers to a monovalent saturated aliphatic group with a carbon atom as the point of attachment, said carbon atom forming part of one or more non-aromatic ring structures, no carbon-carbon double or triple bonds, and no atoms other than carbon and hydrogen. Non-limiting examples include: —CH(CH2)2(cyclopropyl), cyclobutyl, cyclopentyl, or cyclohexyl (Cy). The term “cycloalkanediyl” when used without the “substituted” modifier refers to a divalent saturated aliphatic group with two carbon atoms as points of attachment, no carbon-carbon double or triple bonds, and no atoms other than carbon and hydrogen. The group is a non-limiting example of cycloalkanediyl group. A “cycloalkane” refers to the class of compounds having the formula H—R, wherein R is cycloalkyl as this term is defined above. When any of these terms is used with the “substituted” modifier one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —NHCH3, —NHCH2CH3, —N(CH3)2, —C(O)NH2, —C(O)NHCH3, —C(O)N(CH3)2, —OC(O)CH3, —NHC(O)CH3, —S(O)2OH, or —S(O)2NH2. The term “alkenyl” when used without the “substituted” modifier refers to an monovalent unsaturated aliphatic group with a carbon atom as the point of attachment, a linear or branched, acyclic structure, at least one nonaromatic carbon-carbon double bond, no carbon-carbon triple bonds, and no atoms other than carbon and hydrogen. Non-limiting examples include: —CH═CH2(vinyl), —CH═CHCH3, —CH═CHCH2CH3, —CH2CH═CH2(allyl), —CH2CH═CHCH3, and —CH═CHCH═CH2. The term “alkenediyl” when used without the “substituted” modifier refers to a divalent unsaturated aliphatic group, with two carbon atoms as points of attachment, a linear or branched, a linear or branched acyclic structure, at least one nonaromatic carbon-carbon double bond, no carbon-carbon triple bonds, and no atoms other than carbon and hydrogen. The groups —CH═CH—, —CH═C(CH3)CH2—, —CH═CHCH2—, and —CH2CH═CHCH2— are non-limiting examples of alkenediyl groups. It is noted that while the alkenediyl group is aliphatic, once connected at both ends, this group is not precluded from forming part of an aromatic structure. The terms “alkene” and “olefin” are synonymous and refer to the class of compounds having the formula H—R, wherein R is alkenyl as this term is defined above. Similarly the terms “terminal alkene” and “α-olefin” are synonymous and refer to an alkene having just one carbon-carbon double bond, wherein that bond is part of a vinyl group at an end of the molecule. When any of these terms are used with the “substituted” modifier one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —NHCH3, —NHCH2CH3, —N(CH3)2, —C(O)NH2, —C(O)NHCH3, —C(O)N(CH3)2, —OC(O)CH3, —NHC(O)CH3, —S(O)2OH, or —S(O)2NH2. The groups —CH═CHF, —CH═CHCl and —CH═CHBr are non-limiting examples of substituted alkenyl groups. The term “alkynyl” when used without the “substituted” modifier refers to a monovalent unsaturated aliphatic group with a carbon atom as the point of attachment, a linear or branched acyclic structure, at least one carbon-carbon triple bond, and no atoms other than carbon and hydrogen. As used herein, the term alkynyl does not preclude the presence of one or more non-aromatic carbon-carbon double bonds. The groups —C≡CH, —C≡CCH3, and —CH2C≡CCH3are non-limiting examples of alkynyl groups. An “alkyne” refers to the class of compounds having the formula H—R, wherein R is alkynyl. When any of these terms are used with the “substituted” modifier one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —NHCH3, —NHCH2CH3, —N(CH3)2, —C(O)NH2, —C(O)NHCH3, —C(O)N(CH3)2, —OC(O)CH3, —NHC(O)CH3, —S(O)2OH, or —S(O)2NH2. The term “aryl” when used without the “substituted” modifier refers to a monovalent unsaturated aromatic group with an aromatic carbon atom as the point of attachment, said carbon atom forming part of a one or more six-membered aromatic ring structure, wherein the ring atoms are all carbon, and wherein the group consists of no atoms other than carbon and hydrogen. If more than one ring is present, the rings may be fused or unfused. As used herein, the term does not preclude the presence of one or more alkyl or aralkyl groups (carbon number limitation permitting) attached to the first aromatic ring or any additional aromatic ring present. Non-limiting examples of aryl groups include phenyl (Ph), methylphenyl, (dimethyl)phenyl, —C6H4CH2CH3(ethylphenyl), naphthyl, and a monovalent group derived from biphenyl. The term “arenediyl” when used without the “substituted” modifier refers to a divalent aromatic group with two aromatic carbon atoms as points of attachment, said carbon atoms forming part of one or more six-membered aromatic ring structure(s) wherein the ring atoms are all carbon, and wherein the monovalent group consists of no atoms other than carbon and hydrogen. As used herein, the term does not preclude the presence of one or more alkyl, aryl or aralkyl groups (carbon number limitation permitting) attached to the first aromatic ring or any additional aromatic ring present. If more than one ring is present, the rings may be fused or unfused. Unfused rings may be connected via one or more of the following: a covalent bond, alkanediyl, or alkenediyl groups (carbon number limitation permitting). Non-limiting examples of arenediyl groups include: An “arene” refers to the class of compounds having the formula H—R, wherein R is aryl as that term is defined above. Benzene and toluene are non-limiting examples of arenes. When any of these terms are used with the “substituted” modifier one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —NHCH3, —NHCH2CH3, —N(CH3)2, —C(O)NH2, —C(O)NHCH3, —C(O)N(CH3)2, —OC(O)CH3, —NHC(O)CH3, —S(O)2OH, or —S(O)2NH2. The term “aralkyl” when used without the “substituted” modifier refers to the monovalent group -alkanediyl-aryl, in which the terms alkanediyl and aryl are each used in a manner consistent with the definitions provided above. Non-limiting examples are: phenylmethyl (benzyl, Bn) and 2-phenyl-ethyl. When the term aralkyl is used with the “substituted” modifier one or more hydrogen atom from the alkanediyl and/or the aryl group has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —NHCH3, —NHCH2CH3, —N(CH3)2, —C(O)NH2, —C(O)NHCH3, —C(O)N(CH3)2, —OC(O)CH3, —NHC(O)CH3, —S(O)2OH, or —S(O)2NH2. Non-limiting examples of substituted aralkyls are: (3-chlorophenyl)-methyl, and 2-chloro-2-phenyl-eth-1-yl. The term “heteroaryl” when used without the “substituted” modifier refers to a monovalent aromatic group with an aromatic carbon atom or nitrogen atom as the point of attachment, said carbon atom or nitrogen atom forming part of one or more aromatic ring structures wherein at least one of the ring atoms is nitrogen, oxygen or sulfur, and wherein the heteroaryl group consists of no atoms other than carbon, hydrogen, aromatic nitrogen, aromatic oxygen and aromatic sulfur. Heteroaryl rings may contain 1, 2, 3, or 4 ring atoms selected from are nitrogen, oxygen, and sulfur. If more than one ring is present, the rings may be fused or unfused. As used herein, the term does not preclude the presence of one or more alkyl, aryl, and/or aralkyl groups (carbon number limitation permitting) attached to the aromatic ring or aromatic ring system. Non-limiting examples of heteroaryl groups include furanyl, imidazolyl, indolyl, indazolyl (Im), isoxazolyl, methylpyridinyl, oxazolyl, phenylpyridinyl, pyridinyl (pyridyl), pyrrolyl, pyrimidinyl, pyrazinyl, quinolyl, quinazolyl, quinoxalinyl, triazinyl, tetrazolyl, thiazolyl, thienyl, and triazolyl. The term “N-heteroaryl” refers to a heteroaryl group with a nitrogen atom as the point of attachment. The term “heteroarenediyl” when used without the “substituted” modifier refers to an divalent aromatic group, with two aromatic carbon atoms, two aromatic nitrogen atoms, or one aromatic carbon atom and one aromatic nitrogen atom as the two points of attachment, said atoms forming part of one or more aromatic ring structure(s) wherein at least one of the ring atoms is nitrogen, oxygen or sulfur, and wherein the divalent group consists of no atoms other than carbon, hydrogen, aromatic nitrogen, aromatic oxygen and aromatic sulfur. If more than one ring is present, the rings may be fused or unfused. Unfused rings may be connected via one or more of the following: a covalent bond, alkanediyl, or alkenediyl groups (carbon number limitation permitting). As used herein, the term does not preclude the presence of one or more alkyl, aryl, and/or aralkyl groups (carbon number limitation permitting) attached to the aromatic ring or aromatic ring system. Non-limiting examples of heteroarenediyl groups include: A “heteroarene” refers to the class of compounds having the formula H—R, wherein R is heteroaryl. Pyridine and quinoline are non-limiting examples of heteroarenes. When these terms are used with the “substituted” modifier one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —NHCH3, —NHCH2CH3, —N(CH3)2, —C(O)NH2, —C(O)NHCH3, —C(O)N(CH3)2, —OC(O)CH3, —NHC(O)CH3, —S(O)2OH, or —S(O)2NH2. The term “heterocycloalkyl” when used without the “substituted” modifier refers to a monovalent non-aromatic group with a carbon atom or nitrogen atom as the point of attachment, said carbon atom or nitrogen atom forming part of one or more non-aromatic ring structures wherein at least one of the ring atoms is nitrogen, oxygen or sulfur, and wherein the heterocycloalkyl group consists of no atoms other than carbon, hydrogen, nitrogen, oxygen and sulfur. Heterocycloalkyl rings may contain 1, 2, 3, or 4 ring atoms selected from nitrogen, oxygen, or sulfur. If more than one ring is present, the rings may be fused or unfused. As used herein, the term does not preclude the presence of one or more alkyl groups (carbon number limitation permitting) attached to the ring or ring system. Also, the term does not preclude the presence of one or more double bonds in the ring or ring system, provided that the resulting group remains non-aromatic. Non-limiting examples of heterocycloalkyl groups include aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, tetrahydrofuranyl, tetrahydrothiofuranyl, tetrahydropyranyl, pyranyl, oxiranyl, and oxetanyl. The term “N-heterocycloalkyl” refers to a heterocycloalkyl group with a nitrogen atom as the point of attachment. N-pyrrolidinyl is an example of such a group. The term “heterocycloalkanediyl” when used without the “substituted” modifier refers to an divalent cyclic group, with two carbon atoms, two nitrogen atoms, or one carbon atom and one nitrogen atom as the two points of attachment, said atoms forming part of one or more ring structure(s) wherein at least one of the ring atoms is nitrogen, oxygen or sulfur, and wherein the divalent group consists of no atoms other than carbon, hydrogen, nitrogen, oxygen and sulfur. If more than one ring is present, the rings may be fused or unfused. Unfused rings may be connected via one or more of the following: a covalent bond, alkanediyl, or alkenediyl groups (carbon number limitation permitting). As used herein, the term does not preclude the presence of one or more alkyl groups (carbon number limitation permitting) attached to the ring or ring system. Also, the term does not preclude the presence of one or more double bonds in the ring or ring system, provided that the resulting group remains non-aromatic. Non-limiting examples of heterocycloalkanediyl groups include: When these terms are used with the “substituted” modifier one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —NHCH3, —NHCH2CH3, —N(CH3)2, —C(O)NH2, —C(O)NHCH3, —C(O)N(CH3)2, —OC(O)CH3, —NHC(O)CH3, —S(O)2OH, or —S(O)2NH2. The term “acyl” when used without the “substituted” modifier refers to the group —C(O)R, in which R is a hydrogen, alkyl, cycloalkyl, alkenyl, aryl, aralkyl or heteroaryl, as those terms are defined above. The groups, —CHO, —C(O)CH3(acetyl, Ac), —C(O)CH2CH3, —C(O)CH2CH2CH3, —C(O)CH(CH3)2, —C(O)CH(CH2)2, —C(O)C6H5, —C(O)C6H4CH3, —C(O)CH2C6H5, —C(O)(imidazolyl) are non-limiting examples of acyl groups. A “thioacyl” is defined in an analogous manner, except that the oxygen atom of the group —C(O)R has been replaced with a sulfur atom, —C(S)R. The term “aldehyde” corresponds to an alkane, as defined above, wherein at least one of the hydrogen atoms has been replaced with a —CHO group. When any of these terms are used with the “substituted” modifier one or more hydrogen atom (including a hydrogen atom directly attached to the carbon atom of the carbonyl or thiocarbonyl group, if any) has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —NHCH3, —NHCH2CH3, —N(CH3)2, —C(O)NH2, —C(O)NHCH3, —C(O)N(CH3)2, —OC(O)CH3, —NHC(O)CH3, —S(O)2OH, or —S(O)2NH2. The groups, —C(O)CH2CF3, —CO2H (carboxyl), —CO2CH3(methylcarboxyl), —CO2CH2CH3, —C(O)NH2(carbamoyl), and —CON(CH3)2, are non-limiting examples of substituted acyl groups. The term “alkoxy” when used without the “substituted” modifier refers to the group —OR, in which R is an alkyl, as that term is defined above. Non-limiting examples include: —OCH3(methoxy), —OCH2CH3(ethoxy), —OCH2CH2CH3, —OCH(CH3)2(isopropoxy), —OC(CH3)3(tert-butoxy), —OCH(CH2)2, —O-cyclopentyl, and —O-cyclohexyl. The terms “cycloalkoxy”, “alkenyloxy”, “alkynyloxy”, “aryloxy”, “aralkoxy”, “heteroaryloxy”, “heterocycloalkoxy”, and “acyloxy”, when used without the “substituted” modifier, refers to groups, defined as —OR, in which R is cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heterocycloalkyl, and acyl, respectively. The term “alkoxydiyl” refers to the divalent group —O-alkanediyl-, —O-alkanediyl-O—, or -alkanediyl-O-alkanediyl-. The term “alkylthio” and “acylthio” when used without the “substituted” modifier refers to the group —SR, in which R is an alkyl and acyl, respectively. The term “alcohol” corresponds to an alkane, as defined above, wherein at least one of the hydrogen atoms has been replaced with a hydroxy group. The term “ether” corresponds to an alkane, as defined above, wherein at least one of the hydrogen atoms has been replaced with an alkoxy group. When any of these terms is used with the “substituted” modifier one or more hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —NHCH3, —NHCH2CH3, —N(CH3)2, —C(O)NH2, —C(O)NHCH3, —C(O)N(CH3)2, —OC(O)CH3, —NHC(O)CH3, —S(O)2OH, or —S(O)2NH2. The term “alkylamino” when used without the “substituted” modifier refers to the group —NHR, in which R is an alkyl, as that term is defined above. Non-limiting examples include: —NHCH3and —NHCH2CH3. The term “dialkylamino” when used without the “substituted” modifier refers to the group —NRR′, in which R and R′ can be the same or different alkyl groups, or R and R′ can be taken together to represent an alkanediyl. Non-limiting examples of dialkylamino groups include: —N(CH3)2and —N(CH3)(CH2CH3). The terms “cycloalkylamino”, “alkenylamino”, “alkynylamino”, “arylamino”, “aralkylamino”, “heteroarylamino”, “heterocycloalkylamino”, “alkoxyamino”, and “alkylsulfonylamino” when used without the “substituted” modifier, refers to groups, defined as —NHR, in which R is cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heterocycloalkyl, alkoxy, and alkylsulfonyl, respectively. A non-limiting example of an arylamino group is —NHC6H5. The term “alkylaminodiyl” refers to the divalent group —NH-alkanediyl-, —NH-alkanediyl-NH—, or -alkanediyl-NH-alkanediyl-. The term “amido” (acylamino), when used without the “substituted” modifier, refers to the group —NHR, in which R is acyl, as that term is defined above. A non-limiting example of an amido group is —NHC(O)CH3. The term “alkylimino” when used without the “substituted” modifier refers to the divalent group ═NR, in which R is an alkyl, as that term is defined above. When any of these terms is used with the “substituted” modifier one or more hydrogen atom attached to a carbon atom has been independently replaced by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —NHCH3, —NHCH2CH3, —N(CH3)2, —C(O)NH2, —C(O)NHCH3, —C(O)N(CH3)2, —OC(O)CH3, —NHC(O)CH3, —S(O)2OH, or —S(O)2NH2. The groups —NHC(O)OCH3and —NHC(O)NHCH3are non-limiting examples of substituted amido groups. The use of the word “a” or “an,” when used in conjunction with the term “comprising” in the claims and/or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.” Throughout this application, the term “about” is used to indicate that a value includes the inherent variation of error for the device, the method being employed to determine the value, or the variation that exists among the study subjects. As used in this application, the term “average molecular weight” refers to the relationship between the number of moles of each polymer species and the molar mass of that species. In particular, each polymer molecule may have different levels of polymerization and thus a different molar mass. The average molecular weight can be used to represent the molecular weight of a plurality of polymer molecules. Average molecular weight is typically synonymous with average molar mass. In particular, there are three major types of average molecular weight: number average molar mass, weight (mass) average molar mass, and Z-average molar mass. In the context of this application, unless otherwise specified, the average molecular weight represents either the number average molar mass or weight average molar mass of the formula. In some embodiments, the average molecular weight is the number average molar mass. In some embodiments, the average molecular weight may be used to describe a PEG component present in a lipid. The terms “comprise,” “have” and “include” are open-ended linking verbs. Any forms or tenses of one or more of these verbs, such as “comprises,” “comprising,” “has,” “having,” “includes” and “including,” are also open-ended. For example, any method that “comprises,” “has” or “includes” one or more steps is not limited to possessing only those one or more steps and also covers other unlisted steps. The term “effective,” as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result. “Effective amount,” “Therapeutically effective amount” or “pharmaceutically effective amount” when used in the context of treating a patient or subject with a compound means that amount of the compound which, when administered to a subject or patient for treating a disease, is sufficient to effect such treatment for the disease. As used herein, the term “IC50” refers to an inhibitory dose which is 50% of the maximum response obtained. This quantitative measure indicates how much of a particular drug or other substance (inhibitor) is needed to inhibit a given biological, biochemical or chemical process (or component of a process, i.e. an enzyme, cell, cell receptor or microorganism) by half. An “isomer” of a first compound is a separate compound in which each molecule contains the same constituent atoms as the first compound, but where the configuration of those atoms in three dimensions differs. As used herein, the term “patient” or “subject” refers to a living mammalian organism, such as a human, monkey, cow, sheep, goat, dog, cat, mouse, rat, guinea pig, or transgenic species thereof. In certain embodiments, the patient or subject is a primate. Non-limiting examples of human subjects are adults, juveniles, infants and fetuses. As generally used herein “pharmaceutically acceptable” refers to those compounds, materials, compositions, and/or dosage forms which are, within the scope of sound medical judgment, suitable for use in contact with the tissues, organs, and/or bodily fluids of human beings and animals without excessive toxicity, irritation, allergic response, or other problems or complications commensurate with a reasonable benefit/risk ratio. “Pharmaceutically acceptable salts” means salts of compounds of the present invention which are pharmaceutically acceptable, as defined above, and which possess the desired pharmacological activity. Such salts include acid addition salts formed with inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and the like; or with organic acids such as 1,2-ethanedisulfonic acid, 2-hydroxyethanesulfonic acid, 2-naphthalenesulfonic acid, 3-phenylpropionic acid, 4,4′-methylenebis(3-hydroxy-2-ene-1-carboxylic acid), 4-methylbicyclo[2.2.2]oct-2-ene-1-carboxylic acid, acetic acid, aliphatic mono- and dicarboxylic acids, aliphatic sulfuric acids, aromatic sulfuric acids, benzenesulfonic acid, benzoic acid, camphorsulfonic acid, carbonic acid, cinnamic acid, citric acid, cyclopentanepropionic acid, ethanesulfonic acid, fumaric acid, glucoheptonic acid, gluconic acid, glutamic acid, glycolic acid, heptanoic acid, hexanoic acid, hydroxynaphthoic acid, lactic acid, laurylsulfuric acid, maleic acid, malic acid, malonic acid, mandelic acid, methanesulfonic acid, muconic acid, o-(4-hydroxybenzoyl)benzoic acid, oxalic acid, p-chlorobenzenesulfonic acid, phenyl-substituted alkanoic acids, propionic acid, p-toluenesulfonic acid, pyruvic acid, salicylic acid, stearic acid, succinic acid, tartaric acid, tertiarybutylacetic acid, trimethylacetic acid, and the like. Pharmaceutically acceptable salts also include base addition salts which may be formed when acidic protons present are capable of reacting with inorganic or organic bases. Acceptable inorganic bases include sodium hydroxide, sodium carbonate, potassium hydroxide, aluminum hydroxide and calcium hydroxide. Acceptable organic bases include ethanolamine, diethanolamine, triethanolamine, tromethamine, N-methylglucamine and the like. It should be recognized that the particular anion or cation forming a part of any salt of this invention is not critical, so long as the salt, as a whole, is pharmacologically acceptable. Additional examples of pharmaceutically acceptable salts and their methods of preparation and use are presented inHandbook of Pharmaceutical Salts: Properties, and Use(P. H. Stahl & C. G. Wermuth eds., Verlag Helvetica Chimica Acta, 2002). The term “pharmaceutically acceptable carrier,” as used herein means a pharmaceutically-acceptable material, composition or vehicle, such as a liquid or solid filler, diluent, excipient, solvent or encapsulating material, involved in carrying or transporting a chemical agent. “Prevention” or “preventing” includes: (1) inhibiting the onset of a disease in a subject or patient which may be at risk and/or predisposed to the disease but does not yet experience or display any or all of the pathology or symptomatology of the disease, and/or (2) slowing the onset of the pathology or symptomatology of a disease in a subject or patient which may be at risk and/or predisposed to the disease but does not yet experience or display any or all of the pathology or symptomatology of the disease. A “repeat unit” is the simplest structural entity of certain materials, for example, frameworks and/or polymers, whether organic, inorganic or metal-organic. In the case of a polymer chain, repeat units are linked together successively along the chain, like the beads of a necklace. For example, in polyethylene, —[—CH2CH2—]n—, the repeat unit is —CH2CH2—. The subscript “n” denotes the degree of polymerization, that is, the number of repeat units linked together. When the value for “n” is left undefined or where “n” is absent, it simply designates repetition of the formula within the brackets as well as the polymeric nature of the material. The concept of a repeat unit applies equally to where the connectivity between the repeat units extends three dimensionally, such as in metal organic frameworks, modified polymers, thermosetting polymers, etc. Within the context of the dendrimer, the repeating unit may also be described as the branching unit, interior layers, or generations. Similarly, the terminating group may also be described as the surface group. A “stereoisomer” or “optical isomer” is an isomer of a given compound in which the same atoms are bonded to the same other atoms, but where the configuration of those atoms in three dimensions differs. “Enantiomers” are stereoisomers of a given compound that are mirror images of each other, like left and right hands. “Diastereomers” are stereoisomers of a given compound that are not enantiomers. Chiral molecules contain a chiral center, also referred to as a stereocenter or stereogenic center, which is any point, though not necessarily an atom, in a molecule bearing groups such that an interchanging of any two groups leads to a stereoisomer. In organic compounds, the chiral center is typically a carbon, phosphorus or sulfur atom, though it is also possible for other atoms to be stereocenters in organic and inorganic compounds. A molecule can have multiple stereocenters, giving it many stereoisomers. In compounds whose stereoisomerism is due to tetrahedral stereogenic centers (e.g., tetrahedral carbon), the total number of hypothetically possible stereoisomers will not exceed 2n, where n is the number of tetrahedral stereocenters. Molecules with symmetry frequently have fewer than the maximum possible number of stereoisomers. A 50:50 mixture of enantiomers is referred to as a racemic mixture. Alternatively, a mixture of enantiomers can be enantiomerically enriched so that one enantiomer is present in an amount greater than 50%. Typically, enantiomers and/or diastereomers can be resolved or separated using techniques known in the art. It is contemplated that that for any stereocenter or axis of chirality for which stereochemistry has not been defined, that stereocenter or axis of chirality can be present in its R form, S form, or as a mixture of the R and S forms, including racemic and non-racemic mixtures. As used herein, the phrase “substantially free from other stereoisomers” means that the composition contains ≤15%, more preferably ≤10%, even more preferably ≤5%, or most preferably ≤1% of another stereoisomer(s). “Treatment” or “treating” includes (1) inhibiting a disease in a subject or patient experiencing or displaying the pathology or symptomatology of the disease (e.g., arresting further development of the pathology and/or symptomatology), (2) ameliorating a disease in a subject or patient that is experiencing or displaying the pathology or symptomatology of the disease (e.g., reversing the pathology and/or symptomatology), and/or (3) effecting any measurable decrease in a disease in a subject or patient that is experiencing or displaying the pathology or symptomatology of the disease. The above definitions supersede any conflicting definition in any reference that is incorporated by reference herein. The fact that certain terms are defined, however, should not be considered as indicative that any term that is undefined is indefinite. Rather, all terms used are believed to describe the invention in terms such that one of ordinary skill can appreciate the scope and practice the present invention. B. DENDRIMERS AND DENDRITIC STRUCTURES In some aspects of the present disclosure, dendrimers containing lipophilic and cationic components are provided. Dendrimers are a polymer exhibiting regular dendritic branching, formed by the sequential or generational addition of branched layers to or from a core and are characterized by a core, at least one interior branched layer, and a surface branched layer. (See Petar R. Dvornic and Donald A. Tomalia in Chem. in Britain, 641-645, August 1994.) In other embodiments, the term “dendrimer” as used herein is intended to include, but is not limited to, a molecular architecture with an interior core, interior layers (or “generations”) of repeating units regularly attached to this initiator core, and an exterior surface of terminal groups attached to the outermost generation. A “dendron” is a species of dendrimer having branches emanating from a focal point which is or can be joined to a core, either directly or through a linking moiety to form a larger dendrimer. In some embodiments, the dendrimer structures have radiating repeating groups from a central core which doubles with each repeating unit for each branch. In some embodiments, the dendrimers described herein may be described as a small molecule, medium-sized molecules, lipids, or lipid-like material. These terms may be used to described compounds described herein which have a dendron like appearance (e.g. molecules which radiate from a single focal point). While dendrimers are polymers, dendrimers are preferable to traditional polymers because they have a controllable structure, a single molecular weight, numerous and controllable surface functionalities, and traditionally adopt a globular conformation after reaching a specific generation. Dendrimers can be prepared by sequentially reactions of each repeating unit to produce monodisperse, tree-like and/or generational structure polymeric structures. Individual dendrimers consist of a central core molecule, with a dendritic wedge attached to one or more functional sites on that central core. The dendrimeric surface layer can have a variety of functional groups disposed thereon including anionic, cationic, hydrophilic, or lipophilic groups, according to the assembly monomers used during the preparation. Modifying the functional groups and/or the chemical properties of the core, repeating units, and the surface or terminating groups, their physical properties can be modulated. Some properties which can be varied include, but are not limited to, solubility, toxicity, immunogenicity and bioattachment capability. Dendrimers are often described by their generation or number of repeating units in the branches. A dendrimer consisting of only the core molecule is referred to as Generation 0, while each consecutive repeating unit along all branches is Generation 1, Generation 2, and so on until the terminating or surface group. In some embodiments, half generations are possible resulting from only the first condensation reaction with the amine and not the second condensation reaction with the thiol Preparation of dendrimers requires a level of synthetic control achieved through series of stepwise reactions comprising building the dendrimer by each consecutive group. Dendrimer synthesis can be of the convergent or divergent type. During divergent dendrimer synthesis, the molecule is assembled from the core to the periphery in a stepwise process involving attaching one generation to the previous and then changing functional groups for the next stage of reaction. Functional group transformation is necessary to prevent uncontrolled polymerization. Such polymerization would lead to a highly branched molecule that is not monodisperse and is otherwise known as a hyperbranched polymer. Due to steric effects, continuing to react dendrimer repeat units leads to a sphere shaped or globular molecule, until steric overcrowding prevents complete reaction at a specific generation and destroys the molecule's monodispersity. Thus, in some embodiments, the dendrimers of G1-G10 generation are specifically contemplated. In some embodiments, the dendrimers comprise 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 repeating units, or any range derivable therein. In some embodiments, the dendrimers used herein are G0, G1, G2, or G3. However, the number of possible generations (such as 11, 12, 13, 14, 15, 20, or 25) may be increased by reducing the spacing units in the branching polymer. Additionally, dendrimers have two major chemical environments: the environment created by the specific surface groups on the termination generation and the interior of the dendritic structure which due to the higher order structure can be shielded from the bulk media and the surface groups. Because of these different chemical environments, dendrimers have found numerous different potential uses including in therapeutic applications. In some aspects, the dendrimers of the present disclosure are assembled using the differential reactivity of the acrylate and methacrylate groups with amines and thiols. The dendrimers that may be used herein include secondary or tertiary amines and thioethers formed by the reaction of an acrylate group with a primary or secondary amine and a methacrylate with a mercapto group. Additionally, the repeating units of the dendrimers described herein may contain groups which are degradable under physiological conditions. In some embodiments, these repeating units may contain one or more germinal diethers, esters, amides, or disulfides groups. In some embodiments, the core molecule is a monoamine which allows dendritic polymerization in only one direction. In other embodiments, the core molecule is a polyamine with multiple different dendritic branches which each may comprise one or more repeating units. The dendrimer may be formed by removing one or more hydrogen atoms from this core. In some embodiments, these hydrogen atoms are on a heteroatom such as a nitrogen atom. In some embodiments, the terminating group is a lipophilic groups such as a long chain alkyl or alkenyl group. In other embodiments, the terminating group is a long chain haloalkyl or haloalkenyl group. In other embodiments, the terminating group is an aliphatic or aromatic group containing an ionizable group such as an amine (—NH2) or a carboxylic acid (—CO2H). In still other embodiments, the terminating group is an aliphatic or aromatic group containing one or more hydrogen bond donors such as a hydroxide group, an amide group, or an ester. The dendrimers provided by the present disclosure are shown, for example, above in the summary of the invention section and in the claims below. They may be made using the methods outlined in the Examples section. These methods can be further modified and optimized using the principles and techniques of organic chemistry as applied by a person skilled in the art. Such principles and techniques are taught, for example, inMarch's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure(2007), which is incorporated by reference herein. The dendrimers of the present disclosure may contain one or more asymmetrically-substituted carbon or nitrogen atoms, and may be isolated in optically active or racemic form. Thus, all chiral, diastereomeric, racemic form, epimeric form, and all geometric isomeric forms of a chemical formula are intended, unless the specific stereochemistry or isomeric form is specifically indicated. Dendrimers may occur as racemates and racemic mixtures, single enantiomers, diastereomeric mixtures and individual diastereomers. In some embodiments, a single diastereomer is obtained. The chiral centers of the dendrimers of the present disclosure can have the S or the R configuration. Furthermore, it is contemplated that one or more of the dendrimers may be present as constitutional isomers. In some embodiments, the compounds have the same formula but different connectivity to the nitrogen atoms of the core. Without wishing to be bound by any theory, it is believed that such dendrimers exist because the starting monomers react first with the primary amines and then statistically with any secondary amines present. Thus, the constitutional isomers may present the fully reacted primary amines and then a mixture of reacted secondary amines. Chemical formulas used to represent dendrimers of the present disclosure will typically only show one of possibly several different tautomers. For example, many types of ketone groups are known to exist in equilibrium with corresponding enol groups. Similarly, many types of imine groups exist in equilibrium with enamine groups. Regardless of which tautomer is depicted for a given formula, and regardless of which one is most prevalent, all tautomers of a given chemical formula are intended. The dendrimers of the present disclosure may also have the advantage that they may be more efficacious than, be less toxic than, be longer acting than, be more potent than, produce fewer side effects than, be more easily absorbed than, and/or have a better pharmacokinetic profile (e.g., higher oral bioavailability and/or lower clearance) than, and/or have other useful pharmacological, physical, or chemical properties over, compounds known in the prior art, whether for use in the indications stated herein or otherwise. In addition, atoms making up the dendrimers of the present disclosure are intended to include all isotopic forms of such atoms. Isotopes, as used herein, include those atoms having the same atomic number but different mass numbers. By way of general example and without limitation, isotopes of hydrogen include tritium and deuterium, and isotopes of carbon include13C and14C. It should be recognized that the particular anion or cation forming a part of any salt form of a dendrimer provided herein is not critical, so long as the salt, as a whole, is pharmacologically acceptable. Additional examples of pharmaceutically acceptable salts and their methods of preparation and use are presented inHandbook of Pharmaceutical Salts: Properties, and Use(2002), which is incorporated herein by reference. C. HELPER LIPIDS In some aspects of the present disclosure, one or more helper lipids are mixed with the polymers of the instant disclosure to create a composition. In some embodiments, the polymers are mixed with 1, 2, 3, 4, or 5 different types of helper lipids. It is contemplated that the polymers can be mixed with multiple different lipids of a single type. In some embodiments, the lipid could be a steroid or a steroid derivative. In other embodiments, the lipid is a PEG lipid. In other embodiments, the lipid is a phospholipid. In other embodiments, the dendrimer composition comprises a steroid or a steroid derivative, a PEG lipid, and a phospholipid. 1. Steroids and Steroid Derivatives In some aspects of the present disclosure, the polymers are mixed with one or more steroid or a steroid derivative to create a dendrimer composition. In some embodiments, the steroid or steroid derivative comprises any steroid or steroid derivative. As used herein, in some embodiments, the term “steroid” is a class of compounds with a four ring 17 carbon cyclic structure which can further comprises one or more substitutions including alkyl groups, alkoxy groups, hydroxy groups, oxo groups, acyl groups, or a double bond between two or more carbon atoms. In one aspect, the ring structure of a steroid comprises three fused cyclohexyl rings and a fused cyclopentyl ring as shown in the formula below: In some embodiments, a steroid derivative comprises the ring structure above with one or more non-alkyl substitutions. In some embodiments, the steroid or steroid derivative is a sterol wherein the formula is further defined as: In some embodiments of the present disclosure, the steroid or steroid derivative is a cholestane or cholestane derivative. In a cholestane, the ring structure is further defined by the formula: As described above, a cholestane derivative includes one or more non-alkyl substitution of the above ring system. In some embodiments, the cholestane or cholestane derivative is a cholestene or cholestene derivative or a sterol or a sterol derivative. In other embodiments, the cholestane or cholestane derivative is both a cholestere and a sterol or a derivative thereof. In some embodiments, the compositions may further comprise a molar ratio of the steroid to the dendrimer from about 1:10 to about 1:20. In some embodiments, the molar ratio is from about 1:20, 1:18, 1:16, 1:14, 1:12, 1:10, 1:8, 1:6, 1:4, 1:2, 1:1, 2:1, 4:1, 6:1, 8:1, to about 10:1 or any range derivable therein. In some embodiments, the molar ratio is about 38:50 or about 1:5. 2. PEG or PEGylated Lipid In some aspects of the present disclosure, the polymers are mixed with one or more PEGylated lipids (or PEG lipid) to create a dendrimer composition. In some embodiments, the present disclosure comprises using any lipid to which a PEG group has been attached. In some embodiments, the PEG lipid is a diglyceride which also comprises a PEG chain attached to the glycerol group. In other embodiments, the PEG lipid is a compound which contains one or more C6-C24 long chain alkyl or alkenyl group or a C6-C24 fatty acid group attached to a linker group with a PEG chain. Some non-limiting examples of a PEG lipid includes a PEG modified phosphatidylethanolamine and phosphatidic acid, a PEG ceramide conjugated, PEG modified dialkylamines and PEG modified 1,2-diacyloxypropan-3-amines, PEG modified diacylglycerols and dialkylglycerols. In some embodiments, PEG modified diastearoylphosphatidylethanolamine or PEG modified dimyristoyl-sn-glycerol. In some embodiments, the PEG modification is measured by the molecular weight of PEG component of the lipid. In some embodiments, the PEG modification has a molecular weight from about 100 to about 15,000. In some embodiments, the molecular weight is from about 200 to about 500, from about 400 to about 5,000, from about 500 to about 3,000, or from about 1,200 to about 3,000. The molecular weight of the PEG modification is from about 100, 200, 400, 500, 600, 800, 1,000, 1,250, 1,500, 1,750, 2,000, 2,250, 2,500, 2,750, 3,000, 3,500, 4,000, 4,500, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 12,500, to about 15,000. Some non-limiting examples of lipids that may be used in the present invention are taught by U.S. Pat. No. 5,820,873, WO 2010/141069, or U.S. Pat. No. 8,450,298, which is incorporated herein by reference. In another aspect, the PEG lipid has the formula: wherein: R12and R13are each independently alkyl(C≤24), alkenyl(C≤24), or a substituted version of either of these groups; Reis hydrogen, alkyl(C≤8), or substituted alkyl(C≤8); and x is 1-250. In some embodiments, Reis alkyl(C≤8)such as methyl. R12and R13are each independently alkyl(C≤4-20). In some embodiments, x is 5-250. In one embodiment, x is 5-125 or x is 100-250. In some embodiments, the PEG lipid is 1,2-dimyristoyl-sn-glycerol, methoxypolyethylene glycol. In another aspect, the PEG lipid has the formula: wherein: n1is an integer between 1 and 100 and n2and n3are each independently selected from an integer between 1 and 29. In some embodiments, n1is 5, 10, 15, 20, 25, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100, or any range derivable therein. In some embodiments, n1is from about 30 to about 50. In some embodiments, n2is from 5 to 23. In some embodiments, n2is 11 to about 17. In some embodiments, n3is from 5 to 23. In some embodiments, n3is 11 to about 17. In some embodiments, the compositions may further comprise a molar ratio of the PEG lipid to the dendrimer from about 1:1 to about 1:250. In some embodiments, the molar ratio is from about 1:1, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:110, 1:120, 1:125, 1:150, 1:175, 1:200, 1:225, to about 1:250 or any range derivable therein. In some embodiments, the molar ratio is about 1:25 or about 3:100. 3. Phospholipid In some aspects of the present disclosure, the polymers are mixed with one or more phospholipids to create a dendrimer composition. In some embodiments, any lipid which also comprises a phosphate group. In some embodiments, the phospholipid is a structure which contains one or two long chain C6-C24 alkyl or alkenyl groups, a glycerol or a sphingosine, one or two phosphate groups, and, optionally, a small organic molecule. In some embodiments, the small organic molecule is an amino acid, a sugar, or an amino substituted alkoxy group, such as choline or ethanolamine. In some embodiments, the phospholipid is a phosphatidylcholine. In some embodiments, the phospholipid is distearoylphosphatidylcholine or dioleoylphosphatidylethanolamine. In some embodiments, the compositions may further comprise a molar ratio of the phospholipid to the dendrimer from about 1:10 to about 1:20. In some embodiments, the molar ratio is from about 1:20, 1:18, 1:16, 1:14, 1:12, 1:10, 1:8, 1:6, 1:4, 1:2, 1:1, 2:1, 4:1, 6:1, 8:1, to about 10:1 or any range derivable therein. In some embodiments, the molar ratio is about 38:50 or about 1:5. D. NUCLEIC ACIDS AND NUCLEIC ACID BASED THERAPEUTIC AGENTS 1. Nucleic Acids In some aspects of the present disclosure, the dendrimer compositions comprise one or more nucleic acids. In some embodiments, the dendrimer composition comprises one or more nucleic acids present in a weight ratio to the dendrimer from about 5:1 to about 1:100. In some embodiments, the weight ratio of nucleic acid to dendrimer is from about 5:1, 2.5:1, 1:1, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:60, 1:70, 1:80, 1:90, or 1:100, or any range derivable therein. In some embodiments, the weight ratio is about 1:25 or about 1:7. In addition, it should be clear that the present disclosure is not limited to the specific nucleic acids disclosed herein. The present invention is not limited in scope to any particular source, sequence, or type of nucleic acid, however, as one of ordinary skill in the art could readily identify related homologs in various other sources of the nucleic acid including nucleic acids from non-human species (e.g., mouse, rat, rabbit, dog, monkey, gibbon, chimp, ape, baboon, cow, pig, horse, sheep, cat and other species). It is contemplated that the nucleic acid used in the present disclosure can comprises a sequence based upon a naturally-occurring sequence. Allowing for the degeneracy of the genetic code, sequences that have at least about 50%, usually at least about 60%, more usually about 70%, most usually about 80%, preferably at least about 90% and most preferably about 95% of nucleotides that are identical to the nucleotide sequence of the naturally-occurring sequence. In another embodiment, the nucleic acid is a complementary sequence to a naturally occurring sequence, or complementary to 75%, 80%, 85%, 90%, 95% and 100%. In some aspects, the nucleic acid is a sequence which silences, is complimentary to, or replaces another sequence present in vivo. Sequences of 17 bases in length should occur only once in the human genome and, therefore, suffice to specify a unique target sequence. Although shorter oligomers are easier to make and increase in vivo accessibility, numerous other factors are involved in determining the specificity of hybridization. Both binding affinity and sequence specificity of an oligonucleotide to its complementary target increases with increasing length. It is contemplated that exemplary oligonucleotides of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 or more base pairs will be used, although others are contemplated. Longer polynucleotides encoding 250, 500, 1000, 1212, 1500, 2000, 2500, 3000 or longer are contemplated as well. The nucleic acid used herein may be derived from genomic DNA, i.e., cloned directly from the genome of a particular organism. In preferred embodiments, however, the nucleic acid would comprise complementary DNA (cDNA). Also contemplated is a cDNA plus a natural intron or an intron derived from another gene; such engineered molecules are sometime referred to as “mini-genes.” At a minimum, these and other nucleic acids of the present invention may be used as molecular weight standards in, for example, gel electrophoresis. The term “cDNA” is intended to refer to DNA prepared using messenger RNA (mRNA) as template. The advantage of using a cDNA, as opposed to genomic DNA or DNA polymerized from a genomic, non- or partially-processed RNA template, is that the cDNA primarily contains coding sequences of the corresponding protein. There may be times when the full or partial genomic sequence is preferred, such as where the non-coding regions are required for optimal expression or where non-coding regions such as introns are to be targeted in an antisense strategy. In some embodiments, the nucleic acid comprises one or more antisense segments which inhibits expression of a gene or gene product. Antisense methodology takes advantage of the fact that nucleic acids tend to pair with “complementary” sequences. By complementary, it is meant that polynucleotides are those which are capable of base-pairing according to the standard Watson-Crick complementarity rules. That is, the larger purines will base pair with the smaller pyrimidines to form combinations of guanine paired with cytosine (G:C) and adenine paired with either thymine (A:T) in the case of DNA, or adenine paired with uracil (A:U) in the case of RNA. Inclusion of less common bases such as inosine, 5-methylcytosine, 6-methyladenine, hypoxanthine and others in hybridizing sequences does not interfere with pairing. Targeting double-stranded (ds) DNA with polynucleotides leads to triple-helix formation; targeting RNA will lead to double-helix formation. Antisense polynucleotides, when introduced into a target cell, specifically bind to their target polynucleotide and interfere with transcription, RNA processing, transport, translation and/or stability. Antisense RNA constructs, or DNA encoding such antisense RNA's, may be employed to inhibit gene transcription or translation or both within a host cell, either in vitro or in vivo, such as within a host animal, including a human subject. Antisense constructs may be designed to bind to the promoter and other control regions, exons, introns or even exon-intron boundaries of a gene. It is contemplated that the most effective antisense constructs will include regions complementary to intron/exon splice junctions. Thus, it is proposed that a preferred embodiment includes an antisense construct with complementarity to regions within 50-200 bases of an intron-exon splice junction. It has been observed that some exon sequences can be included in the construct without seriously affecting the target selectivity thereof. The amount of exonic material included will vary depending on the particular exon and intron sequences used. One can readily test whether too much exon DNA is included simply by testing the constructs in vitro to determine whether normal cellular function is affected or whether the expression of related genes having complementary sequences is affected. As stated above, “complementary” or “antisense” means polynucleotide sequences that are substantially complementary over their entire length and have very few base mismatches. For example, sequences of fifteen bases in length may be termed complementary when they have complementary nucleotides at thirteen or fourteen positions. Naturally, sequences which are completely complementary will be sequences which are entirely complementary throughout their entire length and have no base mismatches. Other sequences with lower degrees of homology also are contemplated. For example, an antisense construct which has limited regions of high homology, but also contains a non-homologous region (e.g., ribozyme; see below) could be designed. These molecules, though having less than 50% homology, would bind to target sequences under appropriate conditions. It may be advantageous to combine portions of genomic DNA with cDNA or synthetic sequences to form a siRNA or to generate specific constructs. For example, where an intron is desired in the ultimate construct, a genomic clone will need to be used. The cDNA, siRNA, or a synthesized polynucleotide may provide more convenient restriction sites for the remaining portion of the construct and, therefore, would be used for the rest of the sequence. Other embodiments include dsRNA or ssRNA, which may be used to target genomic sequences or coding/non-coding transcripts. In other embodiments, the dendrimer compositions may comprise a nucleic acid which comprises one or more expression vectors are used in a gene therapy. Expression requires that appropriate signals be provided in the vectors, and which include various regulatory elements, such as enhancers/promoters from both viral and mammalian sources that drive expression of the genes of interest in host cells. Elements designed to optimize messenger RNA stability and translatability in host cells also are defined. The conditions for the use of a number of dominant drug selection markers for establishing permanent, stable cell clones expressing the products are also provided, as is an element that links expression of the drug selection markers to expression of the polypeptide. Throughout this application, the term “expression construct” is meant to include any type of genetic construct containing a nucleic acid coding for a gene product in which part or all of the nucleic acid encoding sequence is capable of being transcribed. The transcript may be translated into a protein, but it need not be. In certain embodiments, expression includes both transcription of a gene and translation of mRNA into a gene product. In other embodiments, expression only includes transcription of the nucleic acid encoding a gene of interest. The term “vector” is used to refer to a carrier nucleic acid molecule into which a nucleic acid sequence can be inserted for introduction into a cell where it can be replicated. A nucleic acid sequence can be “exogenous,” which means that it is foreign to the cell into which the vector is being introduced or that the sequence is homologous to a sequence in the cell but in a position within the host cell nucleic acid in which the sequence is ordinarily not found. Vectors include plasmids, cosmids, viruses (bacteriophage, animal viruses, and plant viruses), and artificial chromosomes (e.g., YACs). One of skill in the art would be well equipped to construct a vector through standard recombinant techniques, which are described in Sambrook et al. (1989) and Ausubel et al. (1994), both incorporated herein by reference. The term “expression vector” refers to a vector containing a nucleic acid sequence coding for at least part of a gene product capable of being transcribed. In some cases, RNA molecules are then translated into a protein, polypeptide, or peptide. In other cases, these sequences are not translated, for example, in the production of antisense molecules or ribozymes. Expression vectors can contain a variety of “control sequences,” which refer to nucleic acid sequences necessary for the transcription and possibly translation of an operably linked coding sequence in a particular host organism. In addition to control sequences that govern transcription and translation, vectors and expression vectors may contain nucleic acid sequences that serve other functions as well and are described infra. 2. siRNA As mentioned above, the present invention contemplates the use of one or more inhibitory nucleic acid for reducing expression and/or activation of a gene or gene product. Examples of an inhibitory nucleic acid include but are not limited to molecules targeted to an nucleic acid sequence, such as an siRNA (small interfering RNA), short hairpin RNA (shRNA), double-stranded RNA, an antisense oligonucleotide, a ribozyme and molecules targeted to a gene or gene product such as an aptamer. An inhibitory nucleic acid may inhibit the transcription of a gene or prevent the translation of the gene transcript in a cell. An inhibitory nucleic acid may be from 16 to 1000 nucleotides long, and in certain embodiments from 18 to 100 nucleotides long. Inhibitory nucleic acids are well known in the art. For example, siRNA, shRNA and double-stranded RNA have been described in U.S. Pat. Nos. 6,506,559 and 6,573,099, as well as in U.S. Patent Publications 2003/0051263, 2003/0055020, 2004/0265839, 2002/0168707, 2003/0159161, and 2004/0064842, all of which are herein incorporated by reference in their entirety. Since the discovery of RNAi by Fire and colleagues in 1998, the biochemical mechanisms have been rapidly characterized. Double stranded RNA (dsRNA) is cleaved by Dicer, which is an RNAase III family ribonuclease. This process yields siRNAs of ˜21 nucleotides in length. These siRNAs are incorporated into a multiprotein RNA-induced silencing complex (RISC) that is guided to target mRNA. RISC cleaves the target mRNA in the middle of the complementary region. In mammalian cells, the related microRNAs (miRNAs) are found that are short RNA fragments (˜22 nucleotides). miRNAs are generated after Dicer-mediated cleavage of longer (˜70 nucleotide) precursors with imperfect hairpin RNA structures. The miRNA is incorporated into a miRNA-protein complex (miRNP), which leads to translational repression of target mRNA. In designing a nucleic acid capable of generating an RNAi effect, there are several factors that need to be considered such as the nature of the siRNA, the durability of the silencing effect, and the choice of delivery system. To produce an RNAi effect, the siRNA that is introduced into the organism will typically contain exonic sequences. Furthermore, the RNAi process is homology dependent, so the sequences must be carefully selected so as to maximize gene specificity, while minimizing the possibility of cross-interference between homologous, but not gene-specific sequences. Particularly the siRNA exhibits greater than 80, 85, 90, 95, 98% or even 100% identity between the sequence of the siRNA and a portion of a EphA nucleotide sequence. Sequences less than about 80% identical to the target gene are substantially less effective. Thus, the greater identity between the siRNA and the gene to be inhibited, the less likely expression of unrelated genes will be affected. In addition, the size of the siRNA is an important consideration. In some embodiments, the present disclosure relates to siRNA molecules that include at least about 19-25 nucleotides, and are able to modulate gene expression. In the context of the present disclosure, the siRNA is particularly less than 500, 200, 100, 50, 25, or 20 nucleotides in length. In some embodiments, the siRNA is from about 25 nucleotides to about 35 nucleotides or from about 19 nucleotides to about 25 nucleotides in length. To improve the effectiveness of siRNA-mediated gene silencing, guidelines for selection of target sites on mRNA have been developed for optimal design of siRNA (Soutschek et al., 2004; Wadhwa et al., 2004). These strategies may allow for rational approaches for selecting siRNA sequences to achieve maximal gene knockdown. To facilitate the entry of siRNA into cells and tissues, a variety of vectors including plasmids and viral vectors such as adenovirus, lentivirus, and retrovirus have been used (Wadhwa et al., 2004). Within an inhibitory nucleic acid, the components of a nucleic acid need not be of the same type or homogenous throughout (e.g., an inhibitory nucleic acid may comprise a nucleotide and a nucleic acid or nucleotide analog). Typically, an inhibitory nucleic acid form a double-stranded structure; the double-stranded structure may result from two separate nucleic acids that are partially or completely complementary. In certain embodiments of the present invention, the inhibitory nucleic acid may comprise only a single nucleic acid (polynucleotide) or nucleic acid analog and form a double-stranded structure by complementing with itself (e.g., forming a hairpin loop). The double-stranded structure of the inhibitory nucleic acid may comprise 16-500 or more contiguous nucleobases, including all ranges derivable thereof. The inhibitory nucleic acid may comprise 17 to 35 contiguous nucleobases, more particularly 18 to 30 contiguous nucleobases, more particularly 19 to 25 nucleobases, more particularly 20 to 23 contiguous nucleobases, or 20 to 22 contiguous nucleobases, or 21 contiguous nucleobases that hybridize with a complementary nucleic acid (which may be another part of the same nucleic acid or a separate complementary nucleic acid) to form a double-stranded structure. siRNA can be obtained from commercial sources, natural sources, or can be synthesized using any of a number of techniques well-known to those of ordinary skill in the art. For example, commercial sources of predesigned siRNA include Invitrogen's Stealth™ Select technology (Carlsbad, CA), Ambion® (Austin, TX), and Qiagen® (Valencia, CA). An inhibitory nucleic acid that can be applied in the compositions and methods of the present invention may be any nucleic acid sequence that has been found by any source to be a validated downregulator of the gene or gene product. In some embodiments, the invention features an isolated siRNA molecule of at least 19 nucleotides, having at least one strand that is substantially complementary to at least ten but no more than thirty consecutive nucleotides of a nucleic acid that encodes a gene, and that reduces the expression of a gene or gene product. In one embodiments of the present disclosure, the siRNA molecule has at least one strand that is substantially complementary to at least ten but no more than thirty consecutive nucleotides of the mRNA that encodes a gene or a gene product. In one embodiments, the siRNA molecule is at least 75, 80, 85, or 90% homologous, particularly at least 95%, 99%, or 100% similar or identical, or any percentages in between the foregoing (e.g., the invention contemplates 75% and greater, 80% and greater, 85% and greater, and so on, and said ranges are intended to include all whole numbers in between), to at least 10 contiguous nucleotides of any of the nucleic acid sequences encoding a target therapeutic protein. The siRNA may also comprise an alteration of one or more nucleotides. Such alterations can include the addition of non-nucleotide material, such as to the end(s) of the 19 to 25 nucleotide RNA or internally (at one or more nucleotides of the RNA). In certain aspects, the RNA molecule contains a 3′-hydroxyl group. Nucleotides in the RNA molecules of the present invention can also comprise non-standard nucleotides, including non-naturally occurring nucleotides or deoxyribonucleotides. The double-stranded oligonucleotide may contain a modified backbone, for example, phosphorothioate, phosphorodithioate, or other modified backbones known in the art, or may contain non-natural internucleoside linkages. Additional modifications of siRNAs (e.g., 2′-O-methyl ribonucleotides, 2′-deoxy-2′-fluoro ribonucleotides, “universal base” nucleotides, 5-C-methyl nucleotides, one or more phosphorothioate internucleotide linkages, and inverted deoxyabasic residue incorporation) can be found in U.S. Publication 2004/0019001 and U.S. Pat. No. 6,673,611 (each of which is incorporated by reference in its entirety). Collectively, all such altered nucleic acids or RNAs described above are referred to as modified siRNAs. In one embodiment, siRNA is capable of decreasing the expression of a particular genetic product by at least 10%, at least 20%, at least 30%, or at least 40%, at least 50%, at least 60%, or at least 70%, at least 75%, at least 80%, at least 90%, at least 95% or more or any ranges in between the foregoing. 3. CRISPR/CAS CRISPRs (clustered regularly interspaced short palindromic repeats) are DNA loci containing short repetitions of base sequences. Each repetition is followed by short segments of “spacer DNA” from previous exposures to a virus. CRISPRs are found in approximately 40% of sequenced eubacteria genomes and 90% of sequenced archaea. CRISPRs are often associated with cas genes that code for proteins related to CRISPRs. The CRISPR/Cas system is a prokaryotic immune system that confers resistance to foreign genetic elements such as plasmids and phages and provides a form of acquired immunity. CRISPR spacers recognize and silence these exogenous genetic elements like RNAi in eukaryotic organisms. Repeats were first described in 1987 for the bacteriumEscherichia coli. In 2000, similar clustered repeats were identified in additional bacteria and archaea and were termed Short Regularly Spaced Repeats (SRSR). SRSR were renamed CRISPR in 2002. A set of genes, some encoding putative nuclease or helicase proteins, were found to be associated with CRISPR repeats (the cas, or CRISPR-associated genes). In 2005, three independent researchers showed that CRISPR spacers showed homology to several phage DNA and extrachromosomal DNA such as plasmids. This was an indication that the CRISPR/cas system could have a role in adaptive immunity in bacteria. Koonin and colleagues proposed that spacers serve as a template for RNA molecules, analogously to eukaryotic cells that use a system called RNA interference. In 2007 Barrangou, Horvath (food industry scientists at Danisco) and others showed that they could alter the resistance ofStreptococcus thermophilusto phage attack with spacer DNA. Doudna and Charpentier had independently been exploring CRISPR-associated proteins to learn how bacteria deploy spacers in their immune defenses. They jointly studied a simpler CRISPR system that relies on a protein called Cas9. They found that bacteria respond to an invading phage by transcribing spacers and palindromic DNA into a long RNA molecule that the cell then uses tracrRNA and Cas9 to cut it into pieces called crRNAs. CRISPR was first shown to work as a genome engineering/editing tool in human cell culture by 2012 It has since been used in a wide range of organisms including bakers yeast (S. cerevisiae), zebra fish, nematodes (C. elegans), plants, mice, and several other organisms. Additionally CRISPR has been modified to make programmable transcription factors that allow scientists to target and activate or silence specific genes. Libraries of tens of thousands of guide RNAs are now available. The first evidence that CRISPR can reverse disease symptoms in living animals was demonstrated in March 2014, when MIT researchers cured mice of a rare liver disorder. Since 2012, the CRISPR/Cas system has been used for gene editing (silencing, enhancing or changing specific genes) that even works in eukaryotes like mice and primates. By inserting a plasmid containing cas genes and specifically designed CRISPRs, an organism's genome can be cut at any desired location. CRISPR repeats range in size from 24 to 48 base pairs. They usually show some dyad symmetry, implying the formation of a secondary structure such as a hairpin, but are not truly palindromic. Repeats are separated by spacers of similar length. Some CRISPR spacer sequences exactly match sequences from plasmids and phages, although some spacers match the prokaryote's genome (self-targeting spacers). New spacers can be added rapidly in response to phage infection. CRISPR-associated (cas) genes are often associated with CRISPR repeat-spacer arrays. As of 2013, more than forty different Cas protein families had been described. Of these protein families, Cas1 appears to be ubiquitous among different CRISPR/Cas systems. Particular combinations of cas genes and repeat structures have been used to define 8 CRISPR subtypes (Ecoli, Ypest, Nmeni, Dvulg, Tneap, Hmari, Apern, and Mtube), some of which are associated with an additional gene module encoding repeat-associated mysterious proteins (RAMPs). More than one CRISPR subtype may occur in a single genome. The sporadic distribution of the CRISPR/Cas subtypes suggests that the system is subject to horizontal gene transfer during microbial evolution. Exogenous DNA is apparently processed by proteins encoded by Cas genes into small elements (˜30 base pairs in length), which are then somehow inserted into the CRISPR locus near the leader sequence. RNAs from the CRISPR loci are constitutively expressed and are processed by Cas proteins to small RNAs composed of individual, exogenously-derived sequence elements with a flanking repeat sequence. The RNAs guide other Cas proteins to silence exogenous genetic elements at the RNA or DNA level. Evidence suggests functional diversity among CRISPR subtypes. The Cse (Cas subtype Ecoli) proteins (called CasA-E inE. coli) form a functional complex, Cascade, that processes CRISPR RNA transcripts into spacer-repeat units that Cascade retains. In other prokaryotes, Cas6 processes the CRISPR transcripts. Interestingly, CRISPR-based phage inactivation inE. colirequires Cascade and Cas3, but not Cas1 and Cas2. The Cmr (Cas RAMP module) proteins found inPyrococcus furiosusand other prokaryotes form a functional complex with small CRISPR RNAs that recognizes and cleaves complementary target RNAs. RNA-guided CRISPR enzymes are classified as type V restriction enzymes. See also U.S. Patent Publication 2014/0068797, which is incorporated by reference in its entirety. i. Cas9 Cas9 is a nuclease, an enzyme specialized for cutting DNA, with two active cutting sites, one for each strand of the double helix. It has been demonstrated that one could disable one or both sites while preserving Cas9's ability to home located its target DNA. Jinek combined tracrRNA and spacer RNA into a “single-guide RNA” molecule that, mixed with Cas9, could find and cut the correct DNA targets. Jinek et al. proposed that such synthetic guide RNAs might be able to be used for gene editing. Cas9 proteins are highly enriched in pathogenic and commensal bacteria. CRISPR/Cas-mediated gene regulation may contribute to the regulation of endogenous bacterial genes, particularly during bacterial interaction with eukaryotic hosts. For example, Cas protein Cas9 ofFrancisella novicidauses a unique, small, CRISPR/Cas-associated RNA (scaRNA) to repress an endogenous transcript encoding a bacterial lipoprotein that is critical forF. novicidato dampen host response and promote virulence. ii. gRNA or sgRNA As an RNA guided protein, Cas9 requires a short RNA to direct the recognition of DNA targets (Mali et al., 2013a). Though Cas9 preferentially interrogates DNA sequences containing a PAM sequence NGG it can bind here without a protospacer target. However, the Cas9-gRNA complex requires a close match to the gRNA to create a double strand break (Cho et al., 2013; Hsu et al., 2013). CRISPR sequences in bacteria are expressed in multiple RNAs and then processed to create guide strands for RNA (Bikard et al., 2013). Because Eukaryotic systems lack some of the proteins required to process CRISPR RNAs the synthetic construct gRNA was created to combine the essential pieces of RNA for Cas9 targeting into a single RNA expressed with the RNA polymerase type III promoter U6 (Mali et al., 2013a, b). Synthetic gRNAs are slightly over 100 bp at the minimum length and contain a portion which is targets the 20 protospacer nucleotides immediately preceding the PAM sequence NGG; gRNAs do not contain a PAM sequence. 4. Modified Nucleobases In some embodiments, the nucleic acids of the present disclosure comprise one or more modified nucleosides comprising a modified sugar moiety. Such compounds comprising one or more sugar-modified nucleosides may have desirable properties, such as enhanced nuclease stability or increased binding affinity with a target nucleic acid relative to an oligonucleotide comprising only nucleosides comprising naturally occurring sugar moieties. In some embodiments, modified sugar moieties are substituted sugar moieties. In some embodiments, modified sugar moieties are sugar surrogates. Such sugar surrogates may comprise one or more substitutions corresponding to those of substituted sugar moieties. In some embodiments, modified sugar moieties are substituted sugar moieties comprising one or more non-bridging sugar substituent, including but not limited to substituents at the 2′ and/or 5′ positions. Examples of sugar substituents suitable for the 2′-position, include, but are not limited to: 2′-F, 2′-OCH3(“OMe” or “O-methyl”), and 2′-O(CH2)2OCH3(“MOE”). In certain embodiments, sugar substituents at the 2′ position is selected from allyl, amino, azido, thio, O-allyl, O—C1-C10alkyl, O—C1-C10substituted alkyl; OCF3, O(CH2)2SCH3, O(CH2)2—O—N(Rm)(Rn), and O—CH2—C(═O)—N(Rm)(Rn), where each Rm and Rn is, independently, H or substituted or unsubstituted C1-C10alkyl. Examples of sugar substituents at the 5′-position, include, but are not limited to: 5′-methyl (R or S); 5′-vinyl, and 5′-methoxy. In some embodiments, substituted sugars comprise more than one non-bridging sugar substituent, for example, T-F-5′-methyl sugar moieties (see, e.g., PCT International Application WO 2008/101157, for additional 5′,2′-bis substituted sugar moieties and nucleosides). Nucleosides comprising 2′-substituted sugar moieties are referred to as 2′-substituted nucleosides. In some embodiments, a 2′-substituted nucleoside comprises a 2′-substituent group selected from halo, allyl, amino, azido, SH, CN, OCN, CF3, OCF3, O, S, or N(Rm)-alkyl; O, S, or N(Rm)-alkenyl; O, S or N(Rm)-alkynyl; O-alkylenyl-O-alkyl, alkynyl, alkaryl, aralkyl, O-alkaryl, O-aralkyl, O(CH2)2SCH3, O(CH2)2—O—N(Rm)(Rn) or O—CH2—C(═O)—N(Rm)(Rn), where each Rmand R is, independently, H, an amino protecting group or substituted or unsubstituted C1-C10alkyl. These 2′-substituent groups can be further substituted with one or more substituent groups independently selected from hydroxyl, amino, alkoxy, carboxy, benzyl, phenyl, nitro (NO2), thiol, thioalkoxy (S-alkyl), halogen, alkyl, aryl, alkenyl and alkynyl. In some embodiments, a 2′-substituted nucleoside comprises a 2′-substituent group selected from F, NH2, N3, OCF3, O—CH3, O(CH2)3NH2, CH2—CH═CH2, O—CH2—CH═CH2, OCH2CH2OCH3, O(CH2)2SCH3, O—(CH2)2—O—N(Rm)(Rn), O(CH2)2O(CH2)2N(CH3)2, and N-substituted acetamide (O—CH2—C(═O)—N(Rm)(Rn) where each Rmand R. is, independently, H, an amino protecting group or substituted or unsubstituted C1-C10alkyl. In some embodiments, a 2′-substituted nucleoside comprises a sugar moiety comprising a 2′-substituent group selected from F, OCF3, O—CH3, OCH2CH2OCH3, O(CH2)2SCH3, O(CH2)2—O—N(CH3)2, —O(CH2)2O(CH2)2N(CH3)2, and O—CH2—C(═O)—N(H)CH3. In some embodiments, a 2′-substituted nucleoside comprises a sugar moiety comprising a 2′-substituent group selected from F, O—CH3, and OCH2CH2OCH3. Certain modified sugar moieties comprise a bridging sugar substituent that forms a second ring resulting in a bicyclic sugar moiety. In some such embodiments, the bicyclic sugar moiety comprises a bridge between the 4′ and the 2′ furanose ring atoms. Examples of such 4′ to 2′ sugar substituents, include, but are not limited to: —[C(Ra)(Rb)]n—, —[C(Ra)(Rb)]n—O—, —C(RaRb)—N(R)—O— or, —C(RaRb)—O—N(R)—; 4′-CH2-2′, 4′-(CH2)2-2′, 4′-(CH2)—O-2′ (LNA); 4′-(CH2)—S-2′; 4′-(CH2)2—O-2′ (ENA); 4′-CH(CH3)—O-2′ (cEt) and 4′-CH(CH2OCH3)—O-2′, and analogs thereof (see, e.g., U.S. Pat. No. 7,399,845); 4′-C(CH3)(CH3)—O-2′ and analogs thereof, (see, e.g., WO 2009/006478); 4′-CH2—N(OCH3)-2′ and analogs thereof (see, e.g., WO2008/150729); 4′-CH2—O—N(CH3)-2′ (see, e.g., US2004/0171570, published Sep. 2, 2004); 4′-CH2—O—N(R)-2′, and 4′-CH2—N(R)—O-2′-, wherein each R is, independently, H, a protecting group, or C1-C12alkyl; 4′-CH2—N(R)—O-2′, wherein R is H, C1-C12alkyl, or a protecting group (see, U.S. Pat. No. 7,427,672); 4′-CH2—C(H)(CH3)-2′ (see, e.g., Chattopadhyaya et al., J. Org. Chem., 2009, 74, 118-134); and 4′-CH2—C(═CH2)-2′ and analogs thereof (see, PCT International Application WO 2008/154401). In some embodiments, such 4′ to 2′ bridges independently comprise from 1 to 4 linked groups independently selected from —[C(Ra)(Rb)]n—, —C(Ra)═C(Rb)—, —C(Ra)═N—, —C(═NRa)—, —C(═O)—, —C(═S)—, —O—, —Si(Ra)2—, —S(═O)x—, and —N(Ra)—; wherein:x is 0, 1, or 2;n is 1, 2, 3, or 4;each Raand Rbis, independently, H, a protecting group, hydroxyl, C1-C12alkyl, substituted C1-C12alkyl, C2-C12alkenyl, substituted C2-C12alkenyl, C2-C12alkynyl, substituted C2-C12alkynyl, C5-C20aryl, substituted C5-C20aryl, heterocycle radical, substituted heterocycle radical, heteroaryl, substituted heteroaryl, C5-C7alicyclic radical, substituted C5-C7alicyclic radical, halogen, OJ1, NJ1J2, SJ1, N3, COOJ1, acyl (C(═O)—H), substituted acyl, CN, sulfonyl (S(═O)2-J1), or sulfoxyl (S(═O)-J1); andeach J1and J2is, independently, H, C1-C12alkyl, substituted C1-C12alkyl, C2-C12alkenyl, substituted C2-C12alkenyl, C2-C12alkynyl, substituted C2-C12alkynyl, C5-C20aryl, substituted C5-C20aryl, acyl (C(═O)—H), substituted acyl, a heterocycle radical, a substituted heterocycle radical, C1-C12aminoalkyl, substituted C1-C12aminoalkyl, or a protecting group. Nucleosides comprising bicyclic sugar moieties are referred to as bicyclic nucleosides or BNAs. Bicyclic nucleosides include, but are not limited to, (A) α-L-Methyleneoxy (4′-CH2—O-2′) BNA, (B) β-D-Methyleneoxy (4′-CH2—O-2′) BNA (also referred to as locked nucleic acid or LNA), (C) Ethyleneoxy (4′-(CH2)2—O-2′) BNA, (D) Aminooxy (4′-CH2—O—N(R)-2′) BNA, (E) Oxyamino (4′-CH2—N(R)—O-2′) BNA, (F) Methyl(methyleneoxy) (4′-CH(CH3)—O-2′) BNA (also referred to as constrained ethyl or cEt), (G) methylene-thio (4′-CH2—S-2′) BNA, (H) methylene-amino (4′-CH2—N(R)-2′) BNA, (I) methyl carbocyclic (4′-CH2—CH(CH3)-2′) BNA, (J) propylene carbocyclic (4′-(CH2)3-2′) BNA, and (K) Methoxy(ethyleneoxy) (4′-CH(CH2OMe)-O-2′) BNA (also referred to as constrained MOE or cMOE). Additional bicyclic sugar moieties are known in the art, for example: Singh et al., Chem. Commun., 1998, 4, 455-456; Koshkin et al., Tetrahedron, 1998, 54, 3607-3630; Wahlestedt et al., Proc. Natl. Acad. Sci. U.S.A., 2000, 97, 5633-5638; Kumar et al., Bioorg. Med. Chem. Lett., 1998, 8, 2219-2222; Singh et al., J. Org. Chem., 1998, 63, 10035-10039; Srivastava et al., J. Am. Chem. Soc., 129(26) 8362-8379 (Jul. 4, 2007); Elayadi et al., Curr. Opinion Invens. Drugs, 2001, 2, 5561; Braasch et al., Chem. Biol., 2001, 8, 1-7; Orum et al., Curr. Opinion Mol. Ther., 2001, 3, 239-243; U.S. Pat. Nos. 7,053,207, 6,268,490, 6,770,748, 6,794,499, 7,034,133, 6,525,191, 6,670,461, and 7,399,845; WO 2004/106356, WO 1994/14226, WO 2005/021570, and WO 2007/134181; U.S. Patent Publication Nos. US 2004/0171570, US 2007/0287831, and US 2008/0039618; U.S. Ser. Nos. 12/129,154, 60/989,574, 61/026,995, 61/026,998, 61/056,564, 61/086,231, 61/097,787, and 61/099,844; and PCT International Applications Nos. PCT/US2008/064591, PCT/US2008/066154, and PCT/US2008/068922. In some embodiments, bicyclic sugar moieties and nucleosides incorporating such bicyclic sugar moieties are further defined by isomeric configuration. For example, a nucleoside comprising a 4′-2′ methylene-oxy bridge, may be in the .alpha.-L configuration or in the .beta.-D configuration. Previously, α-L-methyleneoxy (4′-CH2—O-2′) bicyclic nucleosides have been incorporated into antisense oligonucleotides that showed antisense activity (Frieden et al., Nucleic Acids Research, 2003, 21, 6365-6372). In some embodiments, substituted sugar moieties comprise one or more non-bridging sugar substituent and one or more bridging sugar substituent (e.g., 5′-substituted and 4′-2′ bridged sugars; PCT International Application WO 2007/134181, wherein LNA is substituted with, for example, a 5′-methyl or a 5′-vinyl group). In some embodiments, modified sugar moieties are sugar surrogates. In some such embodiments, the oxygen atom of the naturally occurring sugar is substituted, e.g., with a sulfer, carbon or nitrogen atom. In some such embodiments, such modified sugar moiety also comprises bridging and/or non-bridging substituents as described above. For example, certain sugar surrogates comprise a 4′-sulfur atom and a substitution at the 2′-position (see, e.g., published U.S. Patent Application US 2005/0130923) and/or the 5′ position. By way of additional example, carbocyclic bicyclic nucleosides having a 4′-2′ bridge have been described (see, e.g., Freier et al., Nucleic Acids Research, 1997, 25(22), 4429-4443 and Albaek et al., J. Org. Chem., 2006, 71, 7731-7740). In some embodiments, sugar surrogates comprise rings having other than 5-atoms. For example, in some embodiments, a sugar surrogate comprises a six-membered tetrahydropyran. Such tetrahydropyrans may be further modified or substituted. Nucleosides comprising such modified tetrahydropyrans include, but are not limited to, hexitol nucleic acid (HNA), anitol nucleic acid (ANA), manitol nucleic acid (MNA) (see Leumann, C J. Bioorg. & Med. Chem. (2002) 10:841-854), and fluoro HNA (F-HNA). In some embodiments, the modified THP nucleosides of Formula VII are provided wherein q1, q2, q3, q4, q5, q6and q7are each H. In certain embodiments, at least one of q1, q2, q3, q4, q5, q6and q7is other than H. In some embodiments, at least one of q1, q2, q3, q4, q5, q6and q7is methyl. In some embodiments, THP nucleosides of Formula VII are provided wherein one of R1and R2is F. In certain embodiments, R1is fluoro and R2is H, R1is methoxy and R2is H, and R1is methoxyethoxy and R2is H. Many other bicyclo and tricyclo sugar surrogate ring systems are also known in the art that can be used to modify nucleosides for incorporation into antisense compounds (see, e.g., review article: Leumann, J. C, Bioorganic & Medicinal Chemistry, 2002, 10, 841-854). Combinations of modifications are also provided without limitation, such as 2′-F-5′-methyl substituted nucleosides (see PCT International Application WO 2008/101157 for other disclosed 5′,2′-bis substituted nucleosides) and replacement of the ribosyl ring oxygen atom with S and further substitution at the 2′-position (see U.S. Patent Publication US 2005/0130923) or alternatively 5′-substitution of a bicyclic nucleic acid (see PCT International Application WO 2007/134181 wherein a 4′-CH2—O-2′ bicyclic nucleoside is further substituted at the 5′ position with a 5′-methyl or a 5′-vinyl group). The synthesis and preparation of carbocyclic bicyclic nucleosides along with their oligomerization and biochemical studies have also been described (see, e.g., Srivastava et al., 2007). In some embodiments, the present invention provides oligonucleotides comprising modified nucleosides. Those modified nucleotides may include modified sugars, modified nucleobases, and/or modified linkages. The specific modifications are selected such that the resulting oligonucleotides possess desirable characteristics. In some embodiments, oligonucleotides comprise one or more RNA-like nucleosides. In some embodiments, oligonucleotides comprise one or more DNA-like nucleotides. In some embodiments, nucleosides of the present invention comprise one or more unmodified nucleobases. In certain embodiments, nucleosides of the present invention comprise one or more modified nucleobases. In some embodiments, modified nucleobases are selected from: universal bases, hydrophobic bases, promiscuous bases, size-expanded bases, and fluorinated bases as defined herein. 5-substituted pyrimidines, 6-azapyrimidines and N-2, N-6 and O-6 substituted purines, including 2-aminopropyladenine, 5-propynyluracil; 5-propynylcytosine; 5-hydroxymethyl cytosine, xanthine, hypoxanthine, 2-aminoadenine, 6-methyl and other alkyl derivatives of adenine and guanine, 2-propyl and other alkyl derivatives of adenine and guanine, 2-thiouracil, 2-thiothymine and 2-thiocytosine, 5-halouracil and cytosine, 5-propynyl CH3) uracil and cytosine and other alkynyl derivatives of pyrimidine bases, 6-azo uracil, cytosine and thymine, 5-uracil (pseudouracil), 4-thiouracil, 8-halo, 8-amino, 8-thiol, 8-thioalkyl, 8-hydroxyl and other 8-substituted adenines and guanines, 5-halo particularly 5-bromo, 5-trifluoromethyl and other 5-substituted uracils and cytosines, 7-methylguanine and 7-methyladenine, 2-F-adenine, 2-aminoadenine, 8-azaguanine and 8-azaadenine, 7-deazaguanine and 7-deazaadenine, 3-deazaguanine and 3-deazaadenine, universal bases, hydrophobic bases, promiscuous bases, size-expanded bases, and fluorinated bases as defined herein. Further modified nucleobases include tricyclic pyrimidines such as phenoxazine cytidine([5,4-b][1,4]benzoxazin-2(3H)-one), phenothiazine cytidine (1H-pyrimido[5,4-b][1,4]benzothiazin-2(3H)-one), G-clamps such as a substituted phenoxazine cytidine (e.g., 9-(2-aminoethoxy)-H-pyrimido[5,4-13][1,4]benzoxazin-2(3H)-one), carbazole cytidine (2H-pyrimido[4,5-b]indol-2-one), pyridoindole cytidine (H-pyrido[3′,2′:4,5]pyrrolo[2,3-d]pyrimidin-2-one). Modified nucleobases may also include those in which the purine or pyrimidine base is replaced with other heterocycles, for example 7-deazaadenine, 7-deazaguanosine, 2-aminopyridine and 2-pyridone. Further nucleobases include those disclosed in U.S. Pat. No. 3,687,808, those disclosed in The Concise Encyclopedia Of Polymer Science And Engineering, Kroschwitz, J. I., Ed., John Wiley & Sons, 1990, 858-859; those disclosed by Englisch et al., 1991; and those disclosed by Sanghvi, Y. S., 1993. Representative United States Patents that teach the preparation of certain of the above noted modified nucleobases as well as other modified nucleobases include without limitation, U.S. Pat. Nos. 3,687,808; 4,845,205; 5,130,302; 5,134,066; 5,175,273; 5,367,066; 5,432,272; 5,457,187; 5,459,255; 5,484,908; 5,502,177; 5,525,711; 5,552,540; 5,587,469; 5,594,121; 5,596,091; 5,614,617; 5,645,985; 5,681,941; 5,750,692; 5,763,588; 5,830,653 and 6,005,096, each of which is herein incorporated by reference in its entirety. In some embodiments, the present invention provides oligonucleotides comprising linked nucleosides. In such embodiments, nucleosides may be linked together using any internucleoside linkage. The two main classes of internucleoside linking groups are defined by the presence or absence of a phosphorus atom. Representative phosphorus containing internucleoside linkages include, but are not limited to, phosphodiesters (P═O), phosphotriesters, methylphosphonates, phosphoramidate, and phosphorothioates (P═S). Representative non-phosphorus containing internucleoside linking groups include, but are not limited to, methylenemethylimino (—CH2—N(CH3)—O—CH2—), thiodiester (—O—C(O)—S—), thionocarbamate (—O—C(O)(NH)—S—); siloxane (—O—Si(H)2—O—); and N,N′-dimethylhydrazine (—CH2—N(CH3)—N(CH3)—). Modified linkages, compared to natural phosphodiester linkages, can be used to alter, typically increase, nuclease resistance of the oligonucleotide. In some embodiments, internucleoside linkages having a chiral atom can be prepared as a racemic mixture, or as separate enantiomers. Representative chiral linkages include, but are not limited to, alkylphosphonates and phosphorothioates. Methods of preparation of phosphorous-containing and non-phosphorous-containing internucleoside linkages are well known to those skilled in the art. The oligonucleotides described herein contain one or more asymmetric centers and thus give rise to enantiomers, diastereomers, and other stereoisomeric configurations that may be defined, in terms of absolute stereochemistry, as (R) or (S), α or β such as for sugar anomers, or as (D) or (L) such as for amino acids etc. Included in the antisense compounds provided herein are all such possible isomers, as well as their racemic and optically pure forms. Neutral internucleoside linkages include without limitation, phosphotriesters, methylphosphonates, MMI (3′-CH2—N(CH3)—O-5′), amide-3 (3′-CH2—C(═O)—N(H)-5′), amide-4 (3′-CH2—N(H)—C(═O)-5′), formacetal (3′-O—CH2—O-5′), and thioformacetal (3′-S—CH2—O-5′). Further neutral internucleoside linkages include nonionic linkages comprising siloxane (dialkylsiloxane), carboxylate ester, carboxamide, sulfide, sulfonate ester and amides (See for example: Carbohydrate Modifications in Antisense Research; Y. S. Sanghvi and P. D. Cook, Eds., ACS Symposium Series 580; Chapters 3 and 4, 40-65). Further neutral internucleoside linkages include nonionic linkages comprising mixed N, O, S and CH2component parts. Additional modifications may also be made at other positions on the oligonucleotide, particularly the 3′ position of the sugar on the 3′ terminal nucleotide and the 5′ position of 5′ terminal nucleotide. For example, one additional modification of the ligand conjugated oligonucleotides of the present invention involves chemically linking to the oligonucleotide one or more additional non-ligand moieties or conjugates which enhance the activity, cellular distribution or cellular uptake of the oligonucleotide. Such moieties include but are not limited to lipid moieties such as a cholesterol moiety (Letsinger et al., 1989), cholic acid (Manoharan et al., 1994), a thioether, e.g., hexyl-5-tritylthiol (Manoharan et al., 1992; Manoharan et al., 1993), a thiocholesterol (Oberhauser et al., 1992), an aliphatic chain, e.g., dodecandiol or undecyl residues (Saison-Behmoaras et al., 1991; Kabanov et al., 1990; Svinarchuk et al., 1993), a phospholipid, e.g., di-hexadecyl-rac-glycerol or triethylammonium 1,2-di-O-hexadecyl-rac-glycero-3-H-phosphonate (Manoharan et al., 1995; Shea et al., 1990), a polyamine or a polyethylene glycol chain (Manoharan et al., 1995), or adamantane acetic acid (Manoharan et al., 1995), a palmityl moiety (Mishra et al., 1995), or an octadecylamine or hexylamino-carbonyl-oxycholesterol moiety (Crooke et al., 1996). Representative United States patents that teach the preparation of such oligonucleotide conjugates include, but are not limited to, U.S. Pat. Nos. 4,828,979; 4,948,882; 5,218,105; 5,525,465; 5,541,313; 5,545,730; 5,552,538; 5,578,717, 5,580,731; 5,580,731; 5,591,584; 5,109,124; 5,118,802; 5,138,045; 5,414,077; 5,486,603; 5,512,439; 5,578,718; 5,608,046; 4,587,044; 4,605,735; 4,667,025; 4,762,779; 4,789,737; 4,824,941; 4,835,263; 4,876,335; 4,904,582; 4,958,013; 5,082,830; 5,112,963; 5,214,136; 5,082,830; 5,112,963; 5,214,136; 5,245,022; 5,254,469; 5,258,506; 5,262,536; 5,272,250; 5,292,873; 5,317,098; 5,371,241, 5,391,723; 5,416,203, 5,451,463; 5,510,475; 5,512,667; 5,514,785; 5,565,552; 5,567,810; 5,574,142; 5,585,481; 5,587,371; 5,595,726; 5,597,696; 5,599,923; 5,599,928 and 5,688,941, each of which is herein incorporated by reference. E. KITS The present disclosure also provides kits. Any of the components disclosed herein may be combined in the form of a kit. In some embodiments, the kits comprise a dendrimer or a composition as described above or in the claims. The kits will generally include at least one vial, test tube, flask, bottle, syringe or other container, into which a component may be placed, and preferably, suitably aliquoted. Where there is more than one component in the kit, the kit also will generally contain a second, third or other additional containers into which the additional components may be separately placed. However, various combinations of components may be comprised in a container. In some embodiments, all of the nucleic acid delivery components are combined in a single container. In other embodiments, some or all of the dendrimer delivery components with the instant polymers are provided in separate containers. The kits of the present invention also will typically include packaging for containing the various containers in close confinement for commercial sale. Such packaging may include cardboard or injection or blow molded plastic packaging into which the desired containers are retained. A kit may also include instructions for employing the kit components. Instructions may include variations that can be implemented. F. EXAMPLES The following examples are included to demonstrate preferred embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention. Example 1: Materials and Instrumentation 1. Materials for Chemical Synthesis All amines, thiols, and otherwise unspecified chemicals were purchased from Sigma-Aldrich. 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) was purchased from Avanti Lipids. Lipid PEG2000 was chemically synthesized, as described below. C12-200 was synthesized following the reported procedure (Love et al., 2010). All organic solvents were purchased from Fisher Scientific and purified with a solvent purification system (Innovative Technology). 2. Nucleic Acids and Other Materials for In Vitro and In Vivo Experiments All siRNAs were purchased from Sigma-Aldrich. Let-7g miRNA mimic and its control mimic were purchased from Ambion by Life Technologies. Dulbecco's Modified Eagle Media (DMEM) and fetal bovine serum (FBS) were purchased from Sigma-Aldrich. OptiMEM, DAPI, and Alexa Fluor 488 phalloidin were purchased from Life Technologies. ONE-Glo+Tox was purchased from Promega. Biophen FVII was purchased from Aniara Corporation. The sequence for the sense and antisense strands of siRNAs were as follows: siLuc siRNA against Luciferase). dT are DNA bases. All others are RNA bases. sense:(SEQ ID NO: 3)5′-GAUUAUGUCCGGUUAUGUA[dT][dT]-3′antisense:(SEQ ID NO: 4)3′-UACAUAACCGGACAUAAUC[dT][dT]-5′ siFVII (siRNA against FVII). 2′-Fluoro modified nucleotides are lower case. sense:(SEQ ID NO: 1)5′-GGAucAucucAAGucuuAc[dT][dT]-3′antisense:(SEQ ID NO: 2)3′-GuAAGAcuuGAGAuGAucc[dT][dT]-5′ siCTR (siRNA as control) sense:(SEQ ID NO: 5)5′-GCGCGAUAGCGCGAAUAUA[dT][dT]-3′antisense:(SEQ ID NO: 6)3′-UAUAUUCGCGCUAUCGCGC[dT][dT]-5′ Sigma-Aldrich MISSION siRNA Universal Negative Control #1 (catalog number: SIC001) was used as a non-targeted siRNA in control experiments. 2′ OMe modified control siRNAs (Sigma-Aldrich, proprietary modifications) were used in in vivo studies to reduce immune stimulation. Cy5.5-labeled siRNA (siRNA for imaging) sense:(SEQ ID NO: 3)5′-Cy5.5-GAUUAUGUCCGGUUAUGUA[dT][dT]-3′antisense:(SEQ ID NO: 4)3′-UACAUAACCGGACAUAAUC[dT][dT]-5′ Let-7g miRNA mimic Ambion (Life Technologies) mirVana miRNA mimic (catalog number: 4464070, product ID: MC11758, name: has-let-7g). Exact sequence and modifications not disclosed by Ambion. Mimics mature human Let-7g. Negative Control (CTR) miRNA Mimic Ambion (Life Technologies) mirVana miRNA Mimic, Negative Control #1 (catalog number: 4464061). Exact sequence and modifications not disclosed by Ambion. 3. Robotic Automation Nanoparticle (NP) formulations and in vitro screening were performed on a Tecan Freedom EVO 200 fluid handling robot equipped with an 8-channel liquid handling arm (LiHa), multi-channel arm with 96-channel head (MCA), robotic manipulator arm (RoMa), and an integrated InfiniTe F/M200 Pro microplate reader (Tecan). Two integrated custom heating and stirring chemical reaction stations (V&P Scientific 710E-3HM Series Tumble Stirrers) provided reaction and mixing support. All operations were programmed in EVOware Standard software (Tecan). 4. Synthetic Characterization 1H and13C NMR were performed on a Varian 500 MHz spectrometer. MS was performed on a Voyager DE-Pro MALDI TOF. Flash chromatography was performed on a Teledyne Isco CombiFlash Rf-200i chromatography system equipped with UV-vis and evaporative light scattering detectors (ELSD). Particle sizes and zeta potentials were measured by Dynamic Light Scattering (DLS) using a Malvern Zetasizer Nano ZS (He—Ne laser, λ=632 nm). 5. Nanoparticle Formulation for In Vivo Studies Formulated dendrimer nanoparticles for in vivo studies were prepared using a microfluidic mixing instrument with herringbone rapid mixing features (Precision Nanosystems NanoAssemblr). Ethanol solutions of dendrimers, DSPC, cholesterol, and lipid PEG2000 were rapidly combined with acidic solutions of siRNA as described below. The typical ratio of aqueous:EtOH was 3:1 (volume) and the typical flow rate was 12 mL/minute. 6. Automated, In Vitro Delivery Screening of Modular Degradable Dendrimers Nanoparticle (NP) formulations and in vitro screening were performed on a Tecan Freedom EVO 200 fluid handling robot equipped with an 8-channel liquid handling arm (LiHa), multi-channel arm with 96-channel head (MCA), robotic manipulator arm (RoMa), and an integrated InfiniTe F/M200 Pro microplate reader (Tecan). HeLa cells stably expressing firefly luciferase (HeLa-Luc) were derived from HeLa cells (ATCC) by stable transfection of the luciferase gene using lentiviral infection followed by clonal selection. HeLa-Luc cells were seeded (10,000 cells/well) into each well of an opaque white 96-well plate (Corning) and allowed to attach overnight in phenol red-free DMEM supplemented with 5% FBS. The media was replaced with fresh, FBS-containing media on the second day before starting the transfection. G1DD-siLuc nanoparticles were formulated with the aid of an automated, fluid-handling robot to accelerate the discovery process. All operations were programmed in EVOware Standard software. First, dendrimer reaction solutions were diluted from the original reaction concentration to 12.5 mM in ethanol. Next, the dendrimer solutions were diluted a second time from 12.5 mM to 1 mM in ethanol using the LiHa arm. Then, 89.2 μL of a lipid mixture in ethanol was added into a 96-well clear plate. The lipid mixture was composed of DSPC (0.0690 mM), cholesterol (0.2622 mM), and lipid PEG2000 (0.0138 mM) in ethanol. Subsequently, 30.8 μL of each dendrimer (1 mM) was added to the lipid mixture in the 96-well plate via the LiHa, followed by rapid mixing (15 times; 75 μL mixing volume; 250 μL/second speed). The LiHa added and mixed 8 tips at once. To a second clear 96-well plate, 50 μL of siLuc (20 ng/μL) in citrate buffer (pH=4.3) was added via the LiHa. 30 μL of the ethanol mixture (dendrimer, DSPC, cholesterol, lipid PEG2000) was then added to the 50 μL siLuc solution, followed by rapid mixing (15 times; 75 μL mixing volume; 250 μL/second speed) to form the dendrimer nanoparticles. Next, 120 μL of sterile PBS (lx) was added and mixed using the LiHa to dilute the NPs and increase the pH. Subsequently, the plates were re-formatted to allow for facile transfer to growing cells. Finally, 20 μL of the NP solutions was added to culturing cells using sterile disposable tips via the MCA96 head to avoid contamination. The cells ultimately received 100 ng siLuc (33 nM). The mol ratio of dendrimer to siLuc was 100:1 during this screening phase. The final composition of the formulation was G1DD:cholesterol:DSPC:lipid PEG2000: =50:38:10:2 (by mole). Cells were incubated for 24 h at 37° C., 5% CO2and then firefly luciferase activity and viability was analyzed using One Glo+Tox assay kits (Promega). 7. Dendrimer-Small RNA Formulations for In Vivo Studies Formulated dendrimer nanoparticles for in vivo studies were prepared using a microfluidic mixing instrument with herringbone rapid mixing features (Precision Nanosystems NanoAssemblr). Ethanol solutions of dendrimer, DSPC, cholesterol, and lipid PEG2000 (molar ratio of 50:38:10:2) were rapidly combined with acidic solutions of small RNA to give the final weight ratio of 25:1 (dendrimer:small RNA). The typical ratio of aqueous:EtOH was 3:1 (volume) and the typical flow rate was 12 mL/minute. C12-200 LNPs were prepared according to the reported procedure (Love et al., 2010). Ethanol solutions of C12-200, DSPC, cholesterol, and lipid PEG2000 (molar ratio of 50:38.5:10:1.5) were rapidly combined with acidic solutions of small RNA to give the final weight ratio of 7:1 (C12-200:small RNA). All formulated NPs were purified by dialysis in sterile PBS with 3.5 kD cut-off and the size was measured by Dynamic Light Scattering (DLS) prior to in vivo studies. When applicable, the encapsulation of small RNAs was measured with Ribogreen binding assay (Invitrogen) by taking the small amount of solution and following its protocol. 8. Animal Studies All experiments were approved by the Institutional Animal Care and Use Committees of The University of Texas Southwestern Medical Center and were consistent with local, state and federal regulations as applicable. Female C57BL/6 mice were purchased from Harlan Laboratories (Indianapolis, IN). Transgenic mice bearing MYC-driven liver tumors were generated by crossing the TRE-MYC strain with LAP-tTA strain. Mice bearing the LAP-tTA and TRE-MYC genotype were maintained on 1 mg/mL of dox, and MYC was induced by withdrawing dox. Power analysis was performed to anticipate required number of animals to achieve statistical significance. 9. In Vivo Factor VII Silencing in Mice For in vivo delivery screening, female C57BL/6 mice received tail vein i.v. injections of PBS (negative control, n=3) or dendrimer NPs containing non-targeting siRNA (siCTR, negative control, n=3) or dendrimer NPs containing anti-Factor VII siRNA (siFVII, n=3) diluted in PBS (200 μL or less in total volume). After 48 h, body-weight gain/loss was measured and mice were anaesthetized by isofluorane inhalation for blood sample collection by retro-orbital eye bleed. Serum was isolated with serum separation tubes (Becton Dickinson) and Factor VII protein levels were analyzed by a chromogenic assay (Biophen FVII, Aniara Corporation). A standard curve was constructed using samples from PBS-injected mice and relative Factor VII expression was determined by comparing treated groups to an untreated PBS control. For the therapeutic study, FVII knockdown in transgenic mice were verified with the above blood assay and by qPCR using harvested liver tissues. To evaluate statistical significance, two-tailed Student's t-tests with the 95% confidence level were conducted. 10. Biodistribution Female C57BL/6 mice or transgenic mice bearing liver tumors received tail vein i.v. injections with dendrimer NPs containing Cy5.5-siRNA at 1 mg/kg of siRNA in 200 μL. At 24 h post injection, mice were euthanized and organs were removed. The biodistribution was assessed by imaging whole organs with an IVIS Lumina System (Caliper Life Sciences) with the Cy5.5 filter setting. For confocal imaging, the tissue was cryo-sectioned (7 μm) and fixed using 4% paraformaldehyde at room temperature for 10 min. The slides were washed three times with PBS and blocked for 30 min in PBS with 1% albumin. Sections were then incubated for 30 min with Alexa Fluor 488 Phalloidin (1:200 dilution, Life Technologies) in PBS with 1% albumin. Slides were washed three times with 0.1% Tween 20 and mounted using ProLong Gold Antifade (Life Technologies). Sections were imaged using an LSM 700 point scanning confocal microscope (Zeiss) equipped with a 25× objective. 11. In Vivo Toxicity Evaluation and Let-7g Therapeutic Studies Wild-type mice or transgenic mice bearing liver tumors were randomly divided into different groups. Mice received tail vein i.v. injections of dendrimer NPs containing siCTR. Their body weight was monitored daily. For transgenic mice bearing liver tumors, multiple tail vain injections were performed to simulate repeated dosing. For Let-7g therapeutic studies, transgenic mice bearing liver tumors received weekly tail vein i.v. injections of dendrimer NPs with Let-7g mimic or CTR mimic at a dosage of 1 mg/kg in 200 μL PBS from the age of 26 to 61 days. Processing order randomization was used. No blinding was done. Their body weight, abdomen size, and survival were carefully monitored. To evaluate statistical significance, two-tailed T tests with the 95% confidence level or Mantel-Cox tests were conducted. Example 2: Synthesis and Characterization of PEG Lipids and Dendrimers 1. Synthesis of Library Containing 1,512 First-Generation Degradable Dendrimers (G1DDs) G1DDs were synthesized through two sequential orthogonal reactions. At first, amines with different initial branching centers (IBCs) were separately reacted with the acrylate group of 2-(acryloyloxy)ethyl methacrylate (AEMA) with the mole ratio of amine to AEMA equaling the IBC numbers (e.g. 2A amines: two equivalents of AEMA were added; 6A amines: six equivalents of AEMA were added). Reactions were conducted with the addition of 5 mol % butylated hydroxyltoluene (BHT) for 24 hours at 50° C. Next, each first-step adduct was reacted separately with each thiol at the mole ratio of thiol to adduct equaling the amine IBC numbers (e.g. 2A amine first-step adduct: two equivalents of each thiol was added; 6A amine first-step adduct: six equivalents of each thiol was added). Reactions were conducted with the addition of 5 mol % dimethylphenylphosphine (DMPP) catalyst for 48 hours at 60° C. The 1,512 member library synthesis was accelerated by conducting reactions in glass vials and aluminum reaction blocks. Custom heating and stirring chemical reaction stations (V&P Scientific 710E-3HM Series Tumble Stirrers) were employed. Initial in vitro delivery screening experiments were conducted with crude G1DDs. Follow-up studies to verify activity were performed using purified dendrimers. All in vivo animal experiments were performed with purified G1DDs. Purified G1DDs were obtained by column flash chromatography on a neutral alumina column using a Teledyne Isco chromatography system with the gradient eluent of hexane and ethyl acetate. 2. Synthesis of Higher Generation Degradable Dendrimers (HGDDs) (1A2-G2-SC8 as an Example) Higher generation degradable dendrimers were prepared according to the previous method (Ma et al., 2009). 1A2-G1 was prepared directly after 1A2 amine reacted with one equivalent of AEMA in the presence of 5 mol % BHT at 50° C. for 24 hours. 1A2-G1 (4.00 g, 11.7 mmol) was dissolved in 10 mL DMSO. After addition of 2-aminoethanthiol (1.37 g, 17.5 mmol) into the above solution, the reaction was stirred at room temperature for 30 min. Then 300 mL dichloromethane was immediately added into the reaction solution and was washed with cold brine water (50 mL×3) to remove extra 2-aminoethanthiol. The organic phase was dried with magnesium sulfate and condensed via rotary evaporation to use directly for next step. AEMA (4.75 g, 25.8 mmol) and BHT (227 mg, 1.08 mmol) were added into the above solution. The reaction was stirred at 50° C. and monitored by1H NMR. After the reaction was complete, the solution was repeatedly washed with 20 mL hexane portions until no EAMA was found through TLC plate analysis. The washed solution was dried in vacuum to yield a viscous liquid 1A3-G2 directly for the next step. 1A3-G2 was reacted by following the above two-step synthetic procedure to give the viscous liquid 1A3-G3 directly for next the step. After 1A2-G3 (0.5 g, 0.3 mmol) was dissolved in 0.5 mL DMSO, 1-octanethiol (216 μL, 1.22 mmol) and dimethylphenylphosphine (DMPP) (8.6 μL, 0.061 mmol) was added. The reaction was stirred at 60° C. for 48 hours and then purified by running a neutral alumina column with the gradient eluent of hexane and ethyl acetate. A light-yellow viscous liquid 1A2-G3-SC8 was obtained. 3. Synthesis of Lipid PEG2000 PEG44-OH (80 g, 40 mmol) and pyridine (6.5 mL, 80 mmol) were dissolved in 250 mL anhydrous DCM and cooled at 0° C. Methanesulfonyl chloride (15.5 mL, 200 mmol) in 50 mL DCM was added over 30 min and the mixture was stirred overnight at room temperature. Another 100 mL DCM was added and the organic phase washed with saturated NaHCO3solution (50 mL×3), and then brine (50 mL×3). The resulting solution was concentrated and the residue was recrystallized in isopropanol and dried to yield a white powder PEG2000-Ms (74 g, 93%). PEG2000-Ms (35.41 g, 17.7 mmol) was dissolved in 250 mL of DMF. Then, NaN3(12.4 g, 19.0 mmol) was added into the solution. The reaction was stirred under nitrogen for 2 days at 50° C. After removal of DMF, the residual was dissolved in 300 mL DCM and washed with brine (50 mL×3). After removal of solvents, the residual oil was dissolved in 50 mL of methanol and the product was precipitated three times with 300 mL of diethyl ether to give the desired compound (25.55 g, 72%) as a white powder PEG2000-N3. Propargylamine (0.50 g, 9.1 mmol), BHT (191 mg, 0.91 mmol), and EAMA (2.73 g, 18.2 mmol) were added into a 25 mL reaction vial. The mixture was stirred for 48 hours at 50° C. The reaction was cooled down to give a colorless oil product T3-G1 without purification for use in the next reaction. 4. Characterization of Select Dendrimers 1H NMR (400 MHz, CDCl3, δ): 4.38-4.19 (br, 28H, —OCH2CH2O—), 2.90-2.80 (br, 7H, —C(O)CH(CH3)CH2S—), 2.75-2.71 (br, 14H, —NCH2CH2C(O)—), 2.70-2.49 (br, 28H, —C(O)CH(CH3)CH2S—, —SCH2—), 2.49-2.39 (br, 36H, —N(CH3)2, —NCH2CH2N(CH2CH2)2NCH2—, —CH2N(CH2-)2), 1.57-1.48 (m, 8H, —SCH2CH2CH2—), 1.37-1.28 (br, 8H, SCH2CH2CH2—), 1.28-1.16 (br, 53H, —SCH2CH2(CH2)4CH3, —CHC(CH3)CH2S—), 0.85 (t, J=7.1 Hz, 12H, —(CH2)4CH3).13C NMR (400 MHz, CDCl3, δ): 174.92, 172.03, 62.22, 62.17, 62.13, 62.07, 49.06, 40.23, 40.14, 35.36, 32.68, 32.56, 31.76, 29.60, 29.14, 28.82, 22.58, 16.85, 16.81, 14.04. MS (MALDI-TOF, m/z) Calc. for C109H196N6O28S7: 2261.21, found: 2262.43. 1H NMR (400 MHz, CDCl3, δ): 4.34-4.21 (br, 16H, —OCH2CH2O—), 2.82-2.76 (m, 4H, —SCH2CH(CH3)—), 2.73 (t, J=7.1 Hz, 8H, —C(O)CH2CH2N—), 2.70-2.64 (m, 4H, —SCH2CH(CH3)—), 2.58-2.51 (m, 4H, —SCH2CH(CH3)—), 2.51-2.46 (m, 8H, —CH2CH2S—), 2.45-2.40 (m, 18H, (—C(O)CH2CH2)2NCH2CH2CH2N(CH2-)2), 2.35-2.26 (br, 4H, —CH2CH2N(CH2-)2), 1.65-1.58 (br, 4H, —NCH2CH2CH2N—), 1.57-1.49 (m, 8H, —SCH2CH2CH2—), 1.37-1.28 (br, 8H, —SCH2CH2CH2—), 1.28-1.16 (br, 44H, —SCH2CH2(CH2)4CH3, —CHC(CH3)CH2S—), 0.85 (t, J=7.0 Hz, 12H, —(CH2)4CH3).13C NMR (400 MHz, CDCl3, δ): 174.90, 172.18, 62.18, 62.05, 49.05, 40.14, 35.37, 32.68, 32.40, 31.76, 29.60, 29.15, 28.83, 22.60, 16.81, 14.08. MS (MALDI-TOF, m/z) Calc. for C78H144N4O16S4: 1520.95, found: 1521.32. 1H NMR (400 MHz, CDCl3, δ): 4.32-4.21 (br, 16H, —OCH2CH2O—), 2.82-2.76 (m, 4H, —SCH2CH(CH3)—), 2.73 (t, J=7.0 Hz, 8H, —C(O)CH2CH2N—), 2.69-2.62 (m, 4H, —SCH2CH(CH3)—), 2.58-2.50 (m, 4H, —SCH2CH(CH3)—), 2.50-2.45 (m, 8H, —CH2CH2S—), 2.45-2.38 (m, 12H, (—C(O)CH2CH2)2NCH2—), 2.34-2.24 (br, 4H, —CH2N(CH3)CH2—), 2.24-2.00 (br, 3H, —CH2N(CH3)CH2—) 1.66-1.57 (br, 4H, —NCH2CH2CH2N—), 1.57-1.48 (m, 8H, —SCH2CH2CH2—), 1.37-1.28 (br, 8H, —SCH2CH2CH2—), 1.28-1.16 (br, 45H, —SCH2CH2(CH2)4CH3, —CHC(CH3)CH2S—), 0.85 (t, J=7.0 Hz, 12H, —(CH2)4CH3).13C NMR (400 MHz, CDCl3, δ): 174.90, 172.18, 62.18, 62.05, 49.00, 40.13, 35.36, 32.68, 32.35, 31.76, 29.60, 29.15, 28.83, 22.60, 16.81, 14.04. MS (MALDI-TOF, m/z) Calc. for C75H139N3O16S4: 1465.90, found: 1465.65. 1H NMR (400 MHz, CDCl3, δ): 4.34-4.20 (br, 20H, —OCH2CH2O—), 2.82-2.76 (m, 5H, —SCH2CH(CH3)—), 2.75-2.70 (br, 10H, —C(O)CH2CH2N—), 2.69-2.62 (m, 5H, —SCH2CH(CH3)—), 2.60-2.52 (m, 5H, —SCH2CH(CH3)—), 2.52-2.49 (m, 10H, —CH2CH2S—), 2.49-2.45 (br, 16H, —NCH2CH2N—), 2.45-2.40 (br, 10H, —CH2N—), 1.57-1.48 (br, 10H, —SCH2CH2CH2—), 1.37-1.28 (br, 10H, —SCH2CH2CH2—), 1.28-1.16 (br, 55H, —SCH2CH2(CH2)4CH3, —CHC(CH3)CH2S—), 0.87-0.79 (br, 15H, —(CH2)4CH3).13C NMR (400 MHz, CDCl3, δ): 174.93, 172.13, 62.28, 62.01, 49.04, 40.13, 35.36, 32.68, 32.35, 31.76, 29.60, 29.15, 28.83, 22.59, 16.82, 14.05. MS (MALDI-TOF, m/z) Calc. for C93H173N5O2OS5: 1840.13, found: 1841.37. 5A2-SC8 has also been prepared with 6 arms (structure shown below). 1H NMR (400 MHz, CDCl3, δ): 4.32-4.21 (br, 20H, —OCH2CH2O—), 2.82-2.76 (m, 5H, —SCH2CH(CH3)—), 2.76-2.70 (br, 10H, —C(O)CH2CH2N—), 2.69-2.62 (m, 5H, —SCH2CH(CH3)—), 2.58-2.50 (m, 5H, —SCH2CH(CH3)—), 2.50-2.45 (m, 10H, —CH2CH2S—), 2.45-2.20 (br, 20H, (—(CH2)2NCH2—, —CH2NHCH2—), 1.66-1.57 (br, 6H, —NCH2CH2CH2N—), 1.57-1.48 (br, 10H, —SCH2CH2CH2—), 1.37-1.28 (br, 10H, —SCH2CH2CH2—), 1.28-1.16 (br, 55H, —SCH2CH2(CH2)4CH3, —CHC(CH3)CH2S—), 0.82-0.75 (br, 15H, —(CH2)4CH3).13C NMR (400 MHz, CDCl3, δ): 174.98, 172.13, 62.28, 62.01, 49.04, 40.13, 35.36, 32.68, 32.35, 31.76, 29.60, 29.15, 28.83, 22.61, 16.85, 14.14. MS (MALDI-TOF, m/z) Calc. for C94H174N4O20S5: 1839.13, found: 1838.97. 1H NMR (400 MHz, CDCl3, δ): 4.33-4.20 (br, 24H, —OCH2CH2O—), 2.82-2.77 (m, 6H, —SCH2CH(CH3)—), 2.77-2.71 (br, 12H, —C(O)CH2CH2N—), 2.68-2.62 (m, 6H, —SCH2CH(CH3)—), 2.60-2.52 (m, 6H, —SCH2CH(CH3)—), 2.52-2.48 (br, 12H, —CH2CH2S—), 2.48-2.46 (br, 12H, —NCH2CH2N—), 2.45-2.40 (br, 12H, (—CH2)2N—), 1.57-1.47 (br, 12H, —SCH2CH2CH2—), 1.37-1.28 (br, 12H, —SCH2CH2CH2—), 1.28-1.16 (br, 108H, —SCH2CH2(CH2)8CH3, —CHC(CH3)CH2S—), 0.87-0.80 (br, 18H, —(CH2)8CH3).13C NMR (400 MHz, CDCl3, δ): 174.87, 172.07, 62.16, 62.04, 49.48, 40.47, 40.11, 35.34, 32.69, 32.42, 31.86, 29.61, 29.58, 29.57, 29.50, 29.29, 29.21, 28.85, 22.62, 16.81, 14.06. MS (MALDI-TOF, m/z) Calc. for C132H246N4O24S6: 2463.65, found: 2464.52. Example 3: Library Design and Synthesis of First Generation Degradable Dendrimers (G1DDs) Liver cancer is a challenging host for therapeutic intervention because drug-induced hepatotoxicity can exacerbate the underlying liver disease (Boyerinas et al., 2010). To achieve effective RNAi-mediated therapy, a balance of high potency and low toxicity of the carrier therefore has to be maintained. This requires a versatile strategy to easily tune the delivery carrier in terms of size, chemical structure, and ultimate physical properties (FIG.1A). In some embodiments, dendrimers were designed that exhibit one or more of the following characteristics: optimal, monodisperse materials for chemical and size manipulation (Wu et al., 2004; Carlmark et al., 2009; Killops et al., 2008; Ma et al., 2009; Franc and Kakkar, 2010). Orthogonal reactions were utilized to sequentially react with 2-(acryloyloxy)ethyl methacrylate (AEMA) to diversify first generation degradable dendrimers (G1DDs) through various parameters: core (C), linkage or repeating unit (L), and periphery or terminating group (P) (FIG.1B). In some embodiments, esters were chosen as a starting degradable linkage because polyesters are used in FDA-approved products with minimal toxicity. At each growth step, the ester number increases, which provides an opportunity to identify degradable dendrimers with balanced potency and toxicity. Previous results show that these orthogonal reactions can construct polyester dendrimers with a series of generations (Ma et al., 2009). However, before this strategy was utilized, it was verified that the methods are capable to yield diversified dendrimers using a variety of chemically distinct amine and thiol compounds without purification. To examine the robustness of this chemistry, the most difficult starting materials, tris(2-aminoethyl)amine with six N—H bonds as initial branching centers (IBCs) and tetradecylamine with a 14-carbon-length alkyl chain, were used to test structural limits of the orthogonal Michael addition reactions. Both tris(2-aminoethyl)amine and tetradecylamine quantitatively and selectively reacted with the acrylate functionality in AEMA after 24 hours in the presence of 5 mol % of butylated hydroxyltoluene (BHT) (to inhibit radical formation) at 50° C., while AEMA by itself remains unreacted under these conditions (FIGS.2&3). In the second orthogonal reaction (sulfa-Michael addition), dimethylphenylphosphine was required as a catalyst to achieve the final product in low concentration (the lowest is 125 mM) or small scale (˜20 mg on average) conditions as well as to achieve high conversion (100% by1H NMR) so that the material can be used without purification for subsequent testing or generation expansion (FIGS.4&5). Some of the dendrimers were re-synthesized in larger scale and purified by flash chromatography before conducting in vivo studies. Due to multiple delivery barriers, the potency of small RNA carriers through nanoencapsulation is influenced by various factors, including pKa, topology/structure, and hydrophobicity (Siegwart et al., 2011; Jayaraman et al., 2012; Schaffert et al., 2011; Whitehead et al., 2014). To easily identify degradable dendrimers with high delivery potency, a library of G1DDs was designed with four zones: core binding—periphery stabilization (zone I), core binding—periphery binding (zone II), core stabilization—periphery stabilization (zone III), and core stabilization—periphery binding (zone IV) by chemically diversifying core-forming amines C and periphery-forming thiols P (FIGS.1C &1D). In zones I and II, RNA binding was modulated by amines with one (1An) to six (6An) initial branching centers (IBCs). Corresponding dendrimers therefore contained one to six branches. In zones III and IV, stabilization of RNA-dendrimer NPs was mainly changed with different length of alkyl chains (1Hn and 2Hn). In zones II and IV, binding capability of aminothiols (SNn) was mainly modulated with different amines while in zones I and III, stabilization was changed with alkylthiol (SCn) length and carboxyl- and hydroxyl-alkylthiols (SOn). The entire library of compounds was tested for the dendrimers' efficacy (FIG.6). Example 4: In Vitro G1DD Screening for siRNA Intracellular Delivery Delivery carriers must overcome a series of extracellular and intracellular barriers to enable small RNAs to be active inside of tumor cells. G1DDs were identified which can mediate siRNA to overcome the intracellular barriers by screening of the 1,512 member G1DD library for the ability to deliver siRNA in vitro to HeLa cells that stably expressed luciferase. G1DDs were formulated into nanoparticles (NPs) containing luciferase-targeting siRNA (siLuc) and the helper lipids cholesterol, 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) and lipid PEG2000 (Akinc et al., 2008; Semple et al., 2010). Intracellular delivery potential was assessed by quantifying luciferase reduction and cell viability (FIGS.7-9). In order to extract SAR from the in vitro data, we utilized a dendrimer-inspired tree analysis process (FIGS.7B &9B). Among the 1,512 dendrimers, 88 mediated luciferase silencing of >50% and the hit rate of the whole library was 6%. When the hit rate of all four zones (I-IV) was analyzed, the hit rate of zone I was 10%, while those of zone II, III, and IV were 0%, 2%, and 3%, respectively. This result indicated that these dendrimers with siRNA-binding core and stabilizing periphery (zone I) have much higher intracellular siRNA delivery potential. Within the branching types of zone 1, the hit rates of dendrimers with an SO periphery is as low as 1% while that of the dendrimers with an SC periphery was as high as 15%. Without wishing to be bound by any theory, it is believed that the hydrophobic stabilization from the dendrimer periphery is crucial to efficiently deliver siRNA into cells through nanoencapsulation. This likely results in increased hydrophobic packing that provides additional NP stability (Leung et al., 2012). After branch number and branch lengths of these dendrimers with binding core and SC periphery was further examined, the dendrimers with binding core and three, four, five or six SC5-8 branches or SC9-12 branches have >25% chance to deliver siLuc into HeLa cells with >50% luciferase knockdown. Through in vitro screening of the full G1DD library and the dendritic analysis process, the group of dendrimers which showed increased intracellular siRNA delivery was identified: the groups with binding core/SC periphery and binding core with three to six SC5-8 or SC9-12 branches. Example 5: Identification of Degradable Dendrimers for Effective In Vivo siRNA Delivery and Design of G2-G4 Dendrimers Having identified dendrimers that can overcome intracellular barriers, next, the dendrimers that can overcome extracellular barriers to efficiently deliver siRNA in vivo were identified. By separating these two processes, chemical functionality that overcomes barriers including blood stability, liver (tumor) localization, cellular uptake, and active siRNA release could be identified. Dendrimers were evaluated for their ability to silence Factor VII in hepatocytes because this blood clotting factor can be readily quantified from a small serum sample (Akinc et al., 2008; Semple et al., 2010). 26 of the hit degradable dendrimers were selected to maximize chemical diversity: 22 possessed an optimized chemical structure based on the dendritic analysis process and an additional 4 (2A2-SC14, 2A6-SC14, 2A9-SC14, and 6A1-SO9) were chosen based on their high intracellular siRNA delivery ability. Dendrimers were formulated with anti-Factor VII siRNA (siFVII) and were injected i.v. into mice at a dosage of 1 mg siFVII/kg. FVII activity was quantified 3 days post injection. Despite high in vitro potency, 2A2-SC14, 2A6-SC14, 2A9-SC14, 6A1-SO9 and most three-branch dendrimers showed only minimal in vivo FVII knockdown (FIG.3A). The dendrimers that contained a binding core and four, five or six SC8 or SC12 branches showed higher knockdown. Based upon these studies, SC8 branch dendrimers were generally more effective than SC12 branch compounds. With the in vitro and in vivo high-throughput screening results in hand, we asked whether we could now use that SAR information to rationally design dendrimers with predicted activity to validate our approach. A series of degradable dendrimers were prepared using two strategies: (I) by choosing polyamines with five or six IBCs; and (II) by increasing branches via dendrimer generation expansion (FIG.10). Two natural amines, spermidine (5 IBCs) and spermine (6 IBCs), were chosen to implement strategy I. As to strategy II, 1A2 (one IBC), 2A2 & 2A11 (two IBCs), 3A3 & 3A5 (three IBCs), and 4A1 & 4A3 (four IBCs) were chosen to yield degradable dendrimers with multiple branches via generation expansion (FIGS.10C &11). 24 additional degradable dendrimers were evaluated (FIG.10C) to further examine in vivo SAR. After generation expansion, higher-generation dendrimers of 1A2 (one IBC), 2A2 (two IBCs), and 3A3 & 3A5 (three IBCs) with four or six SC branches had good in vivo siRNA delivery to hepatocytes, while the dendrimers with eight branches were less active. This process transformed amine cores that were inactive in the in vitro screen, and then rationally design higher generation dendrimers which showed in vivo activity. Example 6: In Vivo Toxicity Evaluation of Degradable Dendrimers in Mice Bearing MYC-Driven Liver Tumors To identify degradable dendrimers with the required balance of low toxicity and high potency required for liver cancer treatment, the degradable dendrimers were chose to evaluate their in vivo toxicity. In parallel, we analyzed C12-200 lipidoid LNPs wee chose as the best example of a non-hydrolyzable system previously shown to be potent in mice and non-human primates (Love et al., 2010). Lipidoids, as a class, are benchmark materials at the forefront of clinical research (Kanasty et al., 2013; Love et al., 2010; Sahay et al., 2013). Non-immunogenic control siRNA was used to best evaluate the toxicity of the individual dendrimers themselves. Dendrimer NPs were formulated at a weight ratio of 25:1 (dendrimer:siCTR), higher than necessary to better probe toxicity. C12-200 LNPs were prepared using identical formulation parameters as previously reported (Love et al., 2010). Size and zeta potential of each NP in PBS buffer was characterized. They all possessed similar size, 64-80 nm in diameter, and their surfaces were close to neutral in charge (FIGS.12A &12B). Each formulated NP was injected i.v. into wild type mice at a 4 mg siCTR/kg dose (100 mg dendrimer/kg or 28 mg C12-200/kg). Among the many different ways to evaluate in vivo toxicity, body weight loss can be utilized as a simple and informative parameter. In normal mice, there were minimal body weight changes for the selected NPs, including C12-200 control LNPs. However, among candidates, the mice injected with 5A2-SC8 and 6A3-SC12 experienced quicker recovery and gained weight normally after the first day. Based on these results, 5A2-SC8 and 6A3-SC12 were chose for further evaluation of their in vivo toxicity in chronically ill transgenic mice bearing aggressive liver tumors with single and multiple injections. A well-established Tet-On MYC inducible transgenic liver cancer model was chosen (FIG.13A) (Nguyen et al., 2014). Since tumors are more aggressive when MYC is overexpressed at earlier developmental time points, MYC was induced immediately after birth (p0), which resulted in rapidly growing liver tumors. At the age of 32 days (p32), these sick transgenic mice bearing aggressive liver tumors were injected with 5A2-SC8 or 6A3-SC12 NPs at 3 mg siCTR/kg dosage (75 mg dendrimer/kg or 21 mg C12-200/kg). The mice receiving 5A2-SC8 injection lost about 5% body weight on the first day and quickly returned to their starting weight on the second day while those mice receiving 6A3-SC12 injection still lost 10% body weight by the third day and could not recover (FIG.12D). After multiple injections, these mice died seven days earlier compared to mice that received no treatment because of the toxicity of 6A3-SC12 carrier (FIG.12E). In contrast to the result in WT mice, injection of C12-200 LNPs to mice bearing aggressive tumors lost >20% weight after one day, despite receiving ˜3 times less lipid than 5A2-SC8 injected mice (FIG.12D). These data showed that small changes in chemical structure can produce large changes in toxicity. It also showed that tumor-bearing mice are more sensitive to intervention than healthy mice. Based on these results, 5A2-SC8 emerged as a degradable dendrimer possessing a balance of low toxicity (tolerance in tumor-bearing mice up to 75 mg/kg) and effective in vivo FVII knockdown (>95% at 1 mg siFVII/kg). In addition to being less toxic than benchmark compounds, 5A2-SC8 NPs are more efficacious because these dendrimers reduce clinical concern for dose limiting toxicity and enable a wider therapeutic window. Example 7: Potent Suppression of Liver Tumor Growth Through Systemic Administration of a Let-7g miRNA Mimic In order to evaluate the ability of degradable dendrimer NPs to deliver a therapeutic miRNA mimic without causing additional toxicity, the aggressive, MYC transgenic liver cancer model induced at p0 was again used (Nguyen et al., 2014). These mice developed rapidly growing cancers resembling pediatric hepatoblastoma (HB), a tumor type that shares many of the molecular features of HCC. Abdominal distention from mass effect was grossly visible after 20 days, and tumors grew rapidly. Without intervention, mice died within 60 days after birth. Given the speed and lethality of this model, there are limited opportunities for successful therapy. Since 5A2-SC8 balances low in vivo toxicity and effectiveness for silencing the hepatocellular target FVII, first, whether 5A2-SC8 NPs could deliver siRNA into tumor cells was examined. At the age of 41 days (p41), the livers of these transgenic mice are full of tumors (FIG.14A). On p40, mice were injected intravenously with 5A2-SC8 NPs with Cy5.5-labeled siRNA at a dosage of 1 mg siRNA/kg. 24 hours post-injection, fluorescence imaging showed 5A2-SC8 mediated siRNA accumulation in the cancerous liver, with only minor accumulation in the spleen and kidneys (FIGS.14A-14B). 5A2-SC8 NPs delivered siRNAs into normal and transgenic livers even if the cancerous livers are larger than normal ones (FIG.15A). To further confirm whether 5A2-SC8 NPs can deliver siRNA in vivo into tumor cells, tumor tissues of the liver were collected and imaged 24 hours after intravenous injection. H&E staining showed the tumor tissues are densely full of cellular nuclei and exhibit a cancerous phenotype (FIG.15B). Confocal imaging confirmed that 5A2-SC8 NPs were able to effectively deliver labeled siRNA into tumor cells (FIG.14C). The therapeutic benefit of 5A2-SC8-mediated small RNA delivery in these chronically ill transgenic mice was then evaluated. One of the most important miRNAs is Let-7, a tumor suppressor family downregulated in many tumor types (Boyerinas et al., 2010; Roush and Slack, 2008). Because endogenous Let-7g is known to be downregulated in liver HB (Nguyen et al., 2014), tests were conducted to determine if delivery of a Let-7g mimic in this aggressive, genetically engineered mouse model could inhibit the development of liver cancer. The 5A2-SC8 NPs were verified to be able to enable siRNA delivery in this model. Delivery of a single dose of siFVII i.v. showed potent silencing of FVII protein using a blood assay (FIG.16A) and by qPCR in harvested liver tissues (FIG.16B). This silencing was achieved on p26, which is after tumor development has initiated. Next, 1 mg/kg Let-7g was delivered in 5A2-SC8 NPs i.v. to tumor-bearing mice (p26). Let-7g expression was increased 7-fold in liver tissues 48 hours post-injection (FIG.16C). Then, a therapeutic regimen from p26 by weekly administration of 5A2-SC8 NPs containing Let-7g mimic or Control mimic at 1 mg/kg was started. At p50, the mice that received the Let-7g mimic had grossly smaller abdomens and reduced tumor burden (FIGS.16D-16F). Let-7g caused reduction of abdominal circumference, quantitative of tumor growth (FIG.16E). The effect on tumor growth was confirmed by ex vivo liver imaging (FIG.16F). Most importantly, delivery of Let-7g weekly from 26 to 61 days did not affect weight gain (FIG.16G) and significantly extended survival (FIG.16H). All control mice receiving no treatment and mice receiving 5A2-SC8 NPs with CTR-mimic died around 60 days of age. C12-200 LNPs (Let-7g or control mimic) induced premature death, and required halting of the experiment. Delivery of Let-7g inside of 5A2-SC8 NPs provided a dramatic survival benefit, with one mouse living to 100 days. These results showed that 5A2-SC8 can balance high delivery efficacy with low toxicity to provide a significant therapeutic benefit to chronically ill transgenic mice by effective inhibition of liver tumor growth. Example 8: Evaluation of Different Lipid Compositions for siRNA Delivery To evaluate which lipid composition within the dendrimer nanoparticles lead to improved siRNA delivery, the identity and concentration of different phospholipids and PEG-lipids were varied. Three different cell lines (HeLa-Luc, A549-Luc, and MDA-MB231-Luc) were used. The cells were present at 10K cells per well and a 24 hour incubation. The readout was determined 24 hours post transfection. In the nanoparticles, DSPC and DOPE were used as phospholipids and PEG-DSPE, PEG-DMG, and PEG-DHD were used as PEG-lipids. The compositions contain a lipid or dendrimer:cholesterol:phospholipid:PEG-lipid mole ratio of 50:38:10:2. The mole ratio of lipid/dendrimer to siRNA was 100:1 with 100 ng dose being used. The RiboGreen, Cell-titer Fluor, and OneGlo assays were used to determine the effectiveness of these compositions. Results show the relative luciferase activity in HeLa-Luc cells (FIG.17A), A549-Luc (FIG.17B), and MDA-MB231-Luc (FIG.17C). The six formulations used in the studies include: dendrimer (lipid)+cholesterol+DSPC+PEG-DSPE (formulation 1), dendrimer (lipid)+cholesterol+DOPE+PEG-DSPE (formulation 2), dendrimer (lipid)+cholesterol+DSPC+PEG-DMG (formulation 3), dendrimer (lipid)+cholesterol+DOPE+PEG-DMG (formulation 4), dendrimer (lipid)+cholesterol+DSPC+PEG-DSPE (formulation 5), and dendrimer (lipid)+cholesterol+DOPE+PEG-DHD (formulation 6). Further experiments were run to determine which phospholipids showed the increased delivery of siRNA molecules. A HeLa-Luc cell line was used with 10K cells per well, 24 hour incubation, and readout 24 hours post transfections. The compositions contained either DOPE or DOPC as the phospholipid with PEG-DHD as the PEG-lipid. The ratio of lipid (or dendrimer):cholesterol:phospholipid:PEG-lipid was 50:38:10:2 in a mole ratio with the mole ratio of dendrimer (or lipid) to siRNA of 200:1. These compositions was tested at a 50 ng dose using the Cell-titer Fluor and OneGlo assays. These results are shown inFIGS.18A &18B. Example 9: Evaluation of Dendrimer Nanoparticles for Delivery of sgRNA and Other CRISPR Nucleic Acids To evaluate the compositions to delivery nucleic acids for CRISPR/Cas gene editing, the delivery of sgRNA and mRNA was tested. Cell lines were created that could allow for rapid screening of dendrimer NPs and Z120 for sgRNA delivery. For example, HeLa (cervical cancer) and A549 (lung cancer) cells were established to co-express luciferase and Cas9. Selection and quality control was verified. Guide RNAs were designed according to previously reported methods targeting the first exon of the desired target gene. Targets possessing the highest score indicating cleavage activity and sequence specificity were carried forward for sgRNA preparation using established protocols. DNA oligonucleotides were synthesized commercially, annealed, cloned by BsbI digestion and ligated into a plasmid backbone containing Cas9. In vitro transcription enabled the isolation of sgRNA, which could then be packaged into dendrimer NPs for delivery. A series of 5 different guides were designed for Luciferase. These guides were validated by sgLuc-Cas9 pDNA transfection using commercial reagents to select the best sgRNA sequence. Next, we packaged sgLuc into dendrimer NPs and evaluated delivery in HeLa-Luc-Cas9 cells for delivery of sgRNA. Following a determined number of hours of exposure, luciferase and viability were measured compared to untreated cells using One Glo+Tox (Promega). In a typical experiment, 10K cells were plated per well, followed by 24 hour incubation, addition of dendrimer nanoparticles containing sgLuc, and readout at 24-48 hours post transfection. These compositions contained combinations of dendrimers, DSPC or DOPE, cholesterol, and PEG-lipid. Additionally, the compositions contained various concentrations of MgCl2. Molar ratios of lipid (or dendrimer):cholesterol:PEG-lipid were 50:38.5:0.5 with a mole ratio of lipid to nucleic acid (sgRNA) of 200:1 and a 50 ng dose. Again, the Cell-titer Fluor and OneGlo assays were used to obtain the results. Results without a phospholipid are shown inFIG.19. Similar studies were carried out with phospholipid present. In these compositions, the phospholipid DSPC was used in the formulations. Using the same ratio as above for compositions which did not contain a phospholipid, the phospholipid containing compositions had a mole ratio of 50:38.5:10:0.5 (lipid/dendrimer:cholesterol:phospholipid:PEG-lipid) using the same dosing amount. These compositions were tested using RiboGreen, Cell-titer Fluor, and OneGlo at two time periods, 24 hours and 72 hours. Data obtained at 24 hours is shown inFIG.20Aand 72 hours is shown inFIG.20B. Example 10: Evaluation of Dendrimer Nanoparticles for Delivery of mRNA Similar, to the studies carried out with siRNA, the delivery of mRNA molecules were tested with the dendrimers described herein and Z120. A IGROV1 cell line was used at a concentration of 4K cells per well, 24 hour incubation, and readout at 24 hours and 48 hours post transfection. These compositions contained either DSPC, DOPE, or no phospholipid and PEG-DHD as the PEG-lipid. Molar ratios of lipid (or dendrimer):cholesterol:phospholipid:PEG-lipid were 50:38.5:0(10):2 with a weight ratio of dendrimer to nucleic acid (mRNA) of 5, 10, 20, 30, or 40 to 1 and two different doses: a 50 ng dose and a 100 ng dose. The Cell-titer Fluor and OneGlo assays were used to obtain the results. These results were shown are shown inFIG.21A(24 hours) andFIG.21B(48 hours). Additionally, the delivery of mCherry mRNA into was visualized inFIG.22using a nanoparticle composition with 20:1 ratio N/P and DSPC as the phospholipid and PEG-DHD as the PEG-lipid. All of the compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of certain embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and methods and in the steps or in the sequence of steps of the methods described herein without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain agents which are both chemically and physiologically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims. REFERENCES The following references, to the extent that they provide exemplary procedural or other details supplementary to those set forth herein, are specifically incorporated herein by reference.U.S. Pat. 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11858885 | DETAILED DESCRIPTION Herein, the inventors have synthesized polysaccharide supported TBAF as a stable complex and disclosed its application in aliphatic SN2 fluorination. The present invention provides natural polysaccharide and TBAF complexes in their w/w ratio ranging from 1:0.3 to 1:5. The polysaccharide is selected from the group comprising of pectin, bacterial cellulose, plant cellulose and starch. In embodiment, the complex is synthesized by a process comprising:a) adding Tetrabutylammonium fluoride hydrate and polysaccharide in their respective equivalent amount (w/w) to hexane;b) refluxing mixture of step (a) in inert atmosphere at 80° C. for 1.5 h with vigorous stirring;c) cooling the solution of step (b) to a temperature in the range of 25-30° C., filtering, washing with hexane and drying under high vacuum at a temperature in the range of 25-30° C. to obtain the desired tetrabutylammonium fluoride/polysaccharide complex. The TBAF polysaccharide complexes of the invention thus synthesized are stable, non-hygroscopic and recyclable. In an aspect of the embodiment, the TBAF polysaccharide complexes have been characterized using SEM and TEM images, referFIGS.1and2. In the SEM images, white dots are observed, confirming the loading of TBAF in the polysaccharides. The TEM images show the special threading of TBAF observed with bacterial cellulose. In another aspect of the embodiment, the hygroscopicity of the complexes were evaluated by exposing the complexes at room temperature. After 15 minutes to 2 hours, the complexes were examined visually and the results are shown inFIG.3. The top row indicates the visual comparison after exposure for 15 minutes while the bottom row is after two hours of exposure. The reported TBAF complex is hygroscopic and became a liquid within 15 minutes, while the bacterial cellulosic-TBAF complexes remained stable up to two hours, without being liquefied. The study was continued and the disclosed complexes were found to be stable for 21 days. In another embodiment, the present invention provides the polysaccharide supported TBAF complex is used as a fluorinating agent and can be used for the fluorination of antibiotics, cancer drugs, sugars, steroids, pesticides, herbicides, and fungicide. The complexes provide 40-99% selectivity towards desired product, with minimal side product formation. In an embodiment, the fluorination reactions using the complexes give selectivity towards desired products on recycling the complex up to 4 times. The general process for the fluorination reaction comprises the steps of:i) charging substrate compound and complex in 1:1.5 w/w ratio into acetonitrile solvent;ii) stirring the reaction mixture of step i) at a temperature in the range of 65-70° C. for 3 hrs;iii) cooling the reaction mixture from step ii) to a temperature in the range of 25-35° C., filtering and washing with ethyl acetate solvent;iv) removing the solvent from the reaction mixture obtained at step iii) under reduced pressure;v) purifying the obtained compound at step iv) with flash chromatography by using 20% ethyl acetate in hexane eluent to afford pure fluorinated compound. The representative process for the fluorination of compound 5 is depicted below in scheme-1; wherein X is good leaving group to be replaced with fluorine. Table-1 below summarizes the results obtained by using different mole ratios of bacterial cellulose-TBAF complex at different time intervals. 3-(3,5-dimethoxyphenoxy) propyl methane sulphonate (5a) is used as a substrate and compounds 1-(3-fluoropropoxy)-3,5-dimethoxybenzene (6a) and 1-(allyloxy)-3,5-dimethoxy benzene (6b) are the fluorination products. TABLE 1EntryTimeYieldcNoNBu4(Bac-cell-OH)F.Solvent(h)6a6b11CH3CN290—21.5CH3CN292—42CH3CN288trace5d2CH3CN1.5871462CH3CN1851372CH3Ph271198e2CH3CN2819aAll reactions were carried out on a 1.0 mmol scale of substrate in solvent (8.0 mL) at 70° C.bFluorine complex used equivalent ratio of TBAF (Use 2 eq. of TBAF loaded in 1 eq. bacterial cellulose i.e. 100% of TBAF).cIsolated yields.dReaction carried at 90° C.eReaction carried in an open atmosphere.— not detected. Referring to the scheme-1 and table 1, the fluorination reaction was conducted with bacterial cellulose-TBAF complex using acetonitrile or tri methyl benzene as a solvent at 50-100° C. for a substrate: complex ratio of 1:1 to obtain more that 70% selectivity of desired fluorinated product. The complex used is in the range of 1:1 to 1:2 of TBAF: cellulose. In a preferred embodiment, the cellulose is bacterial cellulose. Table 2 below summarizes the results obtained by using recycled complex. It is found that the complex can be recycled up to 4 times. After completion of reaction, the reaction mass is cooled to 25-35° C. and bacterial cellulose is filtered. It is further washed with ethyl acetate and dried under high-vacuum (2 mbar) to re-use for further loading of TBAF to form complex for further reactions. TABLE 2Yield ofEntryLoading of TBAFfluorinated product1 Recycling70% loading of TBAF94%2 Recycling68% loading of TBAF94%3 Recycling68% loading of TBAF93%4 Recycling66% loading of TBAF94% The invention will now be described with reference to examples, which should not be construed to limit the invention in any manner. Examples Following examples are given by way of illustration and therefore should not be construed to limit the scope of the invention. Example A: General Procedure for the Synthesis of Polysaccharide Sported TBAF Complex (A) To a flame-dried round bottom flask with cooling condenser Tetrabutylammonium fluoride hydrate and polysaccharide (Pectin, Starch and plant cellulose were procured from Sigma, whereas bacterial cellulose was synthesized in the lab by indigenous bacteria which inventors have isolated, refer RSC Advances, 2018, 8, 29797-29805, DOI: 10.1039/c8ra05295f) was added in their respective equivalent amount (w/w) in 100 ml of hexane. This mixture was refluxed in nitrogen atmosphere at 80° C. for 1.5 h with vigorous staring. During the reaction, complex shows the water droplets on sidewall of the condenser, which indicates the completion of the reaction and complex formed. The solution was allowed to cool to 25-30° C., filtered, washed with hexane and dried under high vacuum at 25-35° C. to give the desired tetrabutylammonium fluoride/polysaccharide complexes which was used for the aliphatic nucleophilic fluorination. In this manner complexes were prepared with polysachharides such as pectin, starch, bacterial cellulose and plant cellulose in the ratios 1:0.1 to 1:5 w/w of polysaccharide: TBAF. Example 1: Preparation and Characterization of Pectin+TBAF Complex: NBu4(Pec-OH)F Loading (%)w/wSr. NoPectinTBAFResult111Solid212Sticky Solid313Sticky Solid Example 2: Preparation and Characterization of Bacterial Cellulose+TBAF Complex: NBu4(Bac-Cell-OH)F Loading (%)w/wSr. NoCelluloseTBAFResult111Solid212Solid313Solid414Solid515Slightly StickySolid616Sticky Solid Example 3: Preparation of Characterization of Plant Cellulose+TBAF Complex: NBu4(Pla-Cell-OH)F Loading (%)w/wSr. NoCelluloseTBAFResult111Gel210.9Gel310.8Gel410.7Sticky Solid510.6Sticky Solid610.5Sticky Solid710.4Sticky Solid810.3Solid Example 4: Preparation of Characterization of Starch+TBAF Complex: NBu4(Sta-Cell-OH)F Loading (%)w/wSr. NoCelluloseTBAFResult111Gel210.9Gel310.8Gel410.7Gel510.6Sticky Solid610.5Sticky Solid710.4Sticky Solid810.3Solid Example B: A Representative Fluorination Procedure synthesis of 4-(3-fluoropropoxy)-1,2-dimethoxybenzene: In a flame dried round bottom flask, mesylated substrate compound (0.290 mg, 1 mmol) and NBu4(Bac-cell-OH)F.1 (0.3915 mg, 1.5 eq) in dry Acetonitrile were taken and the reaction vial was flushed with N2 and stirred at 70° C. for 3 h. Cooled reaction mixture was filtered using sintered funnel. The reaction mixture was washed with ethyl acetate and evaporated under reduced pressure. The crude product was purified by flash column chromatography using (20% EtOAc/hexane) to give corresponding fluorinated compound. 4-(3-fluoropropoxy)-1, 2-dimethoxybenzene. 4-(3-fluoropropoxy)-1,2-dimethoxybenzene:1H NMR (400 MHz, CDCl3) δ 6.10 (s, 3 II), 4.71 (t, 0.1=5.8 Hz, 1 II). 4.59 (t, 0.1=5.8 Hz, 1 II), 4.07 (t, J=6.1 Hz, 2 II), 3.78 (s, 6 II), 2.25-2.08 (m, 2 H).3C NMR (101 MHz, CDCl3) δ 161.5, 160.6, 93.3, 93.1, 80.4 (d, J=164.15 Hz), 63.5, (d, J=4.62 Hz), 55.3, 30.4 (d, 0.1=20.04 Hz).19F NMR (400 MHz, CDCl3) δ 222.14 A similar procedure was followed for different substrates to obtain following fluorinated products. 2-fluoro-1-(3-methoxyphenyl)ethan-1-one: 1H NMR (400 MHz, CDCl3) δ 7.45 (d, J=2.3 Hz, 1H), 7.43-7.38 (m, 2H), 7.19-7.15 (m, 1H), 5.52 (d, J=46.71 Hz, 2H), 3.87 (s, 3H);3C NMR (101 MHz, CDCl3) δ 193.1, (d, J=15.33 Hz), 160.0, 134.9, 129.9, 120.6, 120.6, (d, J=2.8 Hz), 112.1, (d, J=1.93 Hz), 84.5, (d, J=182.11 Hz), 55.5;19F NMR (400 MHz, CDCl3) δ 232.60. 1H NMR (400 MHz, CDCl3) δ 7.87 (d, J=8.2 Hz, 2H), 7.49 (d, J=8.7 Hz, 2H), 5.49 (d, J=46.71 Hz, 2H);13C NMR (101 MHz, CDCl3) δ 192.5 (d, J=15.33 Hz), 140.7, 132.1, 129.4 (d, J=2.88 Hz), 129.3, 84.6 (d, 0.1=184.03 Hz);19F NMR (400 MHz, CDCl3) δ 232.60. 1-fluorododecane: 1H NMR (400 MHz, CDCl3) δ 4.50 (t, J=6.1 Hz, 1H), 4.39 (t, J=6.1 Hz, 1H), 1.75−1.63 (m, 2 II), 1.28 (m., 18 II), 0.89 (t, J=6.1 Hz, 211);13C NMR (101 MHz, CDCl3) δ 84.2 (d, 0.1=163.68 Hz), 31.9, 30.4 (d, J=19.27 Hz,) 29.6, 29.6, 29.5, 29.4, 29.3, 25.2, 25.1, 22.7, 14.1;19F NMR (400 MHz, CDCl3) δ 232.60. 1-fluoropentadecane: 1H NMR (400 MHz, CDCl3) δ 4.50 (t, J=6.1 Hz, 1H), 4.39 (t, J=6.1 Hz, 1H), 1.80-1.61 (m, 2H), 1.44-1.26 (m, 24H), 0.90 (t, J=6.1 Hz, 2H);13C NMR (101 MHz, CDCl3) δ 84.2 (d, J=164.15 Hz), 31.9, 30.4 (d, J=19.25 Hz), 29.7, 29.6, 29.5, 29.4, 29.3, 25.2, 25.1, 22.7, 14.1;19F NMR (400 MHz, CDCl3) δ 232.60. 9-(2-fluoroethyl)-9H-carbazole: 1H NMR (400 MHz, CDCl3) δ 8.16 (d, J=7.9 Hz, 2H), 7.55-7.48 (m, 2H), 7.47-7.42 (m, 2H), 7.35-7.28 (m, 2H), 4.87 (t, J=5.4 Hz, 1H), 4.75 (t, J=4.88 Hz, 1H), 4.64 (t, J=5.41 Hz, 1 H), 4.63 (t, J=4.8 Hz, 1 H);13C NMR (101 MHz, CDCl3) δ 140.4, 125.8, 123.0, 120.4, 119.3, 108.5, 81.9 (d, J=172.6 Hz,), 43.2, (d, J=22.3 Hz);19F NMR (400 MHz, CDCl3) δ 232.60. 2-benzyl-4-chloro-1-(3-fluoropropoxy)benzene: 1H NMR (400 MHz, CDCl3) δ 7.33-7.26 (m, 2H), 7.26-7.13 (m, 4H), 7.09 (d, J=2.7 Hz, 1 H), 6.79 (d, J=8.7 Hz, 1H), 4.58 (t, J=5.7 Hz, 1H), 4.46 (t, J=6.0 Hz, 1 H), 4.06 (t, J=6.0 Hz, 2H), 3.95 (s, 2H), 2.19-2.06 (m, 2H)3C NMR (101 MHz, CDCl3) δ 155.1, 140.1, 131.5, 130.3, 128.7, 128.4, 127.1, 126.1, 125.4, 1 12.3, 80.4, (d, J=164.86 Hz), 63.8 (d, J=4.79 Hz), 30.4, (d, J=20.13 Hz);19F NMR (400 MHz, CDCl3) δ 232.60. 1-(3-fluoropropoxy)-1H-benzo[d][1,2,3]triazole: 1H NMR (400 MHz, CDCl3) δ 7.51 (d, J=2.3 Hz, 1H), 7.33 (dd, J=2.3, 8.7 Hz, 1H), 6.82 (d, J=8.7 Hz, 1H). 4.76 (t, J=5.7 Hz, 1H), 4.64 (t, J=5.7 Hz, 1H), 4.14 (t, J=6.0 Hz, 2 H), 2.27-2.17 (m, 2 H);13C NMR (101 MHz, CDCl3) δ 153.6, 132.7, 130.5, 124.1, 114.6, 112.8, 80.4 (d, J=164.85 Hz), 64.9, (d, J=4.79 Hz), 30.2 (d, J=20.13 Hz);19F NMR (400 MHz, CDCl3) δ=232.60. 1-([1,1′-biphenyl]-4-yl)-2-fluoroethan-1-one: 13C NMR (101 MHz, CDCl3) δ 193.0, (d, J=15.34 Hz 146.8, 139.5, 132.3, 129.0, 128.5, 128.4, 127.5, 127.2, 127.1,19F NMR (400 MHz, CHLOROFORM-d) 6=232.60. (6S)-4-(2,2-dimethyl-1,3-dioxolan-4-yl)-6-fluoro-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxole: 1H NMR (400 MHz CDCl3) δ 5.59 (d, J=59.51 Hz 1 H), 4.86 (dd, J=3.5, 5.3 Hz, 1H), 4.78 (t, J=6.1 Hz, 1 II), 4.44-4.38 (m, 1 H), 4.17 (dd, J=3.1, 7.6 Hz, 1 H), 4.12 (dd, J=6.10, 8.39 Hz, 1H), 4.09-4.05 (dd, J=4.4, 8.39 Hz, 1H), 1.46 (d, J=2.3 Hz, 6H), 1.39 (s, 3H), 1.35 (s, 3 H);13C NMR (101 MHz, CDCl3) δ 114.7, 113.7 (d, J=69.09 Hz) 109.4, 84.7 (d, J=42.17 Hz) 82.6, 78.6, 72.7, 66.6, 26.9, 25.8, 25.1, 24.5;19F NMR (400 MHz, CDCl3) δ 232.60. 3-Fluorostigmasterol: 1H NMR (500 MHz, CDCl3) δ 5.34 (d, J=5.0 Hz, 1H), 5.19-5.14 (m, 1H), 5.02 (dd, J=8.6, 15.1 Hz, 1H), 3.34-3.23 (m, 1H), 2.30 (dd, J=2.9, 13.2 Hz, 1H), 2.27-2.20 (m, 1H), 2.10-1.95 (m, 5H), 1.88-1.82 (m, 2H), 1.74-1.69 (m, 1H), 1.58 (s, 3H), 1.55-1.45 (m, 8H), 1.27 (d, J=7.2 Hz, 2H), 1.20-1.15 (m, 3H), 1.01 (s, 4H), 0.85 (d, J=6.1 Hz, 3H), 0.81 (d, J=7.6 Hz, 7H), 0.70 (s, 3 H);3C NMR (126 MHz, CDCl3) δ 141.3, 138.3, 129.2, 121.3, 56.5 (d, J=116.34 Hz), 51.2, 50.3, 42.2, 40.5, 40.0, 39.7, 37.4, 36.9, 31.9, 31.9, 29.4, 28.9, 25.4, 24.4, 21.2, 21.1, 19.4, 19.0, 12.2, 12.0;19F NMR (400 MHz, CDCl3) δ 232.60. Example C: General Process for the Recovery of the Complex for Recycling After completion of the reaction, the reaction mixture was cooled to 25-35° C. bacterial cellulose was filtered, washed with ethyl acetate and dried under high-vacuum (2 mbar) to re-use for further loading if TBAF. Advantages of the Invention Stable complexNon hygroscopicComplex is recyclableComplex provides good selectivity of fluorinated product | 12,932 |
11858886 | DESCRIPTION OF THE INVENTION The present invention can be worked in its entirety based on the following description. It should be understood that the following description is given of preferred embodiments of the present invention, and the present invention is not necessarily limited thereto. In addition, the accompanying drawings are provided to aid understanding of the present invention, and the present invention is not limited thereto. Terms used herein may be defined as follows. The term “coke” may refer to a hydrocarbon having low hydrogen content, particularly a residual solid carbon byproduct. The term “coupling” may refer to a chemical reaction in which two identical molecules react to form a larger molecule in a narrow sense. The term “methane coupling” may refer to a reaction that forms not only C2 hydrocarbons (e.g. ethane, ethylene, acetylene, etc.) from methane, but also larger hydrocarbons (C2+) (e.g. benzene, naphthalene, etc.). The term “pyrolysis” may refer to a reaction in which hydrocarbons are decomposed upon exposure to heat or the like even without the addition of oxygen or oxygen-containing reactants, and in the present disclosure, may be construed to include a reaction that converts a compound into one or more other materials by applying heat thereto. The term “heterogeneous catalyst” may refer to a catalyst that exists in a phase different from that of a reactant during a catalytic reaction, for example, a catalyst that is not dissolved in a reaction medium. For a heterogeneous catalyst, in order for the reaction to occur, at least one reactant has to be diffused and adsorbed to the surface of the heterogeneous catalyst, and after the reaction, the product needs to be desorbed from the surface of the heterogeneous catalyst. The term “support” may refer to a material (typically a solid material) having a high specific surface area, and onto which a catalytically active component is attached or deposited. The term “hydrogenation” may refer to a reaction in which hydrogen content in a compound is increased by chemically adding hydrogen to at least a portion of the compound by bringing the compound into contact with a catalyst in the presence of hydrogen. The term “impregnation” may refer to a method of preparing a catalyst by impregnating a support with a solution in which a catalyst precursor is dissolved and then performing drying and/or firing (or reduction treatment) as necessary. The term “conversion” may refer to the number of moles of the feedstock that are converted into a compound other than the feedstock per unit mole thereof. The term “selectivity” may refer to the number of moles of a target product per unit mole of the converted feedstock. According to an embodiment of the present disclosure, there is provided a process of selectively converting acetylene into ethylene by hydrogenating a gas mixture. The gas mixture may typically be a methane pyrolysis product, particularly a gas mixture remaining after separating C6 or higher hydrocarbons, especially aromatic hydrocarbons, among pyrolysis products of methane. Accordingly, the gas mixture may be substantially free of aromatic hydrocarbons such as benzene, toluene, naphthalene, and the like. According to an embodiment, the gas mixture, which is a feedstock for the hydrogenation reaction, may contain acetylene at a relatively high concentration compared to conventional methane pyrolysis products. As such, the gas mixture containing high-concentration acetylene results from a phenomenon by which methane is mainly converted into acetylene rather than ethylene upon pyrolysis in the presence of hydrogen, under controlled pyrolysis reaction conditions (temperature, pressure, residence time, etc.) for the purpose of increasing the conversion of methane and maximally suppressing coke formation during the pyrolysis. The gas mixture having such a composition may be obtained from a non-oxidative pyrolysis product of methane (particularly, a non-oxidative methane coupling product), a plasma pyrolysis (or coupling) product of methane, and combinations thereof. In particular, the gas mixture applicable in this embodiment is derived from typical methane pyrolysis, particularly a pyrolysis reaction that does not use oxygen (non-oxidative pyrolysis), and is thus substantially free of carbon monoxide, carbon dioxide, etc. According to an embodiment, the concentration of acetylene in the gas mixture may be at least about 2 mol %, particularly about 3 to 10 mol %, and more particularly about 4 to 8 mol %. The concentration of acetylene set forth above is distinguished from that in conventional methane pyrolysis products in which the concentration of acetylene is less than about 2 mol % (particularly about 0.5 to 1 mol %) and the concentration of C2 hydrocarbons other than acetylene, such as ethane and ethylene, is relatively high. The gas mixture may further comprise hydrogen that is formed as a byproduct through a C—C coupling reaction during methane pyrolysis and/or hydrogen that is supplied or reacted together with methane for the purpose of increasing the conversion and suppressing coke formation during methane pyrolysis, as described below. By way of example, the gas mixture may contain hydrogen in an amount of at least about 50 mol %, particularly about 52 to 75 mol %, and more particularly about 60 to 65 mol %. Moreover, the gas mixture may typically contain unconverted methane (i.e. unreacted methane) in the pyrolysis reaction. For instance, the concentration of methane is up to about 48 mol %, particularly about 18 to 45 mol %, and more particularly about 28 to 35 mol %. According to a particular embodiment, the gas mixture may contain about 4 to 7 mol % of acetylene, about 62 to 64 mol % of hydrogen, and about 30 to 33 mol % of methane. According to an exemplary embodiment, the gas mixture may further contain C2 hydrocarbons other than acetylene. Here, C2 hydrocarbons may be ethane and/or ethylene. The concentration of C2 hydrocarbons other than acetylene may be, for example, less than about 1 mol %, particularly less than about 0.75 mol %, and more particularly less than about 0.5 mol %. According to a particular embodiment, the concentration of ethylene in the gas mixture may be, for example, less than about 1 mol %, particularly less than about 0.75 mol %, and more particularly less than about 0.5 mol %. Also, according to an exemplary embodiment, the gas mixture may further contain hydrocarbons, for example C3 to C5 hydrocarbons, remaining after separation of aromatics from methane pyrolysis products. Such hydrocarbons may typically be contained at a concentration of less than about 1 mol %, particularly less than about 0.75 mol %, and more particularly less than about 0.5 mol %. According to an embodiment, acetylene in the gas mixture may be converted into ethylene through a selective hydrogenation using a catalyst. Notably, the hydrogen contained in the gas mixture may be utilized as it is without the need to separately or externally supply hydrogen necessary for the hydrogenation of acetylene. Although hydrogen supplementation from any external sources to reach a hydrogen partial pressure suitable for effective hydrogenation of acetylene is not strictly excluded, the amount of hydrogen that is added may be greatly decreased in such cases. In this regard, the H2/C2H2molar ratio in the reaction product for the selective hydrogenation of acetylene to ethylene may be suitably adjusted within the range of, for example, about 5 to 35, particularly about 8 to 30, more particularly about 9 to 20, and much more particularly about 10 to 15. Meanwhile, the hydrogenation may be carried out in the presence of a catalyst. Here, it is necessary to use a catalyst having activity capable of increasing the conversion of acetylene and the selectivity for ethylene in a gas mixture having high acetylene concentration compared to typical pyrolysis products. To this end, in this embodiment, a hydrogenation is carried out in the presence of a heterogeneous catalyst in which at least two metals, particularly a first metal M1having hydrogenation activity and a second metal M2having a function of inducing selective hydrogenation, are loaded or supported on a porous support. Since this metal function may be quantified with H adatom adsorption energy through DFT (density functional theory) calculations, the first metal M1may exhibit hydrogen adsorption energy of about −4 to −2 eV and the second metal M2may exhibit hydrogen adsorption energy of −1 to 0 eV. The first metal M1may be at least one selected from the group consisting of Pd, Pt, Rh, Ir, Ni, and Co, and particularly may be Pd. Also, the second metal M2may be at least one selected from the group consisting of Cu, Ag, Au, Zn, Ga, and Sn, and particularly may be Cu. According to a particular embodiment, the combination of metals supported on the support may be a combination of Pd and Cu, and the reason for use thereof may be explained by the alloying effect. The hydrogenation catalyst used in this embodiment is a catalyst comprising two types of active metal components, and the first metal (particularly Pd) and the second metal (particularly Cu) may be in a state showing crystallinity, and may also be in an alloy form or in a supported form while intimately or closely contact with each other. In addition, the first metal M1may exist in the form of a single atom, and the second metal M2may exist in the form of nanoparticles. In an exemplary embodiment, the size of the active metals (or each of the first and second metals) in the hydrogenation catalyst may be, for example, about 100 nm or less, particularly about 10 to 70 nm, and more particularly about 20 to 50 nm. According to an embodiment, the amount of the first metal M1in the hydrogenation catalyst may be, for example, about 0.15 to 2 wt %, particularly about 0.2 to 1 wt %, and more particularly about 0.21 to 0.5 wt %. Since the amount of the first metal affects selective hydrogenation activity and selectivity, it may be advantageously controlled within the above range. Also, the amount of the second metal M2may be, for example, about 0.8 to 30 wt %, particularly about 1 to 10 wt %, and more particularly about 1.5 to 5 wt %. If the amount of the second metal is excessively high or low, activity may be insufficient, or nonselective hydrogenation may be induced. Hence, the amount of the second metal may be set within the above range. Meanwhile, in an exemplary embodiment, the first metal M1and the second metal M2may be combined at a predetermined ratio depending upon the properties of each metal. In this regard, the hydrogenation catalyst may satisfy Equation 1 below (based on ICP-OES analysis). 1<WM2WM1<20[Equation1] In Equation 1, WM1is the wt % of the first metal in the hydrogenation catalyst and WM2is the wt % of the second metal in the hydrogenation catalyst. According to an exemplary embodiment, WM2WM1 may be adjusted within the range of, for example, about 2 to 10, particularly about 3 to 8, and more particularly about 4 to 7. If the amount of the first metal M1relative to the second metal M2falls outside a predetermined range, activity may be remarkably deteriorated, or a phenomenon by which selectivity for acetylene decreases during the hydrogenation may occur. Hence, each amount of the active metal components may be appropriately adjusted to fall within the above range. Meanwhile, the support for loading the two metals (the first and second metals) may be at least one selected from the group consisting of alumina, silica, carbon, zirconia, titania, ceria, and silicon carbide. Particularly, alumina, and more particularly gamma-alumina, may be used. According to an exemplary embodiment, the support may be a porous support, and the porosity of the support may be controlled such that the reactant or product does not remain for an excessively long time when diffusing in the support. In this regard, the support may exhibit properties exemplified below:Specific surface area (BET): at least about 300 m2/g, particularly about 400 to 700 m2/g, and more particularly about 500 to 600 m2/g;Pore volume: at least about 0.5 cm3/g, particularly about 0.75 to 2 cm3/g, and more particularly about 1 to 1.5 cm3/g; andAverage pore size: about 50 to 200 Å, particularly about 70 to 180 Å, and more particularly about 100 to 150 Å. Moreover, according to an exemplary embodiment, the support may be prepared in various shapes known in the art, as well as in a powder form. Examples thereof may include a spherical shape (including a hollow shape), a cylindrical shape (including a hollow shape), a granular shape, a tablet shape, a ring shape, a saddle shape, a star shape, a honeycomb shape, a pellet shape, a trilobe shape, a quadrilobe shape, and the like. As such, for illustrative purposes, in order to prepare a support having a specific shape, a molding method known in the art, extrusion, spray drying, pelletizing, oil dropping, etc. may be performed. Also, the average size of the support having a shape exemplified above may be in the range of, for example, about 1 to 5 mm, particularly about 1.5 to 3 mm, and more particularly about 2 to 2.75 mm, which are understood for illustrative purposes. According to an exemplary embodiment, the hydrogenation catalyst may be prepared through any loading techniques known in the art, examples of which may include impregnation, deposition, ion-exchange, deposition-precipitation, etc. Particularly, the impregnation, and more particularly, incipient wetness impregnation or modified incipient wetness impregnation, may be applied. In a particular embodiment, the catalyst may be prepared through an impregnation technique. To this end, the metal may be used in the form of a precursor, particularly a metal compound, more particularly a metal salt, a complex, etc., and may be selected from among types that are soluble in the medium used to prepare the impregnation solution (particularly, an aqueous medium). For example, when the first metal among the active metals is palladium, a precursor thereof may be an organic acid salt or an inorganic acid salt, a complex, a hydroxide, a halide, or a combination thereof. For example, a palladium precursor may be at least one selected from among palladium acetate, palladium chloride, palladium nitrate, palladium ammonium nitrate, palladium sulfate, palladium carbonate, palladium hydroxide, palladium halide, hydrates thereof, and the like, which are understood for illustrative purposes. More typically, palladium ammonium nitrate may be used as the precursor. On the other hand, when the second metal is copper, the precursor thereof may be at least one selected from among, for example, copper hydroxide phosphate, copper nitrate, copper sulfate, copper acetate, copper formate, copper (II) chloride, copper iodide, and the like, and more typically, copper nitrate may be used. According to an exemplary embodiment, the impregnation solution may be prepared by sequentially or simultaneously adding the first metal precursor and the second metal precursor to the medium. Here, the total concentration of the active metal precursors (the first metal precursor and the second metal precursor) in the impregnation solution may be adjusted within the range of, for example, about 0.01 to 2 μM, particularly about 0.1 to 1 μM, and more particularly about 0.25 to 0.75 μM, depending upon the amounts of the first and second metals that are supported in the final catalyst and the ratio between the first metal and the second metal. In addition, the pH of the solution containing the first metal precursor and the second metal precursor may be adjusted within the range of, for example, about 1 to 3, particularly about 1.2 to 2, and more particularly about 1.3 to 1.5, in order to effectively disperse the metal precursor in the support. To this end, an acid component known in the art may be added to the impregnation solution. Such an acid component may be at least one selected from among nitric acid, sulfuric acid, hydrochloric acid, oxalic acid, and the like. The impregnation process is not limited to a particular process, so long as the metal precursor solution (i.e. the composite precursor solution of the first and second metals) is able to sufficiently contact the pores in the support. For example, the metal precursor solution may be sprayed for contact or impregnation, thus forming a precursor solid. Alternatively, the support may be immersed in the metal precursor solution, for example, at about 15 to 80° C. (particularly at about 20 to 50° C., more particularly at room temperature) for about 0.5 to 3 hours (particularly about 1 to 2 hours). However, these conditions are set forth for illustrative purposes. After impregnation of the support with the active metals as described above, a drying process may be performed, for example, under an oxygen-containing atmosphere (particularly, ambient air). Here, the drying temperature may be set within the range of, for example, about 60 to 150° C., particularly about 70 to 100° C., but is not limited thereto. Also, the drying time may be set within the range of, for example, about 3 to 24 hours, particularly about 6 to 12 hours. Through the drying process, the metal precursor may be more closely attached to the support. Ultimately, there may be provided a structure in which the support is covered with the active metal precursors, for example is, a core-shell structure. After the solid in which the first metal precursor and the second metal precursor are attached or deposited onto the support is obtained as described above, the metal component may be converted into a reduced or elemental form through reduction treatment. Here, although calcination or heat treatment before reduction treatment is not excluded, the reduction treatment of the precursor solid without calcination may be adopted. The reduction treatment may be performed using hydrogen alone or hydrogen diluted with an inert gas (e.g. N2, He, Ar, etc.), and may be carried out in the temperature range of, for example, about 200 to 400° C., particularly about 220 to 380° C., and more particularly about 250 to 350° C. Here, the heating rate may be set within the range of, for example, about 3 to 10° C./min, particularly about 4 to 8° C./min, and more particularly about 5 to 7° C./min. Also, the reduction treatment time is not particularly limited, and may be adjusted within the range of, for example, about 0.5 to 24 hours, particularly about 1 to 12 hours. Illustratively, when the reducing gas is diluted with the inert gas, the concentration of the reducing gas may be in the range of, for example, about 5 to 20 vol %. In addition, the pressure during the reduction treatment may be in the range of, for example, approximately atmospheric pressure to 10 bar (typically atmospheric pressure). According to an embodiment, the gas mixture containing high-concentration acetylene is hydrogenated in the presence of the catalyst described above. Here, the hydrogenation temperature may be set within the range from room temperature to 250° C., particularly about 40 to 200° C., and more particularly about 50 to 150° C. Also, the hydrogenation pressure may be set within the range of, for example, about 0.2 to 1 bar, particularly about 0.3 to 0.8 bar, and more particularly about 0.4 to 0.7 bar. According to an exemplary embodiment, the hydrogenation may be performed in a batch or continuous mode, but a continuous mode is preferable in terms of economic feasibility of operation and the like. Here, the reactor is not particularly limited, but, for example, a gaseous fixed-bed reactor, a fluidized-bed reactor, etc. may be used, and a fixed-bed reactor may be advantageously used. Moreover, the gas hourly space velocity (GHSV) is determined depending upon both the productivity of ethylene and the conversion through catalytic contact. If the gas hourly space velocity is excessively low, productivity may be deteriorated, whereas if the gas hourly space velocity is excessively high, contact with the catalyst may become insufficient. In consideration thereof, the gas hourly space velocity may be adjusted within the range of, for example, about 1 to 15 L/gcat·hr−1, particularly about 2 to 10 L/gcat·hr−1, and more particularly about 3 to 5 L/gcat·hr−1. According to an exemplary embodiment, the conversion of acetylene in the gas mixture as the feedstock may be in the range of, for example, at least about 95%, particularly at least about 97.5%, and more particularly about 99 to 99.9%, and also, the selectivity for ethylene may be in the range of, for example, at least about 95%, particularly at least about 97.5%, and more particularly about 99 to 99.9%. Here, the above numerical ranges are understood for illustrative purposes. The hydrogenation product may be separated or purified using a combination of techniques known in the art (e.g. distillation, PSA, etc.) to thus recover ethylene and hydrogen therefrom. However, the hydrogenation product may still contain methane and hydrogen remaining after the hydrogenation, and methane and a portion of hydrogen may be recycled during the separation. Here, methane and hydrogen may be recycled individually or in the form of a mixed gas. For example, methane and hydrogen may be recycled in the form of a mixed gas and introduced into a pyrolysis reactor together with a fresh methane-containing feedstock (or a combination thereof with hydrogen). In this case, the CH4/H2molar ratio in the recycle flow may be adjusted within the range of, for example, about 0.05 to 1, more particularly about 0.1 to 0.8, and more particularly about 0.2 to 0.5. Combination of Pyrolysis and Hydrogenation An exemplary process for producing ethylene by combining a methane pyrolysis process and an acetylene hydrogenation is shown inFIG.1. This example is provided to deepen understanding of the present disclosure, and in particular, the pyrolysis process before the hydrogenation may be implemented in various ways, and is not necessarily limited to the embodiment as exemplified below. With reference to the above drawing, a methane-containing gas1as a feedstock is introduced into a pyrolysis reactor101as a gas mixture2of methane and hydrogen combined with a recycled mixed gas (a mixed gas of methane and hydrogen;12). For example, the methane-containing gas1, which is composed exclusively of methane or contains not only methane but also a diluent gas, may be introduced into the pyrolysis reactor101. For example, the diluent gas may be at least one selected from the group consisting of nitrogen, carbon dioxide, and hydrogen sulfide, the amount of which may be at most about 20 mol %, particularly up to about 10 mol %, more particularly up to about 5 mol %, and much more particularly up to about 3 mol %, but the above ranges are set forth for illustrative purposes. Here, the pyrolysis reactor is not limited to a specific type, but may be a radial tube reactor due to its good heat transfer efficiency. Moreover, the material for a pyrolysis reactor, particularly a non-oxidative direct conversion reactor, may be at least one selected from among alumina, SiC, FeCrAl alloy, Inconel (NiCr), and the like. Meanwhile, methane is a non-polar molecule similar to the stable structure of an inert gas, and the binding energy of C—H is 435 kJ/mol, and the thermodynamic stability thereof is high. High chemical and thermodynamic stability makes it difficult to convert methane into various compounds. According to the present embodiment, C2+ hydrocarbons and hydrogen byproducts are generated from methane through a direct non-oxidative coupling reaction or a plasma coupling reaction in the pyrolysis process. Hereinafter, a pyrolysis process involving a direct non-oxidative coupling reaction is mainly described. For the pyrolysis, a radical reaction is carried out after methane is activated to a methyl radical. The reaction temperature and pressure conditions may be sophisticatedly controlled to increase the conversion of methane and suppress coke formation. By way of example, the pyrolysis temperature may be adjusted within the range of, for example, about 1000 to 1400° C., particularly about 1050 to 1350° C., more particularly about 1100 to 1300° C., and much more particularly about 1150 to 1250° C. Also, the pyrolysis pressure may be adjusted within the range of, for example, about 0.1 to 1 bar, particularly about 0.2 to 0.8 bar, more particularly about 0.3 to 0.7 bar, and much more particularly about 0.4 to 0.6 bar. Also, the gas hourly space velocity (GHSV) may be set within the range of, for example, about 300 to 3600 hr−1, particularly about 720 to 1800 hr−1, more particularly about 900 to 1600 hr−1, and much more particularly about 1200 to 1440 hr−1. In the illustrated embodiment, as described above, the recycled mixed gas introduced into the reactor together with the fresh methane-containing feedstock contains methane and hydrogen, and thus a pyrolysis reaction occurs in the presence of hydrogen, which is effective at increasing the conversion of methane and suppressing the formation of coke materials. Under these reaction conditions, methane may be mainly converted into acetylene rather than ethylene, among C2 hydrocarbons. In this regard, the composition of the materials within the pyrolysis reactor may satisfy the requirement represented by Equation 2 below. PH2PCH4≥0[Equation2] wherein, PH2is the partial pressure of hydrogen in the mixed gas introduced into the reactor and PH4is the partial pressure of methane in the mixed gas introduced into the reactor. According to an exemplary embodiment, PH2PCH4 may be adjusted within the range of, for example, about 0.5 to 3, particularly about 0.7 to 2.5, and more particularly about 0.9 to 1.5. According to an exemplary embodiment, the pyrolysis may be carried out in the presence of a catalyst (e.g. a supported catalyst), and a metal having a methane activation function may be at least one selected from among iron (Fe), chromium (Cr), vanadium (V), molybdenum (Mo), tungsten (W), and the like. Also, the support that is used may be a porous support made of an inorganic oxide material, for example, at least one selected from among alumina, silica, titania, zirconia, magnesia, ceria, and the like. Also, the amount of the active metal in the catalyst may be adjusted within the range of, for example, about 0.1 to 10 wt %, particularly about 0.3 to 8 wt %, and more particularly about 0.5 to 5 wt %. The catalyst composition described above is provided for illustrative purposes, and the present disclosure is not necessarily limited thereto. According to an exemplary embodiment, the conversion of methane resulting from the pyrolysis under the reaction conditions described above may be in the range of about 10 to 50%. Here, the lower the methane conversion, the higher the selectivity for C2+ hydrocarbons. For example, the selectivity for C2+ hydrocarbons in the methane conversion range of 0 to 10% may be at least about 99.9%, the selectivity for C2+ hydrocarbons in the methane conversion range of 10 to 20% may be at least about 99.5%, the selectivity for C2+ hydrocarbons in the methane conversion range of 20 to 30% may be at least about 95%, the selectivity for C2+ hydrocarbons in the methane conversion range of 30 to 40% may be at least about 90%, and the selectivity for C2+ hydrocarbons in the methane conversion range of 40 to 50% may be at least about 80%. If the methane conversion is excessively increased, the selectivity for C2+ hydrocarbons may be lowered to about 70%, whereas if the methane conversion is excessively decreased, the yield may be insufficient. Accordingly, it may be advantageous to maintain the methane conversion in the range of, for example, about 10 to 50%, particularly about 20 to 40%, and more particularly about 30 to 35%. In addition, the selectivity for acetylene in the pyrolysis product may be in the range of, for example, at least about 55%, particularly at least about 60%, and more particularly about 65 to 70%, and the selectivity for aromatics (especially benzene) may be in the range of, for example, about 30% or less, particularly about 5 to 25%, and more particularly about 10 to 20%. According to an exemplary embodiment, the pyrolysis product may further contain at least one compound selected from among ethane, ethylene, C3-C5 hydrocarbons, and the like, in addition to acetylene and aromatics, and the amount thereof may be, for example, about 40 vol % or less, particularly about 30 vol % or less, and more particularly about 20 vol % or less, based on the amount of the pyrolysis product. Referring again toFIG.1, the pyrolysis product3passes through a vacuum pump102to form a depressurized flow4, followed by rapid cooling to, for example, about −20 to 25° C. (particularly about −10 to 0° C.) in a quench tower103. In the illustrated embodiment, the gas mixture is separated into an overhead flow5containing C5−hydrocarbons and hydrogen and a bottom flow7containing C6+hydrocarbons (particularly benzene and hydrocarbons larger than C6). Here, the bottom flow7is separated into benzene20and a heavier fraction21in a benzene column105, and benzene may be recovered. On the other hand, the overhead flow5is a fraction containing methane, hydrogen, and acetylene as described above, and is a gas mixture which may optionally further contain C2 hydrocarbons (ethane and/or ethylene) other than acetylene, and C3-C5 hydrocarbons. This gas mixture may be introduced into an acetylene converter104, so the selective hydrogenation of acetylene as described above may be performed. Thereafter, a hydrogenation product6is pressurized to, for example, about 10 to 50 bar (particularly about 15 to 30 bar) while passing through a process gas compressor106, and the pressurized flow8may be cooled to, for example, about −75 to −45° C. (particularly about −60 to −55° C.) by a cold box107. The cooled flow9is transferred to a demethanizer108, from which a mixed gas10of methane and lighter hydrogen is discharged as the overhead flow, while C2+ hydrocarbons11are discharged as the bottom flow and then separated into C2 hydrocarbons16and C3-C5 hydrocarbons17in a deethanizer110. Thereafter, the C2 hydrocarbons16are separated into ethylene18and C2 hydrocarbons19other than ethylene in a C2 splitter111. Each of the demethanizer108, the deethanizer110, and the C2 splitter111operates under cryogenic conditions. On the other hand, the mixed gas10is separated into a recycle flow12and a recovery flow13, and the recycle flow is combined with the methane-containing feedstock and then introduced into the pyrolysis reactor101. The recovery flow13is introduced into a pressure swing adsorber109and separated into hydrogen14and methane15. In the above-described embodiment, since the principle of operation of the separation and purification unit after the pyrolysis reaction and the selective hydrogenation is known in the art, further description of details pertaining thereto is omitted. According to another embodiment, the process shown inFIG.1may be implemented in a manner that changes the arrangement of the quench tower, vacuum pump, acetylene converter, etc. while maintaining the basic configuration thereof. For example, when the quench tower, vacuum pump, and acetylene converter are sequentially disposed downstream of the methane pyrolysis reactor, the acetylene converter may operate under a pressure of atmospheric pressure or higher. In addition, the processing units may be sequentially arranged in the order of the vacuum pump, acetylene converter, and quench tower, or in the order of the acetylene converter, vacuum pump, and quench tower. Alternatively, although the processing units may be arranged in the order of the acetylene converter, vacuum pump, and quench tower or in the order of the acetylene converter, quench tower, and vacuum pump, when C6+ hydrocarbons are fed to the acetylene conversion catalyst, the catalyst lifetime may be shortened, which may be regarded undesirable. A better understanding of the present invention may be obtained through the following examples, which are merely set forth to illustrate the present invention and are not to be construed as limiting the scope of the present invention. EXAMPLE Preparation of Catalyst A trilobe-shaped alumina support was purchased from Saint-Gobain (USA) and used without further purification. Before supporting with active metals, the support was dried overnight at 80° C. in a convection oven. Palladium ammonium nitrate (Sigma, 99.9%) as a first metal precursor, and copper nitrate (Sigma, 99.9%), gold nitrate (Sigma, 99.9%), or silver nitrate (Sigma, 99.9%) as a second metal precursor were dissolved in an acid aqueous solution (acid component: 10 wt %, nitric acid). The metals were supported using a modified incipient wetness impregnation technique, and the resulting solid was dried at 80° C. in a convection oven and reduced with hydrogen at 300° C. for 6 hours (heating rate: 5° C./min). The catalyst in which a metal alloy was supported on an alumina support was represented by x % Pdy % M (in which x and y represent the wt % of each metal, and M represents a second metal (Cu, Ag, or Au)). Methane Pyrolysis and Hydrogenation Methane pyrolysis and hydrogenation were performed in a continuous flow system. The structure of the apparatus used in the present Example is schematically shown inFIG.2. With reference to this drawing, the experimental apparatus broadly includes a pyrolysis furnace201, a chiller202, a hydrogenation reactor203, an online gas chromatograph204, and a vacuum pump205. The flow between the hydrogenation reactor203and the vacuum pump205was mainly used, and the above flow was changed with the online gas chromatograph204during analysis. Also, TC and P are a thermocouple and a pressure controller, respectively. Specifically, in the methane pyrolysis zone, an alumina tube reactor (99.9%, ½″ O.D) was disposed at the center of an electric furnace equipped with a molybdenum silicide (MoSi2) heating element. Before reaction, the reactor was heat-treated at 700° C. for 2 hours under flowing air (10 mL·min−1, 99.9%) in order to remove impurities (heating rate: 10° C./min). A gas mixture of nitrogen, methane (99.999%, Rigas), and hydrogen (UHP, Riga) was introduced into the reactor using a mass flow controller (5850E, Brooks Instrument). The pyrolysis product effluent flow was quenched at −10° C., thus collecting trace amounts of polycyclic aromatics. The quenched gas was introduced into a hydrogenation zone in which a stainless steel reactor (½″ O.D, 300 mm L) was disposed at the center of an electric furnace. For all experiments, the reaction system operated below atmospheric pressure, and the reaction pressure was regulated using a vacuum controller (Buchi, V800) controlled by a diaphragm and a chemical-resistant solenoid valve (Parker). The transfer line was heated to 100° C. to prevent potential condensation. The product was sampled at intervals of 2 hours using an online gas chromatograph (Agilent Technology, 7890A) equipped with an HP-PLOT/Al2O3capillary column (50 m×0.32 mm×8.0 mm) for FID (flame ionized detection), or with an HP-Molesieve capillary column (30 m×0.53 mm×20 mm) for TCD (thermal conductivity detection). The GC column was configured to separate hydrogen, nitrogen, and hydrocarbons in order to provide information on the conversion of methane and quantitatively analyze the concentrations of ethylene, ethane, acetylene, and benzene. The trace amounts of C3-05 products were also combined. In addition, the microkinematic simulation used in Example was performed using the CANTERA software package. Results and Discussion Methane Pyrolysis Simulation In order to characterize the optimal reaction conditions for converting methane into value-added hydrocarbons as main product species, taking into consideration four reaction parameters (temperature: 1150-1250° C.; pressure: 0.1-10 bar; H2/CH4ratio: 0-1; and residence time: 0-10 seconds), methane pyrolysis simulation was performed. The effect of each reaction parameter on the methane conversion and the product yield were plotted as contour lines inFIGS.3and4. Each graph shown inFIG.3shows the effect of a combination of four reaction parameters. The methane conversion increased with an increase in residence time, regardless of temperature, whereas it decreased with an increase in the H2/CH4ratio. However, the results varied depending on the operating pressure. At temperatures up to 1150° C., the methane conversion showed a volcano-shaped pattern. As shown in graph a inFIG.3, at 1100° C., the methane conversion started from about 45% at 0.2 bar, showed a peak value of 60% at 1 bar, and then decreased to 45% at 10 bar (residence time: 6 seconds) (black arrow). Meanwhile, at 1250° C., the methane conversion gradually decreased with an increase in the reaction pressure (yellow arrow in graph d ofFIG.3d), starting from 87% at 0.2 bar and showing 10% at 10 bar (H2/CH4=0; residence time: 6 seconds). A similar tendency was observed at 1250° C. regardless of whether hydrogen was additionally supplied (graphs d, h and l ofFIG.3). It should be noted that the operating pressure is represented as a logarithmic scale inFIG.3and that the methane conversion is sensitive to the reaction pressure, especially pressure lower than atmospheric pressure. In addition, the highest methane conversion was achieved below atmospheric pressure with an increase in the reaction temperature. Supposedly, this result is because the overall conversion of methane was thermodynamically inhibited by gaseous hydrogen which has been readily formed in the methane pyrolysis. Next, the hydrocarbon yield was reviewed, where the yields of specific hydrocarbon species (ethane, ethylene, acetylene, and benzene) were measured in the simulation, and the results thereof are shown inFIG.4. With the H2/CH4ratio fixed at 0, the yield of a particular hydrocarbon product increased with an increase in the reaction pressure and residence time, regardless of temperature (yellow arrows in graphs a to c ofFIG.4). The highest hydrocarbon yield at 1100° C. occurred in a range similar to that for the highest conversion shown in graph i ofFIG.4, regardless of whether hydrogen was supplied. However, when the temperature was elevated up to 1200° C. (graphFIG.4), the highest yield of a particular product was obtained at 0.5 bar for a residence time of 3 seconds, which is distinct from the highest observed conversion of methane (graph g ofFIG.3). These differences reflect conversion of methane into other hydrocarbons, mostly polycyclic aromatic hydrocarbons. The simulation results support the notion that controlling the reaction pressure and supplying hydrogen are important considerations in the methane pyrolysis for selectively producing heavier hydrocarbons. As such, the effects of low pressure and the supply of hydrocarbons and hydrogen together on the selectivity of hydrocarbons during methane pyrolysis can be confirmed by plotting conversion versus selectivity, as shown inFIG.5. In this simulation, in order to understand the influence of the reaction pressure and hydrogen supply, experimental conditions at a predetermined temperature of 1200° C. were classified into three zones: when hydrogen was supplied (graphs A to C ofFIG.5), when hydrogen was not supplied (graphs D to I ofFIG.5), when the operating pressure was less than atmospheric pressure (graphs G to I ofFIG.5), and when the operating pressure exceeded atmospheric pressure (graphs A to F ofFIG.5). The measured conversion of methane versus the selectivity for hydrocarbons (ethane, ethylene, acetylene, and benzene) allows prediction of the ideal product composition, which is strongly dependent on operating conditions. Comparing graphs A and D ofFIG.5, when hydrogen was supplied together, total methane conversion was decreased but selectivity for hydrocarbons was increased. For example, under normal operating conditions, C2+C6 selectivity obtainable at a methane conversion of 50% was about 60% (the dotted lines in graphs A to I ofFIG.5), but was about 80% when hydrogen was also supplied. This improvement may be deemed to be mainly due to an increase in C2 selectivity (graphs B and E ofFIG.5). This indicates that hydrogen has a significant effect of inhibiting the formation of polycyclic aromatics. Then, when the operating pressure is set below atmospheric pressure in the methane pyrolysis, the selectivity range for the methane conversion may be narrowed. For example, for a methane conversion of about 50%, selectivity was 60 to 80% at 1 to 10 bar, but was about 85% at 0.1 to 0.5 bar. These distinct results suggest that, when the operating pressure is adjusted below atmospheric pressure and hydrogen is supplied together, selectivity for C2+C6 hydrocarbons during the methane pyrolysis can be maximized. Experimental Validation Additional experiments were performed by setting the methane pyrolysis pressure below atmospheric pressure while supplying hydrogen. In order to sample the gaseous product discharged from a reactor equipped with a vacuum pump, volatile solids in the gas effluent flow were collected under mild conditions. As such, for the collected hydrocarbons, trace amounts of polycyclic aromatic hydrocarbons such as naphthalene, anthracene, and pyrene were also analyzed (data not shown). The gaseous product was then rapidly transferred to the analyzer over about 1 minute (FIG.2). The results of the methane pyrolysis experiment are shown inFIGS.6A and6B. Operating conditions including a temperature of 1240° C., a H2/CH4ratio of 1, a pressure of 0.5 bar, and a GHSV of 1415 hr−1were selected as the base experimental conditions for the methane pyrolysis. Under these conditions, the average conversion of methane was 34%, and the selectivity for heavy hydrocarbons to benzene was 93%. When the operating pressure was increased to 0.6 bar, the initial conversion increased to 41% and then gradually decreased to 36%, which can be seen as a problem related to heat transfer due to the formation of coke on the wall of the alumina tube reactor. On the other hand, when the reaction pressure started at 0.4 bar, the average conversion of methane was rapidly decreased to 21%, which was consistent with a simulation result showing that the methane conversion was sensitive to the reaction pressure as described above. When the temperature was raised under a fixed operating pressure, the increased initial conversion of 43% decreased to 32% after 30 hours. This result indicates that a reaction temperature suitable for stable hydrocarbon production in the methane pyrolysis should be selected. In addition, stable methane conversion of 26% and hydrocarbon selectivity of 95% were obtained under the mildest conditions of 1220° C. and 0.5 bar. Meanwhile,FIG.7shows experimental results plotting conversion versus selectivity for particular hydrocarbons. Similar to the simulation shown inFIG.7, the experimental results were classified into three zones depending on whether hydrogen was supplied and on the reaction pressure. In this experiment, in order to achieve the target methane conversion, the temperature was adjusted within the range of 1000 to 1260° C. According to the experimental results, high selectivity for hydrocarbons (C2+C6) was obtained at a methane conversion of less than 10% (the black squares inFIG.7). However, when the methane conversion increased to about 40%, hydrocarbon selectivity was decreased sharply to about 30%, mainly due to the formation of polycyclic aromatic hydrocarbons and/or coke. When hydrogen was supplied thereto, the selectivity achievable at a methane conversion of 40% was about 80% (the blue triangles inFIG.7). This is a result of the improved C2 selectivity, and indicates that hydrogen has a significant effect on suppressing the formation of polycyclic aromatic hydrocarbons. Moreover, when methane pyrolysis was carried out below atmospheric pressure, selectivity was increased. For example, the selectivity for hydrocarbons at a methane conversion of 50% was about 90% at an operating pressure of 0.3 to 0.5 bar. Based on the experimental results, the highest hydrocarbon yield was observed when the average conversion of methane was 36.9% at 1275° C. and 0.3 bar. These experimental results suggest that the methane pyrolysis is promising for production of three main species, namely acetylene, hydrogen, and benzene, under conditions in which the formation of coke precursors such as polycyclic aromatic hydrocarbons is suppressed. Evaluation of Performance of Hydrogenation Catalyst An effluent gas having a unique chemical composition was produced through the methane pyrolysis described above, and the methane pyrolysis product, in which the methane conversion was maintained at 30% and C7 or higher hydrocarbons were removed, was introduced as a feedstock for the hydrogenation. Polycyclic aromatic hydrocarbons were removed from methane pyrolysis products and trace amounts of C3-C5 hydrocarbons were not considered, and the composition thereof is shown in Table 1 below. TABLE 1ClassificationPartial pressure in gas mixture (Bar)Methane conversion (%)CH4H2C2H4C2H2C6H6100.4350.5440.0040.0170.000200.3770.5850.0050.0320.001300.3220.6250.0060.0450.002400.2680.6640.0060.0580.003500.2170.7010.0060.0700.005 As shown in Table 1, when the methane conversion was about 30%, respective concentrations of methane, hydrogen, and acetylene in the gas mixture introduced into the hydrogenation reactor were 32.2%, 62.5%, and 4.5%, which were higher than for the gas composition used with palladium catalysts in commercial acetylene converters over the past few decades. In consideration thereof, in the present Example, a catalyst in which each of PdCu, PdAu, and PdAg was supported on an alumina support was applied. For screening, a catalyst was prepared by controlling the metal composition in a simple manner through incipient wetness impregnation. FIG.8Ashows the overall yield of acetylene and benzene obtained from a hybrid system of methane pyrolysis and hydrogenation using a PdCu catalyst. As shown in this drawing, during the hydrogenation, 99.5% of acetylene was converted into ethylene using the PdCu catalyst, and deactivation of the catalyst was not observed even after 65 hours. The yields of ethylene and C2+C6 in the hybrid system were 20% and 24%, respectively. Although the PdAg catalyst and the PdAu catalyst showed lower catalytic performance than the PdCu catalyst, the PdAg catalyst also exhibited relatively high selectivity (98%) at a methane conversion of about 60%, and is thus regarded as promising (FIG.8B). When using the PdAu catalyst, a high acetylene conversion was obtained, but ethane was the main product, indicating that the usefulness thereof in the selective hydrogenation of a gas mixture containing high-concentration acetylene and hydrogen is limited. These results suggest that the hybrid system according to the present Example has great potential in the continuous production of value-added ethylene from methane. Meanwhile, the weight ratio between Pd and Cu supported on the hydrogenation catalyst was adjusted as shown in Table 2 below. TABLE 20.2Pd0.2Pd1Cu0.2Pd2Cu0.2Pd3Cu1CuActive metal(Comparative Example)(Example)(Example)(Example)(Comparative Example)Pd (wt %)0.2150.2150.2170.215—Cu (wt %)—0.8191.6762.2481.336 TABLE 3Temp.AcetyleneSelectivity (%)Catalyst(° C.)conversion (%)C2H6C2H40.2Pd5099.991.98.1(ComparativeExample)0.2Pd1Cu5096.710.589.5(Example)0.2Pd2Cu5014.94.595.5(Example)0.2Pd2Cu10099.54.096.0(Example)0.2Pd3Cu10097.53.097.0(Example)1Cu300172.697.4(ComparativeExample) As shown in Tables 2 and 3, in the presence of 0.2Pd not containing Cu (Comparative Example), a high conversion was realized compared to when using 0.2Pd1Cu, 0.2Pd2Cu, and 0.2Pd3Cu, all of which contained Cu, but the selectivity for ethylene was low, and moreover, in the presence of 1 Cu not containing Pd (Comparative Example), acetylene hydrogenation capability was remarkably low. In the presence of the catalysts containing Pd and Cu according to Examples, it was confirmed that conversion was decreased but selectivity for ethylene was increased at the same temperature with an increase in Cu content. In particular, the tendency toward increased selectivity with an increase in Cu content from 1 wt % to 3 wt % indicates that Pd atoms are arranged on Cu nanoparticles having low acetylene hydrogenation performance in the catalyst to thus create an environment in which Pd atoms can selectively hydrogenate acetylene, thereby realizing selective hydrogenation of high-concentration acetylene. As is apparent from the above description, a method of producing ethylene and hydrogen from a gas mixture according to an embodiment of the present disclosure is capable of producing ethylene at high yield by selectively hydrogenating acetylene in a gas mixture in the presence of a bimetallic supported catalyst, taking into consideration the composition of products containing acetylene at a relatively high concentration depending on reaction conditions during methane pyrolysis. Also, hydrogen can be recovered from the gas mixture, and thus can be utilized for applications that add value, and can be used as a hydrogen source necessary for the selective hydrogenation of acetylene, thereby obviating the need for separate supply of hydrogen from external sources. In addition, when methane and/or hydrogen among hydrogenation products are recycled to the upstream methane pyrolysis reaction, it is possible to increase the conversion of methane and suppress coke formation during the methane pyrolysis. In particular, selectivity for acetylene can be increased, making it possible to form a gas mixture having a composition in which acetylene accounts for most C2 hydrocarbons in methane pyrolysis products. As such, the method according to the present embodiment is particularly advantageous for commercialization, such as improvement in the overall efficiency of conversion of methane into value-added platform chemicals, etc., through a selective hydrogenation process alone or in combination with processes upstream and downstream thereof. Simple modifications or variations of the present invention can be easily devised by those of ordinary skill in the art, and all such modifications or variations can be considered to be included in the scope of the present invention. | 50,753 |
11858887 | DETAILED DESCRIPTION OF EMBODIMENTS The present disclosure is based on the development of simple, short reaction time (5 hours or less) and effective method for producing a modified cellulose-based materials, such as cellulosic fabric, cardboard and others that comprises, chemically bound thereto, via a specially developed group of bifunctional linkers, one or more functional agents. The binding of such functional agents were shown to provide the cellulose fabric with, inter alia, higher durability and strength upon long term use. For example, one type of modification of a cellulose-based (comprising) fabric provided the fabric with an improved aesthetic finish/look and feel. An improved finish of a cellulosic matrix can be classified as a functional finish, e.g. dyeing, waterproof finish, flame-retardant finish, anti-moth finish, antistatic finish, antimicrobial, antibacterial, electro-conductive. In some other modifications, the modification provided the fabric with improved performance, namely, an improved function, e.g. smoothness, stability/durability etc. The modification of the cellulosic fabric, as well as other polymeric matrices, is achieved by the use of a bifunctional linker. Thus, in accordance with a first of its aspects, the present disclosure provides a bifunctional linker compound having the following general formula (I): whereinR1and R2may be the same or different and represent a group selected from vinyl, alkyl vinyl, propargyl, alkyl propagyl, allenyl, alkyl allenyl, alkylthio and alkyl azide;R3is a alkyl;X1and X2may be the same or different and each is selected from the group consisting of —O—(CH2)nor —S—(CH2)n, where n is independently with respect to X1and X2an integer from 1 to 4;W is a group selected from —OH, —SH, halo, epoxy, and —OR4where R4is a alkyl; andR5is selected from the group consisting of alkylene and a carbonyl or R5is a valence bond;said compound is for use as a bifunctional linker for coupling at least one functional moiety to a polymer containing matrix. In some embodiments, R1is different from R2. In some embodiments, R1and R2are identical. In some embodiments, R1and R2, being the same or different, can each comprise a short chain carbohydrate. In the context of the present when referring to a short chain carbohydrate it is to be understood as meaning any chain, saturated or unsaturated carbohydrate, comprising from one or two carbon atom (depending on the type of the group) and not more than 20 carbon atoms, at times, not more than 18, or even not more than 16 carbon atoms. In some embodiments, the short chain carbohydrate comprise 2 carbon atoms, at times, 3 carbon atoms, 4, 5, 6, 7, 8, 9, 10, 11 or even up to 12 carbon atoms. In some embodiments, R1and R2are independently selected from the group consisting of vinyl, C3-C12alkyl vinyl, propargyl, C3-C12alkyl propargyl, C3-C12allenyl, C4-C12alkyl allenyl, C1-C12alkylthio and C1-C12alkyl azide. In some embodiments, R1is C3-C12alkyl vinyl (i.e. containing at least one double bond that is terminal to the carbohydrate (alkyl) chain). In some embodiments, R1is an alkyl vinyl (e.g. allyl). In some embodiments, R1is an allyl. In some embodiments, R1is C3-C12a propargyl (i.e. containing at least one triple bond terminal to the carbohydrate chain). In some embodiments, R1is C1-C12alkylthio. In some embodiments, R1is C1-C12alkyl azide. In some embodiments, R2is C3-C12alkyl vinyl (i.e. containing at least one double bond that is terminal to the carbohydrate (alkyl) chain). In some embodiments, R2is an allyl. In some embodiments, R2is C3-C12a propargyl (i.e. containing at least one triple bond terminal to the carbohydrate chain). In some embodiments, R2is C1-C12alkylthio. In some embodiments, R2is C1-C12alkyl azide. In some embodiments, R1and R2are the same and represent —C1-C4-vinyl, preferably, —CH2—CH═CH2. In some embodiments, R3is a short alkyl chain. In some embodiments, R3is C1-C4alkyl. In some embodiments, R3is selected from a methyl, an ethyl or propyl group. Preferably, R3is a methyl group. In some embodiments, X1is —O—(CH2)n—, when n is an integer of any one of 1, 2, 3 or 4. In some embodiments, n is 1 or 2. In on preferred embodiment, X1is —O—CH2—. In some embodiments, X2is —O—(CH2)n—, when n is an integer of any one of 1, 2, 3 or 4. In some embodiments, n is 1 or 2. In on preferred embodiment, X2is —O—CH2—. In some embodiments, R5is a carbonyl group. In some embodiments, when said R5is a carbonyl group, W represents —OH or —Cl, preferably —OH. In some specific embodiments, compound of formula (I) is bis-allyl propionic acid (known also by the abbreviated name BAPA) and has the structure represented by formula (IA): In some embodiments, R5is an alkylene, preferably C1-C5alkylene. In some embodiments, R5is selected from the group consisting of methylene or ethylene. In some embodiments, R5is a valence bond. In some embodiments, when R5is a valence bond, W is an epoxy. In some specific embodiments, the compound of formula (I) is epoxy BAPA, and has the specific structure represented by formula (IB): The compound of formula (I) is used as a bifunctional linker for coupling at least one functional moiety to a polymer-containing matrix. When referring to a bifunctional linker it is to be understood as a compound that provides a chemical connection between two different entities, at least one of the entities being the polymer-containing matrix. The linker is thus, in the context of the present disclosure, one that can chemically bind, on its one end to the polymer-containing matrix (e.g. to the surface of the polymer-containing matrix), and on its other end, to one or more functional moieties. In the context of the present disclosure, the binding of the at least one functional moiety is via at least one of the R1and R2groups and the binding of the linker to the polymer-containing matrix is via the W group. In the context of the present disclosure, when referring to a chemical bond it is to be understood as encompassing a covalent bond. In some embodiments, the chemical bond is a covalent bond. As noted above, the linker binds via its one end to a polymer containing matrix. In the context of the present disclosure, when referring to such polymeric matrix it is to be understood as matrix (structure) comprising a single type of polymer (i.e. homopolymer) or plurality of polymers, e.g. co-polymer, the matrix/structure comprising surface exposed reactive groups to which the linker binds. In the context of the present disclosure the term “reactive groups” it is to be understood as encompassing polar groups, capable of covalently binding to the linker. Such reactive groups may include, without being limited thereto, hydroxyl, carbonyl, carboxyl, amino, thiol alkyne, alkene, epoxide. In some embodiments, the exposed reactive moieties comprise a hydroxyl group. In some embodiments, the polymer-containing matrix is one comprising an organic/natural polymer(s). In some embodiments, the polymer-containing matrix is one comprising a synthetic polymer(s) or semi synthetic polymer(s). In some embodiments, the polymer-containing matrix comprises a combination of organic and synthetic polymers. In some embodiments, the polymer-containing matrix comprises plant-derived polymers. In some embodiments, the polymer-containing matrix comprises polysaccharides. In some embodiments, the polysaccharide is selected from the group consisting of cellulose, hemi-cellulose and lignin. In some embodiments, the polymer-containing matrix comprises cellulose or modified cellulose. In some embodiments, the polymer-containing matrix comprises or consists essentially of cellulosic polymers. In some other embodiments, the polymer-containing matrix comprises any one or combination of a material selected from the group consisting of viscose, wool, silk, rayon, cellophane. Each of said polymeric materials contain one or more functional groups that can be covalently linked to the bifunctional linker disclosed herein. In some embodiments, the polymer-containing matrix comprises synthetic polymers. In some embodiments, the plastic comprises any one or combination of polyethylene, polypropylene, polyamides, polyurethanes and polyesters. In some embodiments, cellulose (or other polymer that can bind to the bifunctional linker) can be added to a polymer containing matrix (that has no functional groups to link to the bifunctional linker) as an additive, e.g. to allow the linking of the bifunctional linker to the matrix's surface. In some embodiments, the polymer-containing matrix comprises semi-synthetic polymers. When referring to semi-synthetic polymers it is to be understood as encompassing at least one naturally occurring polymer that has been treated/modified to carry reactive groups for covalent attachment therethrough to the linker. In some embodiments, the semi-synthetic polymer is cellulose acetate. In some embodiments, the polymer-containing matrix comprises polymeric fibers. In the context of the present disclosure, when referring to a matrix comprising fibers, it is to be understood as encompassing any type of fibers, including, without being limited thereto, microbifers, co-extruded fibers, fibrilsall collectively referred to herein by the term fibers. In some embodiments, the polymer-containing matrix comprises woven, non-woven or a combination of woven and non-woven fibers. In some embodiments, the polymer-containing matrix comprises woven fibers. In some embodiments, the polymer-containing matrix comprises woven cellulose-containing fibers. In some embodiments, the polymer-containing matrix is a woven cellulose containing fabric. In some embodiments, the polymer-containing matrix comprises cotton fibers. In some embodiments, the polymer-containing matrix is a cotton fabric. In some embodiments, the polymer-containing matrix is a fabric as used in the textile industry. In some embodiments, the polymer-containing matrix comprises nonwoven fibers. This may be a fabric-like material (nonwoven fibers) where the fibers (typically long fibers) are bonded together by chemical, mechanical, heat and/or solvent treatment, or any other treatment that is neither woven nor knitted. In some embodiments, the polymer-containing matrix comprise nonwoven fibers, e.g. of a kind used in the medical industry or in the disposable products industry. Without being limited thereto, fabric-like material comprising nonwoven fibers may include disposable non-woven sheets, e.g. used in disposable gowns, gloves, drapes and covers; masks; scrub suits; caps; shoe covers; bath wipes; wound dressings etc. The polymer-containing matrix is modified with a functional moiety (via the bifunctional linker) to improve the characteristics of the matrix. The term “functional moiety” means, in the context of the present disclosure, any chemical entity/compound that attributes to at least the surface of the polymer-containing matrix a new feature/functional characteristic. In some embodiments, the functional moiety provides the matrix with higher durability and/or strength and/or stability/resistance to external damaging effects. In some embodiments, the functional moieties is of a kind that provided the polymer-containing matrix with an improved aesthetic finish/look and feel. An improved finish of a matrix can be classified as a functional finish, e.g. any one of dyeing, waterproof finish (water proof agent), flame-retardant finish (flame retardant), anti-moth finish (anti-moth agent), antistatic finish (antistatic agent), antimicrobial (e.g. antibacterial agent), electro-conductive (electro-conducting material), texture modifying agent (an agent improving textile finish and resilience to treatments), moist-preserving agents, thermal isolating agents, thermal reflective agents, patterning agents (e.g. agents for photo-mask-selective UV passage), an agent adapted for dry finishes treatments such as brushing, calendaring, laminating, embossing, heat setting, polishing and laser treatment; each constituting an independent embodiment of the present disclosure. In some other embodiments, the functional moieties provide the matrix with improved performance, e.g. an improved function, e.g. smoothness, stability/durability, texture etc. In some embodiments, the functional moiety is selected from the group of moieties known to be used in the textile industry. In some embodiments the functional moieties are at least as one of a dye or reactive dye, or a dye enhancer. Reactive dyes are to be understood as dyes that include a functional group through which fixation to the linker is made. Reactive dyes are categorized by functional group and include, for example, groups such as monochlorotirazine, monofluorochlorotriazine, dichlorotriazine, difluorochloropyrimidine, dichloroquinoxaline, trichloropyrimidine, or groups such as vinylsulfone and vinyl amide. In some embodiments the functional moiety is a softening agent. Examples of softening agents are those typically used in the textile industry. In some embodiments the functional moiety is an anti-delamination agent. Examples of anti-delamination agent are those typically used in the textile industry. In some embodiments the functional moiety is an antimicrobial agent. Antimicrobials are protective agents that, being bacteriostatic, bactericidal, fungistatic and fungicidal, also offer special protection against the various forms of material rotting, e.g. textile rotting. An example of an antimicrobial agents that can be used for modification of the polymer-containing matrix include, without being limited thereto, is Triclosan (2,4,4-hydrophenyl trichloro (II) ether), a member of the antiseptic and disinfectant family. In some embodiments the functional moiety is a fluorescent pigment. Examples of fluorescent pigments are those typically used in the textile industry, such as, without being limited thereto, coumarin dyes. In some embodiments the functional moiety is an electro-conductive agent. Examples of electro-conductive agent that can be used, without being limited thereto, comprise organic polymers selected from polythiophenes, polypyrroles, polyanilines and their derivatives, or any combination thereof. In some embodiments the functional moiety comprises quantum dots (semiconductor nanocrystals). In some embodiments the quantum dots comprise organic quantum dots such as, without being limited thereto, coal derived quantum dots. In some embodiments, the bifunctional linker is linked to the polymer-containing matrix in a reaction involving an anhydride form thereof. Thus, also provided by the present disclosure is an anhydride form of the bifunctional linker of formula (II): where R1, R2, R3, R5, X1, and X2have the meaning as defined with respect to the compound of formula (I) and W′ is O. In some embodiments, the anhydride is represented by general formula (III): where R1, R2, R3, X1, and X2have the meaning as defined with respect to the compound of formula (I). Compound (II) or (III) are an anhydride of the bifunctional linker of formula (I). Thus, the same definitions and embodiments provided above with respect to compound of formula (I) apply also to the anhydride of formula (II) or (III), mutatis mutandis. In one preferred embodiment, the anhydride is a bis-allyl propionic acid (BAPA) anhydride. The present disclosure also provides processes for the preparation of the bifunctional linker of formula (I) and for the preparation of the anhydride of formula (II) or (III). With respect to the preparation of the bifunctional linker of formula (I), the process comprises reacting a starting compound (a propionic acid derivative) of formula (IV): where X1, X2and R3are as defined with respect to formula (I), with a nucleophilic reagent containing R1and/or R2and a leaving group. In some embodiments, compound of formula (IV) is used for the preparation of the bifunctional linker of formula (I) where R1and R2are identical (i.e. the same nucleophilic reagent is used for both substitutions). Yet, in some other embodiments, R1and R2can be different, this being achieved, for example, by carrying out protection of one of the hydroxyl groups of compound of Formula (V) using one equivalent of a protecting group and separating the mixture of products. Once one of the hydroxyl groups is protected, functionalization with a nucleophilic reagent of the unprotected hydroxyl, followed by de-protection and reaction of the second hydroxyl with a different nucleophilic reagent. When referring to a leaving group in the context of the present disclosure it is to be understood as meaning a leaving group known or suitable for use in a nucleophilic substitution reaction (SN1and/or SN2). Non-limiting examples of a leaving group include halides, tosylate and mesylate. In some embodiments, the leaving group is a bromide. The formation of the bifunctional linker is known in the art and is also illustrated in Figure JA, e.g. when bis-allyl propionic acid (BAPA) is formed by the use of allyl bromide. In some embodiments, the nucleophilic substitution taking place in the preparation of the compound of formula (I) requires elevated temperatures. In some embodiments, the reaction is at a temperature of between 100° C. to 180° C., at times between 120° C. to 160° C. The temperature will be determined based on the type of nucleophile used in the reaction. In some embodiments, the starting compound of formula (IV) is allowed to react with the nucleophilic reagent for at least one minute, at times, for at least 1, 2, 5, 10, 15, 30 or even 40 minutes and at times for more than an hour. The end of the reaction can be determined by techniques known in the art, depending on the functional agent. For the purpose of modifying the surface of the polymer containing matrix, the bifunctional linker of formula (I) needs to first be converted to its anhydride form. The present disclosure also provides a method of preparing an anhydride of the compound of formula (I). The anhydride form is represented by the general formula (II): wherein R1, R2, R3, R5X1, X2, X3, and W′ have the meaning as defined above with respect to the bifunctional linker/compound of formula (I). In some embodiments, the anhydride is represented by the general formula (III): In some embodiments, the anhydride is formed by reacting the bifunctional linker of general formula (I): where X1, X2and R1, R2, R3, R5and W are as defined with for formula (I). The conversion to the anhydride form requires reaction of the bifunctional compound of formula (I) with a coupling reagent (coupling reaction). In some embodiments, the coupling reagent is a carbodiimide. In some embodiments, the carbodiimide is selected from the group consisting of N,N′-diisopropylcarbodiimide (DIC), N,N′-Dicyclohexylcarbodiimide (DCC). In some embodiments, the carbodiimide is N,N′-Dicyclohexylcarbodiimide (DCC). The formation of BAPA anhydride is known in the art. In some embodiments, the formation of the anhydride requires a reaction period of several hours. The conversion of BAPA to its anhydride form is known in the art and is also illustrated inFIGS.1B, and1Cwhere BAPA is reacted with DCC to form BAPA anhydride. The anhydride is then used for the modification of the surface of a polymer-containing matrix. This is achieved by exposing the surface of the matrix that contains the polar reactive groups, e.g. hydroxyl groups (as with cellulose fibers) to the anhydride. The reaction conditions may vary, depending, inter alia, on the type of anhydride used. In some embodiments, the reaction being carried out at room temperature (20-25° C.), in the presence of a reaction medium comprising a pyridine derivative in a polar aprotic solvent. The pyridine derivative can be any one known in esterification and amidation. In some embodiments, the pyridine derivative is a dialkylaminopyridine. In some embodiments, the pyridine derivative is 4-dimethylaminopyridine (DMAP). In some embodiments, the polar aprotic solvent is selected from the group consisting of dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dihalomethane. In some embodiments, the polar aprotic solvent is dichloromethane (DCM). In some embodiments, the reaction medium comprises also an amine containing organic compound, such as, without being limited thereto, pyridine or pyridine derivative, dimethylaminopyridine (DMAP), and trimethylamine. In some embodiments, the amine containing compound is pyridine. At time, the modification reaction takes place for a period of at least 1 hour, at times, for a period of at least 2, 3, 4, 5, hours. The resulting modified polymer containing matrix comprises the polymers of the matrix having, covalently bound thereto, a plurality of the bifunctional linker defined herein. As noted above, the binding of the linker to the surface is such that the R1and R2are left free for functionalization by a functional agent as illustrated below. Further illustrated below, in accordance with some embodiments, the binding of the linker to the surface is by the formation of an ester or ether linkage with the polymer chain. The modification of surface carrying hydroxyl reactive groups is illustrated inFIG.2. Specifically, as illustrated, hydroxyl groups are reacted with BAP anhydride in the presence of DMAP and pyridine, both dissolved in DCM. The reaction is carried out, in this exemplary embodiment for 24 hours, at room temperature. Once the modified surface is formed, it may then be reacted with any desirable functional agent to form a functionalized polymeric matrix. The functionalization of the modified surface was found to be an speedy reaction when the modified surface and the functional agent are exposed to UV light (in the presence of a radical initiator). As illustrated in the exemplary embodiment ofFIG.4, the modified surface, in this embodiment, BAPA modified surface, is brought into contact with the functional agent and by the aid of UV light, the functional agent is reacted with the allyl moieties of BAPA. In some embodiments, functionalization is achieved using thermal energy (i.e. thermal initiation). For example, it has been found that when the functional agent is black or very dark colored, thermal activation of the reaction is preferable. Radical initiators are known in the art as compounds that promote radical reactions (by facilitating the production of radical species). In some embodiments, the radical initiator is a substance selected from the group consisting of, without being limited thereto, 2,2-Dimethoxy-2-phenylacetophenone (DMPA) and 4,4′-Azobis(4-cyanovaleric acid). In some embodiments, functionalization is achieved using thiols to generate repetitively branched molecules for example dendritic linker. In some embodiments, the thiol is 2-Mercaptoethanol. In some embodiments, functionalization is to provide a fluorescent marker, e.g. when the functional agent is a fluorescent compound. In some embodiments, the functional agent comprises coumarin. In some embodiments, the functional agent is a compound having electrical conductivity. In some embodiments, a functional agent having electrical conductivity is one comprising polythiophene. The formation of exemplary functionalized surfaces is illustrated inFIG.5, which is further discussed below. In these two illustrated embodiments, the bifunctional linker is reacted by a thiol-ene click reaction. A thiol-ene click reaction is known in the art as a radical reaction which is initiated by a photochemical process (UV light) or by thermal initiation. As used herein, the forms “a”, “an” and “the” include singular as well as plural references unless the context clearly dictates otherwise. For example, the term “bifunctional linker” includes one or more such compounds. Further, as used herein, the term “comprising” is intended to mean that the polymer containign matrix (for example) can include a polymer but not excluding other elements, such as non-polymeric material. The term “consisting essentially of” is used to define for example, matrices, which include polymers exclude other elements that may have an essential significance on properties of the matrix. “Consisting of” shall thus mean excluding more than trace elements of elements other than the polymers forming the matrix. Embodiments defined by each of these transition terms are within the scope of this invention. Further, all numerical values, e.g. when referring the amounts or ranges approximations are also included, the values being varied (+) or (−) by up to 20%, at times by up to 10% of from the stated values. It is to be understood, even if not always explicitly stated that all numerical designations are preceded by the term “about”. The invention will now be exemplified in the following description of experiments that were carried out in accordance with the present disclosure. It is to be understood that these examples are intended to be in the nature of illustration rather than of limitation. Obviously, many modifications and variations of these examples are possible in light of the above teaching. It is therefore, to be understood that within the scope of the appended claims, the invention may be practiced otherwise, in a myriad of possible ways, than as specifically described hereinbelow. Non-Limiting Examples Example 1: Preparation of Bis-Allyl Propionic Acid, BAPA and BAPA Anhydride and BAPA-acyl chloride Materials: Cellulose filter paper (Whatman brand), was used as a cellulose substrate and was dried in a vacuum oven at 65° C. for 14 hours prior to use. 2,2-Bis(hydroxymethyl)propionic acid (Bis-MPA), allyl bromide, thionyl chloride (SOCl2), N,N′-dicyclohexylcarbodiimide (DCC), pyridine, 4-dimethyl(aminopyridine) (DMAP) 1H,1H,2H,2H-perfluorodecanethiol, 1-decanethiol, 2-mercaptoethanol, 2,2-dimethoxy-2-phenyl-acetophenone (DMPA) were purchased from Sigma-Aldrich. Trimethylamine (Et3N), toluene, dichloromethane (DCM), dry DCM and ethyl alcohol were purchased from Bio-lab ltd. Concentrated hydrochloric acid (HCl) and sodium hydroxide (NaOH) pellets were purchased from Merck. All the materials were used as received. Experimental Procedure Preparation of BAPA (Precursor for the Synthesis of the Molecular Linkers “2” and “3” Below). Bis-MPA (20 gr, 0.15 mol) and NaOH (58 gr, 1.44 mol) were added to a two neck round bottom flask containing 300 mL of toluene. The reaction vessel was heated to 110° C. and the mixture was left about 30 min. under vigorous stirring. Then, allyl bromide (125 gr, 1.04 mol) was added to the vessel and the reaction mixture was refluxed overnight. After the reaction was completed, the mixture was acidified (pH ca. 1-2) concentrated HCl. The mixture was washed using 200 mL of water and then 200 mL of brine solution. The organic phase was dried with MgSO4, followed by removal of the solvent under vacuum. The crude product was purified using column chromatography to give a slightly viscous and yellowish liquid (25.4 gr, 77%). The synthesis of BAPA is also known in the art [Montanez, Maria I., et al. “Accelerated growth of dendrimers via thiolene and esterification reactions.” Macromolecules 43.14 (2010): 6004-6013.]. Generally, the synthesis was carried out according the Scheme provided inFIG.1A. Preparation of Bis(Allyl Propionic Acid) Anhydride (“Linker 2”). BAPA (10 gr, 46.73 mmol) and DCC (4.82 gr, 23.36 mmol) were added to a round bottom flask containing 25 mL of DCM. The mixture was stirred overnight at room temperature. The DCC-urea by product was removed by vacuum filtration using glass filter, followed by removal of the solvent under vacuum. The product was isolated as a slightly viscous and yellowish liquid (8.33 gr, 87%). Generally, the synthesis was carried out according the Scheme provided inFIG.1B. A synthesis of BAPA anhydride is also known in the art (Malkoch, Michael, Eva Malmstrom, and Anders Hult. “Rapid and efficient synthesis of aliphatic ester dendrons and dendrimers.” Macromolecules 35.22 (2002): 8307-8314.). Preparation of Bis(Allyl Propionoyl Chloride) (“Linker 3”). Generally, the synthesis was carried out according the Scheme provided inFIG.1C. Specifically, BAPA (2.5 g, 0.012 mol) was charged in a flame dried flask and cooled to 0° C. Next, SOCl2(10 mL, 0.14 mol) was added dropwise to the neat BAPA with stirring. Upon completion of the addition, the reaction was further stirred for 3 hours at room temperature, followed by evaporation of the excess SOCl2under reduced pressure. Product (3) inFIG.1Cwas obtained quantitatively as a yellow oil and used without further purification.1H NMR (400 MHz, CDCl3): δ 5.86 (m, 2H), 5.27 (dq, J=17.2, 1.6 Hz, 2H), 5.18 (dq, J=10.5, 1.3 Hz, 2H), 4.00 (dt, J=5.5, 1.3 Hz, 4H), 3.60 (s, 4H), 1.34 (s, 3H) ppm;13C NMR (100 MHz, CDCl3): δ 176.5 (C), 134.4 (CH), 117.3 (CH2), 72.5 (CH2), 71.6 (CH2), 58.5 (C), 18.1 (CH3) ppm; Cold cluster CI-MS: m/z 233.2 [M+H]+. Example 2: Modification of Cellulose Filter Paper with Linker Molecule Surface Modification of Cellulose Filter Paper with Molecular Linker 2. Generally, the surface modification of the cellulose filter with the linker molecule was carried out according the Scheme provided inFIG.2. Specifically, filter paper (WHATMAN, number 4) (53.7 mg, 2×3 cm) was washed with acetone and then vacuum dried at 65° C. for 14 hours prior to use. Next, filter paper was immersed into a glass flask containing molecular linker 2 (2.5 gr, 6.1 mmol), DMAP (2.3 gr, 19 mmol) and pyridine (410 μl, 5 mmol) in DCM (8 mL). The reaction was carried out at room temperature for 24 hours using shaker, followed by soxhlet extraction with DCM for 24 hours to remove residual reactants. Subsequently, the filter paper was washed with deionized water, EtOH and finally washed again with DCM, followed by vacuum drying at 65° C. for 14 hours. Surface Modification of Cellulose Filter Paper with Linker 3. Generally, the modification of the cellulose filter paper with the linker was carried out according the Scheme provided inFIG.3. Specifically, filter paper (WHATMAN, number 4) (80.1 mg 3×3 cm) was washed with acetone and then vacuum dried at 65° C. for 14 hours prior to use. Next, filter paper was introduced into a flame-dried glass flask containing dry DCM (8 mL), DMAP (0.475 mmol, 58 mg) and Et3N (1.45 ml, 10.45 mmol). Next, a solution of the molecular linker 3 (2.2 gr, 9.5 mmol) in 4 ml of dry DCM was added to the flask and the reaction was stirred at 50° C. for 2 hours. Upon cooling to room temperature, the modified filter paper was extracted twice with DCM, washed with deionized water and EtOH and further extracted using soxhlet in DCM for 18 hours. Finally, the filter paper was dried at 65° C. for 14 hours. FIGS.4A-4B, which are further discussed below, show that the modification with linker 2 or linker 3 both resulted in an increase in hydrophobicity of the surface. Example 3: Characterization of Cellulose Filter Paper Modified with Molecular Linkers 2 and 3 Contact Angle Measurements. The modifications describes in Example 2, with linker 2 and linker 3, resulted in an increase in hydrophobicity of the surface. This is evident from the contact angle measurements of cellulose filter paper modified with each molecular linker as shown inFIGS.4A and4B. X-Ray Photoelectron Spectroscopy Measurements. High-resolution X-ray Photoelectron Spectroscopy (XPS) analysis of the unmodified filter paper, filter paper modified with molecular linker 2 and filter paper modified with molecular linker 3 are presented in Table 1. TABLE 1High-resolution X-ray Photoelectron Spectroscopy (XPS) analysisUnmodifiedLinker 2- modifiedLinker 3- modifiedSamplepaperpaperpaperC1 intensity18.1%24.2%26.2%(C—C, C—H)C2 intensity63.2%54.8%56.9%(C—O)C3 intensity17.3%15.9%13.8%(O—C—O)C4 intensity1.4%5.0%3.1%(O—C═O)O/C ratio0.660.550.55 Example 4: Incorporation of Functional Materials into Linker-Modified Cellulose Filter Paper Procedure for Covalent Binding of 1H, 1H, 2H, 2H-Perfluorodecanethiol. Generally, the incorporation was carried out according the synthetic route provided inFIG.5. Specifically, bis(allyl propionic acid) anhydride modified cellulose paper (36 mg, 1.6×2.5 cm) was placed into a solution containing 1H,1H,2H,2H-perfluorodecanethiol (0.5 gr, 1.04 mmol), DMPA (5 wt %) and 1 ml DCM. Next, the reaction vessel was sealed and purged with argon for 1 min. The reaction mixture was irradiated for 15 min. at 365 nm using UV lamp. This procedure was repeated for the other side of the filter paper. After the reaction was completed, the modified cellulose paper was extracted with DCM using soxhlet for 18 hours and dried in a vacuum oven at 65° C. for 14 hours. Procedure for Covalent Binding of 1-Decanethiol. Generally, the incorporation was carried out according the synthetic route provided inFIG.6. Specifically, bis(allyl propionic acid) anhydride modified cellulose paper (36 mg, 1.6×2.5 cm) was placed into a solution containing 1-decanethiol (0.5 gr, 2.87 mmol), DMPA (5 wt %) and 1 ml DCM. Next, the reaction vessel was sealed and purged with argon for 1 min. The reaction mixture was irradiated for 15 min. at 365 nm using UV lamp. This procedure was repeated for the other side of the filter paper. After the reaction was completed, the modified cellulose paper was extracted with DCM using soxhlet for 18 hours and dried in a vacuum oven at 65° C. for 14 hours. Procedure for Covalent Binding of Mercaptoethanol. Generally, the incorporation was carried out according the Scheme provided inFIG.7. Specifically, filter paper modified with molecular linker 2 (26.05 mg, 3×1 cm) was vacuum dried at 65° C. for 14 hours and then added to a solution containing 2-mercaptoethanol (1 gr, 12.8 mmol), DMPA (5 wt %) in 3 ml DCM. The reaction vessel was sealed and purged with argon for 1 min. and thereafter irradiated with a 365 nm UV lamp for 20 min. Subsequently, the filter paper was extracted with DCM via soxhlet to remove residual reactants and dried in a vacuum oven at 65° C. for 14 hours. Attachment of Coumarin-Thiol to the Filter Paper Modified with Linker Generally, the incorporation of a linker was carried out according the Scheme provided inFIG.8. A modified cellulose paper (18.45 mg, 1.5×1.2 cm) was placed into a solution containing DCM (800 μL), coumarin-thiol (30 mg, 0.093 mmol) and DMPA (5 wt %). The reaction vessel was sealed and purged with argon for 1 min., followed by irradiation with a 365 nm UV lamp for 20 min. Subsequently, the filter paper was extracted with DCM using soxhlet for 18 hours and dried in a vacuum oven at 65° C. for 14 hours. The reaction was also performed in a similar manner using the same molar amounts on unmodified cellulose paper as a control. Example 5: Characterization of Linker-Modified Filter Paper Bonded to Functional Materials The contact angle measurements of the cellulose filter paper modified with molecular linker 2, molecular linker 3 or perfluorodecanethiol are presented inFIG.9. They show that the binding of the functional agent to the molecular linker increased the hydrophobicity of the linker-filter paper. Further, a low resolution XPS of perfluorodecanethiol-modified filter paper is presented inFIG.10. This Figure confirms the binding of the perfluorodecanethiol functional agent to the filter paper. Further, solid-state fluorescence measurement of the molecular linker- and coumarin-modified filter paper (excitation at 435 nm) is presented inFIG.11. This figure shows the fluorescence intensity of the functional agent on the modified filter paper as compared to the filter paper carrying only the linker, without the functional agent. | 35,822 |
11858888 | DETAILED DESCRIPTION Before the present disclosure is described in greater detail, it is to be understood that this disclosure is not limited to particular embodiments described, and as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present disclosure will be limited only by the appended claims. Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure, the preferred methods and materials are now described. All publications and patents cited in this specification are herein incorporated by reference as if each individual publication or patent were specifically and individually indicated to be incorporated by reference and are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited. The citation of any publication is for its disclosure prior to the filing date and should not be construed as an admission that the present disclosure is not entitled to antedate such publication by virtue of prior disclosure. Further, the dates of publication provided could be different from the actual publication dates that may need to be independently confirmed. As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure. Any recited method can be carried out in the order of events recited or in any other order that is logically possible. Embodiments of the present disclosure will employ, unless otherwise indicated, techniques of medicine, organic chemistry, biochemistry, molecular biology, pharmacology, toxicology, and the like, which are within the skill of the art. Such techniques are explained fully in the literature. It must be noted that, as used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a support” includes a plurality of supports. In this specification and in the claims that follow, reference will be made to a number of terms that shall be defined to have the following meanings unless a contrary intention is apparent. As used herein, the following terms have the meanings ascribed to them unless specified otherwise. In this disclosure, “comprises,” “comprising,” “containing” and “having” and the like can have the meaning ascribed to them in U.S. patent law and can mean “includes,” “including,” and the like; “consisting essentially of” or “consists essentially” or the like, when applied to methods and compositions encompassed by the present disclosure refers to compositions like those disclosed herein, but which may contain additional structural groups, composition components or method steps (or analogs or derivatives thereof as discussed above). Such additional structural groups, composition components or method steps, etc., however, do not materially affect the basic and novel characteristic(s) of the compositions or methods, compared to those of the corresponding compositions or methods disclosed herein. Prior to describing the various embodiments, the following definitions are provided and should be used unless otherwise indicated. Definitions As used herein, the nomenclature alkyl, alkoxy, carbonyl, etc. is used as is generally understood by those of skill in the chemical art. As used in this specification, alkyl groups can include straight-chained, branched and cyclic alkyl radicals containing up to about 20 carbons, or 1 to 16 carbons, and are straight or branched. Exemplary alkyl groups herein include, but are not limited to, methyl, ethyl, propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl and isohexyl. As used herein, lower alkyl refer to carbon chains having from about 1 or about 2 carbons up to about 6 carbons. Suitable alkyl groups may be saturated or unsaturated. Further, an alkyl may also be substituted one or more times on one or more carbons with substituents selected from a group consisting of C1-015 alkyl, allyl, allenyl, alkenyl, C3-C7 heterocycle, aryl, halo, hydroxy, amino, cyano, oxo, thio, alkoxy, formyl, carboxy, carboxamido, phosphoryl, phosphonate, phosphonamido, sulfonyl, alkylsulfonate, arylsulfonate, and sulfonamide. Additionally, an alkyl group may contain up to 10 heteroatoms, in certain embodiments, 1, 2, 3, 4, 5, 6, 7, 8 or 9 heteroatom substituents. Suitable heteroatoms include nitrogen, oxygen, sulfur and phosphorous. As used herein, “cycloalkyl” refers to a mono- or multicyclic ring system, in certain embodiments of 3 to 10 carbon atoms, in other embodiments of 3 to 6 carbon atoms. The ring systems of the cycloalkyl group may be composed of one ring or two or more rings which may be joined together in a fused, bridged or spiro-connected fashion. As used herein, “aryl” refers to aromatic monocyclic or multicyclic groups containing from 3 to 16 carbon atoms. As used in this specification, aryl groups are aryl radicals, which may contain up to 10 heteroatoms, in certain embodiments, 1, 2, 3 or 4 heteroatoms. An aryl group may also be optionally substituted one or more times, in certain embodiments, 1 to 3 or 4 times with an aryl group or a lower alkyl group and it may be also fused to other aryl or cycloalkyl rings. Suitable aryl groups include, for example, phenyl, naphthyl, tolyl, imidazolyl, pyridyl, pyrroyl, thienyl, pyrimidyl, thiazolyl and furyl groups. As used in this specification, a ring is defined as having up to 20 atoms that may include one or more nitrogen, oxygen, sulfur or phosphorous atoms, provided that the ring can have one or more substituents selected from the group consisting of hydrogen, alkyl, allyl, alkenyl, alkynyl, aryl, heteroaryl, chloro, iodo, bromo, fluoro, hydroxy, alkoxy, aryloxy, carboxy, amino, alkylamino, dialkylamino, acylamino, carboxamido, cyano, oxo, thio, alkylthio, arylthio, acylthio, alkylsulfonate, arylsulfonate, phosphoryl, phosphonate, phosphonamido, and sulfonyl, and further provided that the ring may also contain one or more fused rings, including carbocyclic, heterocyclic, aryl or heteroaryl rings. As used herein, alkenyl and alkynyl carbon chains, if not specified, contain from 2 to 20 carbons, or 2 to 16 carbons, and are straight or branched. Alkenyl carbon chains of from 2 to 20 carbons, in certain embodiments, contain 1 to 8 double bonds, and the alkenyl carbon chains of 2 to 16 carbons, in certain embodiments, contain 1 to 5 double bonds. Alkynyl carbon chains of from 2 to 20 carbons, in certain embodiments, contain 1 to 8 triple bonds, and the alkynyl carbon chains of 2 to 16 carbons, in certain embodiments, contain 1 to 5 triple bonds. As used herein, “heteroaryl” refers to a monocyclic or multicyclic aromatic ring system, in certain embodiments, of about 5 to about 15 members where one or more, in one embodiment 1 to 3, of the atoms in the ring system is a heteroatom, that is, an element other than carbon, including but not limited to, nitrogen, oxygen or sulfur. The heteroaryl group may be optionally fused to a benzene ring. Heteroaryl groups include, but are not limited to, furyl, imidazolyl, pyrrolidinyl, pyrimidinyl, tetrazolyl, thienyl, pyridyl, pyrrolyl, N-methylpyrrolyl, quinolinyl and isoquinolinyl. As used herein, “heterocyclyl” refers to a monocyclic or multicyclic non-aromatic ring system, in one embodiment of 3 to 10 members, in another embodiment of 4 to 7 members, in a further embodiment of 5 to 6 members, where one or more, in certain embodiments, 1 to 3, of the atoms in the ring system is a heteroatom, that is, an element other than carbon, including but not limited to, nitrogen, oxygen or sulfur. In embodiments where the heteroatom(s) is(are) nitrogen, the nitrogen is optionally substituted with alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, cycloalkyl, heterocyclyl, cycloalkylalkyl, heterocyclylalkyl, acyl, guanidino, or the nitrogen may be quaternized to form an ammonium group where the substituents are selected as above. As used herein, “aralkyl” refers to an alkyl group in which one of the hydrogen atoms of the alkyl is replaced by an aryl group. As used herein, “halo”, “halogen” or “halide” refers to F, Cl, Br or I. As used herein, “haloalkyl” refers to an alkyl group in which one or more of the hydrogen atoms are replaced by halogen. Such groups include, but are not limited to, chloromethyl and trifluoromethyl. As used herein, “aryloxy” refers to RO—, in which R is aryl, including lower aryl, such as phenyl. As used herein, “acyl” refers to a —COR group, including for example alkylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, or heteroarylcarbonyls, all of which may be optionally substituted. As used herein, “ω-3”, “ω-6”, etc. refers to the customary nomenclature of polyunsaturated fatty acids or their derivatives, wherein the position of a double bond (C═C) is at the carbon atom counted from the end of the carbon chain (methyl end) of the fatty acid or fatty acid derivative. For example, “ω-3” means the third carbon atom from the end of the carbon chain of the fatty acid or fatty acid derivative. Similarly, “ω-3”, “ω-6”, etc. also refers to the position of a substituent such as a hydroxyl group (OH) located at a carbon atom of the fatty acid or fatty acid derivative, wherein the number (e.g. 3, 6, etc.) is counted from the end of the carbon chain of the fatty acid or fatty acid derivative. As used herein, the abbreviations for any protective groups and other compounds, are, unless indicated otherwise, in accord with their common usage, recognized abbreviations, or the IUPAC-IUB Commission on Biochemical Nomenclature (see, (1972)Biochem.11:942-944). As used herein, wherein in chemical structures of the compounds of the disclosure are shown having a terminal carboxyl group “—COOR” the “R” is intended to designate a group covalently bonded to the carboxyl such as an alkyl group. In the alternative, the carboxyl group is further intended to have a negative charge as “—COO−” and R is a cation including a metal cation, an ammonium cation and the like. As used herein “subject” is an animal, typically a mammal, including human, such as a patient. As used herein, “pharmaceutically acceptable derivatives” of a compound include salts, esters, enol ethers, enol esters, acetals, ketals, orthoesters, hemiacetals, hemiketals, acids, bases, solvates, hydrates or prodrugs thereof. Such derivatives may be readily prepared by those of skill in this art using known methods for such derivatization. The compounds produced may be administered to animals or humans without substantial toxic effects and either are pharmaceutically active or are prodrugs. Pharmaceutically acceptable salts include, but are not limited to, amine salts, such as but not limited to N,N′-dibenzylethylenediamine, chloroprocaine, choline, ammonia, diethanolamine and other hydroxyalkylamines, ethylenediamine, N-methylglucamine, procaine, N-benzylphenethylamine, 1-para-chlorobenzyl-2-pyrrolidin-1′-ylmethylbenzimidazole, diethylamineand other alkylamines, piperazine and tris(hydroxymethyl)aminomethane; alkali metal salts, such as but not limited to lithium, potassium and sodium; alkali earth metal salts, such as but not limited to barium, calcium and magnesium; transition metal salts, such as but not limited to zinc; and other metal salts, such as but not limited to sodium hydrogen phosphate and disodium phosphate; and also including, but not limited to, salts of mineral acids, such as but not limited to hydrochlorides and sulfates; and salts of organic acids, such as but not limited to acetates, lactates, malates, tartrates, citrates, ascorbates, succinates, butyrates, valerates and fumarates. Pharmaceutically acceptable esters include, but are not limited to, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, cycloalkyl and heterocyclyl esters of acidic groups, including, but not limited to, carboxylic acids, phosphoric acids, phosphinic acids, sulfonic acids, sulfinic acids and boronic acids. Pharmaceutically acceptable enol ethers include, but are not limited to, derivatives of formula C═C(OR) where R is hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, cycloalkyl ar heterocyclyl. Pharmaceutically acceptable enol esters include, but are not limited to, derivatives of formula C═C(OC(O)R) where R is hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, cycloalkyl ar heterocyclyl. Pharmaceutically acceptable solvates and hydrates are complexes of a compound with one or more solvent or water molecules, or 1 to about 100, or 1 to about 10, or one to about 2, 3 or 4, solvent or water molecules. As used herein, amelioration of the symptoms of a particular disorder by administration of a particular compound or pharmaceutical composition refers to any lessening, whether permanent or temporary, lasting or transient that can be attributed to or associated with administration of the composition. The term “therapeutically effective amount” as used herein refers to that amount of an embodiment of the composition or pharmaceutical composition being administered that will relieve to some extent one or more of the symptoms of the disease or condition being treated, and/or that amount that will prevent, to some extent, one or more of the symptoms of the condition or disease that the subject being treated has or is at risk of developing. As used interchangeably herein, “subject,” “individual,” or “patient,” refers to a vertebrate, preferably a mammal, more preferably a human. Mammals include, but are not limited to, murines, simians, humans, farm animals, sport animals, and pets. The term “pet” includes a dog, cat, guinea pig, mouse, rat, rabbit, ferret, and the like. The term farm animal includes a horse, sheep, goat, chicken, pig, cow, donkey, llama, alpaca, turkey, and the like. A “pharmaceutically acceptable excipient,” “pharmaceutically acceptable diluent,” “pharmaceutically acceptable carrier,” or “pharmaceutically acceptable adjuvant” means an excipient, diluent, carrier, and/or adjuvant that are useful in preparing a pharmaceutical composition that are generally safe, non-toxic and neither biologically nor otherwise undesirable, and include an excipient, diluent, carrier, and adjuvant that are acceptable for veterinary use and/or human pharmaceutical use. “A pharmaceutically acceptable excipient, diluent, carrier and/or adjuvant” as used in the specification and claims includes one and more such excipients, diluents, carriers, and adjuvants. As used herein, a “pharmaceutical composition” or a “pharmaceutical formulation” is meant to encompass a composition or pharmaceutical composition suitable for administration to a subject, such as a mammal, especially a human and that refers to the combination of an active agent(s), or ingredient with a pharmaceutically acceptable carrier or excipient, making the composition suitable for diagnostic, therapeutic, or preventive use in vitro, in vivo, or ex vivo. In general a “pharmaceutical composition” is sterile, and preferably free of contaminants that are capable of eliciting an undesirable response within the subject (e.g., the compound(s) in the pharmaceutical composition is pharmaceutical grade). Pharmaceutical compositions can be designed for administration to subjects or patients in need thereof via a number of different routes of administration including oral, intravenous, buccal, rectal, parenteral, intraperitoneal, intradermal, intracheal, intramuscular, subcutaneous, inhalational and the like. The term “administration” refers to introducing a composition of the present disclosure into a subject. One preferred route of administration of the composition is topical administration. However, any route of administration, such as oral, intravenous, subcutaneous, peritoneal, intra-arterial, inhalation, vaginal, rectal, nasal, introduction into the cerebrospinal fluid, or instillation into body compartments can be used. As used herein, “treatment” and “treating” refer to the management and care of a subject for the purpose of combating a condition, disease or disorder, in any manner in which one or more of the symptoms of a disease or disorder are ameliorated or otherwise beneficially altered. The term is intended to include the full spectrum of treatments for a given condition from which the patient is suffering, such as administration of the active compound for the purpose of: alleviating or relieving symptoms or complications; delaying the progression of the condition, disease or disorder; curing or eliminating the condition, disease or disorder; and/or preventing the condition, disease or disorder, wherein “preventing” or “prevention” is to be understood to refer to the management and care of a patient for the purpose of hindering the development of the condition, disease or disorder, and includes the administration of the active compounds to prevent or reduce the risk of the onset of symptoms or complications. The patient to be treated is preferably a mammal, in particular a human being. Treatment also encompasses any pharmaceutical use of the compositions herein, such as use for treating a disease as provided herein. Discussion Inflammatory, degenerative, and neurodegenerative diseases include a large number of diseases that affect a very large number of people worldwide. In most cases, these diseases and related conditions and disorders are difficult to treat, and remain as an unmet medical need. Inflammatory diseases in the scope of this disclosure include acute and chronic disorders where homeostasis is disrupted by an abnormal or dysregulated inflammatory response. These conditions are initiated and mediated by a number of inflammatory factors, including oxidative stress, chemokines, cytokines, breakage of blood/tissue barriers, autoimmune diseases or other conditions that engage leukocytes, monocytes/macrophages or parenchymal cells that induce excessive amounts of pro-cell injury, pro-inflammatory/disruptors of homeostasis mediators. These diseases occur in a wide range of tissues and organs and are currently treated, by anti-inflammatory agents such as corticosteroids, non-steroidal anti-inflammatory drugs, TNF modulators, COX-2 inhibitors, etc. Degenerative diseases include conditions that involve progressive loss of vital cells and tissues that result in progressive impairment of function, such as loss of cartilage in knees, hip joints or other joints such as in osteoarthritis. Other degenerative diseases engages cellular and intercellular homeostasis perturbations and includes heart disease, atherosclerosis, cancer, diabetes, intestinal bowel disease, osteoporosis, prostatitis, rheumatoid arthritis, etc. Neurodegenerative diseases include some of the major diseases of the brain, retina, spinal cord and peripheral nerves, whereby a progressive demise of cellular organization leads to impaired function. These are due to immune or inflammatory disorders and/or to inherited conditions or aging. They include multiple sclerosis, Alzheimer's disease, Parkinson's disease, amyotrophic lateral sclerosis, retina degenerative diseases such as age-related macular degeneration, inherited eye diseases such as retinitis pigmentosa, glaucoma, etc. Retinal degenerative diseases are the leading causes of blindness that affects very large numbers of people. Retinal degeneration is the deterioration of the retina caused by the progressive and eventual death of the photoreceptor cells of the retina. Examples of common retinal degenerative diseases include retinitis pigmentosa, age-related macular degeneration, and Stargardt disease. Retinitis pigmentosa affects between 50,000 and 100,000 people in the United States alone, and macular degeneration is the leading cause of vision loss for those aged 55 and older in the United States, affecting more than 10 million people. There are no effective treatments for these and other retinal degenerative diseases. Despite progress made in understanding the pathophysiology of inflammatory and degenerative diseases, the detailed molecular mechanisms involved in the initiation and progression of these conditions remain poorly understood. For retinal degenerative diseases, the detailed molecular mechanisms involved in the progressive loss of photoreceptor cells remain unknown, and available treatments today are not able to effectively treat these major diseases and prevent loss of sight. What is needed is a method for the prevention and treatment of retinal degenerative diseases that ensures the survival of the retina photoreceptor cells. Available treatments today are not able to effectively treat these major diseases or to slow-down their progressive impairment of vital functions. What is needed is a method that ensures the survival of critical cells undergoing oxidative stress or other homeostatic disruptions. Therefore, there is a major therapeutic void for the management of inflammatory, neuroinflammatory, degenerative and neurodegenerative diseases. This disclosure provides compounds, compositions and methods for the effective prevention and treatment of inflammatory and degenerative diseases, including neurodegenerative diseases and retinal degenerative diseases. The disclosure is based on new findings regarding the key protective role of certain omega-3 very long chain-polyunsaturated fatty acids (n3 VLC-PUFA) and related hydroxylated derivatives. In particular, described herein are methods and compounds for the protection of the retina by inducing the survival of photoreceptors. The methods describe herein involve the use of compounds that induce survival signaling in both the retinal pigment epithelial cells and photoreceptors. Recent investigations have shown that certain polyunsaturated fatty acids (PUFA) are enzymatically converted to bioactive derivatives that play important roles in inflammation and related conditions. Notable among these are the omega-3 (n3) fatty acids containing 22 carbons including eicosapentaenoic acid (EPA or C20:5n3) (20 carbons, 5 double bonds, omega-3), docosapentaenoic acid (DPA or C22:5n3), and especially docosahexaenoic acid (DHA or C22:6n3) (22 carbons, 6 double bonds, omega-3). These PUFA are converted via lipoxygenase-type enzymes to biologically active hydroxylated PUFA derivatives. Most important among these are specific types of hydroxylated derivatives that are generated in certain inflammation-related cells via the action of a lipoxygenase (LO) enzyme (e.g. 15-LO, 12-LO), and result in the formation of mono-, di- or tri-hydroxylated PUFA derivatives with potent actions including anti-inflammatory, pro-resolving, neuroprotective or tissue-protective actions, among others. For example, neuroprotectin D1 (NPD1), a dihydroxy derivative from DHA formed in cells via the enzymatic action of 15-lipoxygenase (15-LO) was shown to have a defined R/S and Z/E stereochemical structure (10R,17S-dihydroxy-docosa-4Z,7Z,11E, 13E,15Z,19Z-hexaenoic acid) and a unique biological profile that includes stereoselective potent anti-inflammatory, homeostasis-restoring, pro-resolving, bioactivity. NPD1 has been shown to modulate neuroinflammatory signaling and proteostasis, and to promote nerve regeneration, neuroprotection, and cell survival. Other important types of omega-3 fatty acids are the omega-3 very-long-chain polyunsaturated fatty acids (n3 VLC-PUFA or VLC-PUFA), which are produced in cells containing elongase enzymes that elongate PUFA with lower number of carbons to VLC-PUFA containing between 24 to 36 carbons. Representative types of VLC-PUFA include C32:6n3 (32 carbons, 6 double bonds, omega-3), C34:6n3, C32:5n3, and C34:5n3, which are biogenically derived through the action of elongase enzymes, particularly ELOVL4 (ELOngation of Very Long chain fatty acids 4). These fatty acids are also acylated in complex lipids including sphingolipids and phospholipids particularly in certain molecular species of phosphatidyl choline. These VLC-PUFA are thought to display functions in membrane organization, and their significance to health is increasingly recognized. The biosynthesis and biological functions of VLC-PUFA have been the subject of a number of recent investigations that have suggested potential roles in certain diseases. An increasing number of studies have demonstrated the importance of VLC-PUFA in the retina, an integral part of the central nervous system. For example, the autosomal dominant Stargardt-like macular dystrophy (STGD3), a Juvenile-onset retinal degenerative disease is caused by mutations in exon 6 of the ELOVL4 gene that leads to a truncated ELOVL4 protein (a key elongase enzyme) without an endoplasmic reticulum (ER) retention/retrieval signal, resulting in severe decrease in the biosynthesis of VLC-PUFA. Low retinal levels of VLC-PUFA and abnormally low n3/n6 ratios also occur in age-related macular degeneration (AMD) donor eyes as compared to age-matched control eye donors. Recessive ELOVL4 mutations display clinical features of ichthyosis, seizures, mental retardation, and spastic quadriplegia that resembles Sjogren-Larsson syndrome (SLS) with severe neurologic phenotype implying the significance of VLC-PUFA synthesis for the central nervous system and cutaneous development. VLC-PUFA were found to be incorporated in phospholipids of the photoreceptor outer membrane, and were shown to play important roles in the longevity of photoreceptors, and in their synaptic function and neuronal connectivity. Therefore, bioactive derivatives based on VLC-PUFA, which are able to prevent the apoptosis of photoreceptor cells may provide therapeutic benefits for various types of retinal degenerative diseases, including Stargardt-like macular dystrophy (STGD3), and X-linked juvenile retinoschisis (XLRS) an inherited early onset retinal degenerative disease caused by mutations in the RS1 gene, which is the leading cause of juvenile macular degeneration in males. This condition denotes a significant photoreceptor synaptic impairment for which there is no available treatment Although VLC-PUFA are attracting increasing attention, their detailed biological role and functional significance remains poorly understood, and their potential use in medicine has not been fully appreciated. In particular, the detailed role and potential beneficial use of VLC-PUFA and their synthetic derivatives as potential therapeutics remains to be established. Moreover, the potential use of VLC-PUFA in inflammatory, degenerative diseases, and neurodegenerative diseases of the retina and the brain, such as stroke, Alzheimer's disease, autism spectrum disorders, schizophrenia, Parkinson's disease, remains to be developed. The structures, properties, and potential effects of VLC-PUFA in cells and tissues, such as the retina, where they are known to play dominant roles were evaluated. Experiments were done using human retinal pigment epithelial (RPE) cells, which are neuroectoderm-derived post-mitotic cells of the retina, an integral part of the central nervous system. These cells are richly endowed with a multitude of mechanisms to protect themselves from injury and to protect other cells, particularly the survival of photoreceptors. They are the most active phagocyte of the human body, critical for the health of photoreceptors and vision, and have the ability to secrete neurotrophins and other beneficial substances. In pathological conditions they recapitulate aspects of Alzheimer's disease by processing amyloid precursor protein and contributing to the formation of Drusen, analogously to the senile amyloid plaques. Thus, these are among the reasons that some of the experimental data included in this disclosure were obtained with RPE cells. Therefore, the data provided herein are representative of the expected activities of the provided compounds in other cells and tissues where VLC-PUFA are known to be generated or be present. Based on the data detailed herein, we postulate that VLC-PUFA are expressed in certain forms of these cells, and in a paracrine fashion they induce the expression of protective phonotypes of these cells. These cells appear between the RPE and the photoreceptors, a zone of immune privilege regulated by immunosuppressive RPE signals and other factors. There is a growing evidence that a reduced presence of VLC-PUFA in certain cells and tissues is associated with degenerative, neurodegenerative, and retinal degenerative diseases, which are linked to excessive and persistent inflammatory environment. The naturally occurring VLC-PUFA are biosynthesized via the actions of elongase enzymes, such as ELOVL4, which add two carbons at a time starting from DHA (which has 22 carbon atoms), as summarized inFIG.13. Thus, biogenetically derived VLC-PUFA contain only an even number of carbons ranging from 24 of up to 42 carbons. Such naturally occurring VLC-PUFA have been detected in the form of free acids or as components of cellular lipids in mammalian tissues. Due to the requirement of elongase enzymes in their biosynthesis, VLC-PUFA containing an odd number of carbons are not known to exist in nature. This disclosure was conceived on the hypothesis that therapeutic interventions for these VLC-PUFA related diseases can be developed by providing pharmacologically effective amounts of compounds that mimic the structures and biological activities of locally generated VLC-PUFA. While there are several VLC-PUFA fatty acids that have been identified in cells and tissues, their biological roles have been presumed to be due to these naturally generated fatty acids and the corresponding phospholipids. In this disclosure we describe for the first time compounds having carbon chains analogous to VLC-PUFA that in addition to having 6 or 5 C═C bonds, they also contain one or two hydroxyl groups. Based on the hypothesis that compounds of this type may be responsible for the protective and neuroprotective actions of VLC-PUFA, we sought to identify their existence in human retinal pigment epithelial cells in culture in the presence of a VLC-PUFA added in its fatty acid form. As shown inFIG.2, we had obtained evidence of the formation of mono-hydroxy and di-hydroxy VLC-PUFA derivatives with molecular structures that are analogous to DHA-derived 17-hydroxy-DHA and the di-hydroxy compound NPD1 (10R,17S-dihydroxy-docosa-4Z,7Z,11E,13E,15Z,19Z-hexaenoic acid). Given the very small (nanogram) quantities of these hydroxylated derivatives of VLC-PUFA, it was not possible to identify their complete structure and stereochemistry (R or S hydroxy groups, Z or E double bonds). Moreover, the detected compounds were not identified from tissues naturally occurring in nature, but from the result of an artificial experiment combining a human cell and a VLC-PUFA. Therefore, the natural occurrence of the provided mono- and di-hydroxylated is not known at this time. The provided compounds are not obtained from natural sources but they are prepared by adapting methods known in the art, starting with commercially available materials. The provided preparation methods were designed to be suitable to the unique hydrophobic properties of VLC-PUFA, which differ significantly from compounds having a total number of carbons of 22 carbons or less. The provided compounds are chemically modified pharmaceutically acceptable derivatives to enhance their chemical and biological stability, and to enable their use in therapeutic applications involving various forms of drug delivery. Rather than provide VLC-PUFA in the form occurring in nature, this disclosure provides compounds that have stereochemically pure structures and are chemically synthesized and modified to have additional structural features and properties that enable them to exert pharmacological activity. The disclosure also provides pharmacologically effective compositions of the provided compounds that enhance their ability to be delivered to a subject in a manner that can reach the targeted cells and tissues. It is currently known that:(a) Mutations in the elongase enzyme ELVOL4 leads to retinal degenerative diseases; (b) ELOVL4 is a key enzyme involved in the conversion of DHA (C22:6) into VLC-PUFA; (c) Genetic ablation of the protein that is necessary to capture DHA into retinal cells containing ELOVL4 products result in a drastically decreased levels of the VLC-PUFAs with consequent retinal degeneration; and (d) Oxidative stress (OS) is associated with the early stages of degenerative, neurodegenerative, and retinal degenerative diseases. While not wishing to be bound by any one theory, it was considered that VLC-PUFA or their endogenously produced derivatives may play a direct role in neuronal protection and survival, which can provide the basis for a new concept for the treatment of inflammatory, degenerative and neurodegenerative diseases. The present disclosure is supported by the following new and unexpected data herein disclosed: (a) VLC-PUFA C32:6 and C34:6 are protective against OS in RPE cells (FIGS.4,5,6,7,8,9,10). (b) Protection against OS by VLC-PUFA is not inhibited by inhibitors of the 15 LOX-1 enzyme (FIG.5A). Since 15 LOX-1 is associated with the conversion of DHA into NPD1, the observed actions of VLC-PUFA suggest that there are different enzymes associated with their protective role. (c) Cell-derived hydroxylated derivatives (29-hydroxy-34:6 and 22,29-dihydroxy-34:6) could be detected in cultures of VLC-PUFA C34:6 from human retinal pigment epithelial cells in culture (FIG.2). (d) Chemical synthesis afforded stereochemically pure di-hydroxylated derivatives of VLC-PUFA C32:6 and C34:6, named herein as elovanoids ELV1 and ELV2 respectively, prepared as sodium salts or methyl esters (FIG.3). (e) The synthetic elovanoids ELV1 and ELV2 as sodium salts or methyl esters exhibited more potent activity against OS than the related VLC-PUFA (FIG.4). (f) The potent activities of elovanoids ELV1 and ELV2 co-related with potent downregulation of the proapoptotic proteins of the Bcl2 family Bid (FIG.6), Bim (FIG.7), Bax (FIG.8B). (g) The potent activities of elovanoids ELV1 and ELV2 co-related with potent upregulation of the antiapoptotic proteins of the Bcl2 family Bcl-xL (FIG.8A) and Bcl2 (FIG.9). (h) VLC-PUFA C32:6 and C34:6 mediate the upregulation of SIRT1 in ARPE-19 cells (FIG.10). (i) The elovanoid ELV2 (as the sodium salt or methyl ester) potently protects neuronal cells in primary cultures from NMDA-induced toxicity (FIG.11). (j) The synthetic elovanoids ELV2-Na and ELV2-Me were shown to have potent in vivo neuroprotective effects in a rat model of ischemic stroke after 2 hours of middle cerebral occlusion (MCAo) (FIG.12). Both elovanoid derivatives exhibited greater in vivo potency than DHA or NPD1, suggesting a remarkable neuroprotection and a potential therapeutic benefit for the treatment of ischemic stroke and other neurodegenerative diseases or disorders. (k) The greater potency of elovanoid ELV2 (as sodium salt or methyl ester) vs the docosanoids (DHA, NPD1) (FIG.12) may be due to either a different mechanism of action, a different metabolic profile that increases their bioavailability, or a different localization (e.g. intracellular receptors in the nuclear membrane) due to their longer fatty acid length and potentially greater hydrophobicity and structural rigidity. (i) Taken together, the above previously unknown data, including the structure and activity of the elovanoids, and the potent neuroprotective activities of elovanoid derivatives such as ELV1 and ELV2, provide the basis for the present disclosure. The compounds and compositions provided by this disclosure are able to restore homeostasis and induce survival signaling in certain cells undergoing oxidative stress or other homeostatic disruptions. The disclosure also provides methods of use of the provided compounds and compositions containing a hydroxylated derivative of very long chain polyunsaturated fatty acids, as the free carboxylic acids or their pharmaceutically acceptable salts, or as their corresponding esters or other prodrug derivatives. The provided compounds can be readily prepared by adapting methods known in the art, starting with commercially available materials. The bioactivity of the provided compounds, as exemplified by the elovanoid derivatives ELV1 and ELV2, is attributed to their ability to reach the targeted human cells and exert their biological actions either by entering into the cell or/and by acting at a membrane bound receptor. Alternatively, the provided compounds can act via intracellular receptors (e.g. nuclear membrane), and thus they would work specifically by affecting key signaling events. Administration of a pharmaceutical composition, containing a provided compound and a pharmaceutically acceptable carrier, restores the homeostatic balance and promotes the survival of certain cells that are essential for maintaining normal function. The provided compounds, compositions, and methods can be used for the preventive and therapeutic treatment of inflammatory, degenerative, and neurodegenerative diseases. This disclosure targets critical steps of the initiation and early progression of these conditions by mimicking the specific biology of intrinsic cellular/organs responses to attain potency, selectivity, devoid of side effects and sustained bioactivity. Other compositions, compounds, methods, features, and advantages of the present disclosure will be or become apparent to one having ordinary skill in the art upon examination of the following drawings, detailed description, and examples. It is intended that all such additional compositions, compounds, methods, features, and advantages be included within this description, and be within the scope of the present disclosure. Compounds Described herein are compounds and compositions based on very long chain polyunsaturated fatty acids and their hydroxylated derivatives. In some embodiments the provided compounds and compositions are based on compounds with the general structures of A or B, wherein n is a number selected from a group consisting of 0 to 19 and the compounds are carboxylic acids or their pharmaceutically acceptable salts. Compounds of structure A are based on very long chain polyunsaturated fatty acids with a total of 23 to 42 carbon atoms in the carbon chain and 6 alternating cis-carbon-carbon double bonds starting at positions ω-3 (omega-3), ω-6, ω-9, ω-12, ω-15 and ω-18. Compounds of structure B are based on very long chain polyunsaturated fatty acids with a total of 23 to 42 carbon atoms in the carbon chain and preferably 5 alternating cis-carbon-carbon double bonds starting at positions ω-3 (omega-3), ω-6, ω-9, ω-12 and ω-15. In preferred embodiments, n is a number selected from a group consisting of 0 to 13. In further preferred embodiments, n is a number selected from 1, 3, 5, 7, 9, 11 or 13, and the fatty acid contains a total of 24, 26, 28, 30, 32, 34 or 36 carbon atoms. In other preferred embodiments, n is a number selected from a group consisting of 0, 2, 4, 6, 8, 10 or 12, and the fatty acid contains a total of 23, 25, 27, 19, 31, 33 or 35 carbon atoms. In other embodiments the disclosure provides compounds that are carboxyl derivatives of very long chain polyunsaturated fatty acids of the general structures C or D, wherein n is a number selected from a group consisting of 0 to 19 and the carboxyl derivative is an ester or a pharmaceutically acceptable salt, wherein the R group is selected from a group consisting of methyl, ethyl, alkyl, or a cation selected from a group consisting of: ammonium cation, iminium cation, or a metal cation. Compounds of structure C are ester derivatives of very long chain polyunsaturated fatty acids with a total of 23 to 42 carbon atoms in the carbon chain and preferably 6 alternating cis-carbon-carbon double bonds starting at positions ω-3 (omega-3), ω-6, ω-9, ω-12, ω-15 and ω-18. Compounds of structure D are carboxyl derivatives of very long chain polyunsaturated fatty acids with a total of 24 to 42 carbon atoms in the carbon chain and preferably 5 alternating cis-carbon-carbon double bonds starting at positions ω-3 (omega-3), ω-6, ω-9, ω-12 and ω-15. In preferred embodiments, n is a number selected from a group consisting of 0 to 13. In further preferred embodiments, n is a number selected from 1, 3, 5, 7, 9, 11 or 13, and the fatty acid contains a total of 24, 26, 28, 30, 32, 34 or 36 carbon atoms. In other preferred embodiments, n is a number selected from a group consisting of 0, 2, 4, 6, 8, 10 or 12, and the fatty acid contains a total of 23, 25, 27, 19, 31, 33 or 35 carbon atoms. In some preferred embodiments, the R group is methyl or ethyl, or a metal cation selected from a group consisting of sodium, potassium, magnesium, zinc, or calcium cation. In an exemplary preferred embodiment, the present disclosure provides compounds of the general formula C, wherein: n is a number selected from a group consisting of zero 1, 3, 5, 7, 9, 11 or 13, wherein the fatty acid chain contains a total of 24, 26, 28, 30, 32, 34 or 36 carbon atoms; and As used herein and in other structures of the present disclosure, the compounds of the disclosure are shown having a terminal carboxyl group “—COOR” the “R” is intended to designate a group covalently bonded to the carboxyl such as an alkyl group. In the alternative, the carboxyl group is further intended to have a negative charge as “—COO−” and R is a cation including a metal cation, an ammonium cation and the like. R is selected from a group consisting of methyl, ethyl, alkyl, or a cation selected from a group consisting of: ammonium cation, iminium cation, or a metal cation. In some preferred embodiments the metal cation is selected from a group consisting of sodium, potassium, magnesium, zinc or calcium cation. In some preferred embodiments, the R group is methyl or ethyl, or a metal cation selected from a group consisting of sodium, potassium, magnesium, zinc or calcium cation. In a further preferred embodiment, the present disclosure provides compounds of the general formula C, wherein: n is 9 or 11, wherein the fatty acid chain contains a total of 32 or 34 carbon atoms; and R is selected from a group consisting of methyl, ethyl, alkyl, or a cation selected from a group consisting of: ammonium cation, iminium cation, or a metal cation. In some preferred embodiments the metal cation is selected from a group consisting of sodium, potassium, magnesium, zinc, or calcium cation. In other preferred embodiments, the carboxyl derivative is part of a glycerol-derived phospholipid, wherein R is a glycerol phospholipid that may contain an additional polyunsaturated fatty acid, as exemplified in structures E and F. In other embodiments the provided compounds have the general structures of G or H, wherein n is a number selected from a group consisting of 0 to 19, and the carboxylate R group is selected from a group consisting of an ester or a pharmaceutically acceptable salt, wherein the R group is selected from a group consisting of hydrogen, methyl, ethyl, alkyl, or a cation selected from a group consisting of: ammonium cation, iminium cation, or a metal cation. Compounds of structure G are mono-hydroxylated derivatives of very long chain polyunsaturated fatty acids with a total from 23 to 42 carbon atoms in the carbon chain, a hydroxyl group at position ω-6, and with 6 carbon-carbon double bonds starting at positions ω-3, ω-7, ω-9, ω-12, ω-15 and ω-18. Compounds of structure H are mono-hydroxylated derivatives of very long chain polyunsaturated fatty acids with a total from 23 to 42 carbon atoms in the carbon chain, a hydroxyl group at position ω-6, and with 5 carbon-carbon double bonds starting at positions ω-3, ω-7, ω-9, ω-12, and ω-15. In preferred embodiments, n is a number selected from a group consisting of 1 to 13. In further preferred embodiments, n is a number selected from 1, 3, 5, 7, 9, 11 or 13, and the fatty acid contains a total of 24, 26, 28, 30, 32, 34 or 36 carbon atoms. In other preferred embodiments, n is a number selected from a group consisting of 0, 2, 4, 6, 8, 10 or 12, and the fatty acid contains a total of 23, 25, 27, 19, 31, 33 or 35 carbon atoms. As used herein and in other structures of the present disclosure, the compounds of the disclosure are shown having a terminal carboxyl group “—COOR” the “R” is intended to designate a group covalently bonded to the carboxyl such as an alkyl group. In the alternative, the carboxyl group is further intended to have a negative charge as “—COO−” and R is a cation including a metal cation, an ammonium cation and the like. R is selected from a group consisting of methyl, ethyl, alkyl, or a cation selected from a group consisting of: ammonium cation, iminium cation, or a metal cation. In some preferred embodiments the metal cation is selected from a group consisting of sodium, potassium, magnesium, zinc or calcium cation. In some preferred embodiments, the R group is methyl or ethyl, or a metal cation selected from a group consisting of sodium, potassium, magnesium, zinc or calcium cation. In an exemplary preferred embodiment, the disclosure provides compounds of the general formula G or H, wherein: n is 9 or 11, and the fatty acid chain contains a total of 32 or 34 carbon atoms. In some preferred embodiments, the provided compounds G and H are predominately one enantiomer with a defined (S) or (R) chirality at the carbon bearing the hydroxyl group. In an exemplary preferred embodiment, the present disclosure provides a compound selected from a group consisting of I, J, K, or L, having the following structures herein n is 9 or 11, and the fatty acid chain contains a total of 32 or 34 carbon atoms, and the R group is methyl or ethyl, or a metal cation selected from a group consisting of sodium, potassium, magnesium, or calcium cation. In an exemplary preferred embodiment, the present disclosure provides compound (S,16Z,19Z,22Z,25Z,27E,31Z)-29-hydroxytetratriaconta-16,19,22,25,27,31-hexaenoic acid (OR═OH), its sodium salt (OR═ONa), or its methyl ester (OR═OMe) In other embodiments the provided compounds have the general structures of M or N, wherein n is a number selected from a group consisting of 0 to 19, and the carboxylate R group is selected from a group consisting of an ester or a pharmaceutically acceptable salt, wherein the R group is selected from a group consisting of hydrogen, methyl, ethyl, alkyl, or a cation selected from a group consisting of: ammonium cation, iminium cation, or a metal cation. Compounds of structure M are di-hydroxylated derivatives of very long chain polyunsaturated fatty acids with a total from 23 to 42 carbon atoms in the carbon chain, two hydroxyl groups at positions ω-6 and ω-13, and 6 carbon-carbon double bonds at positions ω-3, ω-7, ω-9, ω-11, ω-15 and ω-18. Compounds of structure N are di-hydroxylated derivatives of very long chain polyunsaturated fatty acids with a total from 23 to 42 carbon atoms in the carbon chain, two hydroxyl groups at positions ω-6 and ω-13, and 5 carbon-carbon double bonds at positions ω-3, ω-7, ω-9, ω-11 and ω-15. In preferred embodiments, n is a number selected from a group consisting of 1 to 13. In further preferred embodiments, n is a number selected from 1, 3, 5, 7, 9, 11 or 13, and the fatty acid contains a total of 24, 26, 28, 30, 32, 34 or 36 carbon atoms. In other preferred embodiments, n is a number selected from a group consisting of 0, 2, 4, 6, 8, 10 or 12, and the fatty acid contains a total of 23, 25, 27, 19, 31, 33 or 35 carbon atoms. As used herein and in other structures of the present disclosure, the compounds of the disclosure are shown having a terminal carboxyl group “—COOR” the “R” is intended to designate a group covalently bonded to the carboxyl such as an alkyl group. In the alternative, the carboxyl group is further intended to have a negative charge as “—COO−” and R is a cation including a metal cation, an ammonium cation and the like. R is selected from a group consisting of methyl, ethyl, alkyl, or a cation selected from a group consisting of: ammonium cation, iminium cation, or a metal cation. In some preferred embodiments the metal cation is selected from a group consisting of sodium, potassium, magnesium, zinc or calcium cation. In some preferred embodiments, the R group is methyl or ethyl, or a metal cation selected from a group consisting of sodium, potassium, magnesium, zinc or calcium cation. In an exemplary preferred embodiment, the disclosure provides compounds of the general formula M or N, wherein: n is 9 or 11, and the fatty acid chain contains a total of 32 or 34 carbon atoms. In a preferred embodiment, the present disclosure provides a compound selected from a group consisting of O, P, Q, R, S, T, U or V, having the following structures, wherein n is 9 or 11, and the fatty acid chain contains a total of 32 or 34 carbon atoms, and the R group is methyl or ethyl, or a metal cation selected from a group consisting of sodium, potassium, magnesium, zinc or calcium cation. In an exemplary preferred embodiment, the present disclosure provides a compound selected from the group consisting of: (14Z,17Z,20R,21E,23E,25Z,27S,29Z)-20,27-dihydroxydotriaconta-14,17,21,23,25,29-hexaenoic acid; sodium (14Z,17Z,20R,21E,23E, 25Z,27S,29Z)-20,27-dihydroxydotriaconta-14,17,21,23,25,29-hexaenoate; methyl (14Z,17Z, 20R,21E,23E,25Z,27S,29Z)-20,27-dihydroxydotriaconta-14,17,21,23,25,29-hexaenoate; (16Z,19Z,22R,23E,25E,27Z,29S,31Z)-22,29-dihydroxytetratriaconta-16,19,23,25,27,31-hexaenoic acid; sodium (16Z,19Z,22R,23E,25E,27Z,29S,31Z)-22,29-dihydroxytetratriaconta-16,19,23,25,27,31-hexaenoate; or methyl (16Z,19Z,22R,23E,25E,27Z,29S,31Z)-22,29-dihydroxy-tetratriaconta-16,19,23,25,27,31-hexaenoate, which have the following structures: In other embodiments the provided compounds have the general structures of W or Y, wherein n is a number selected from a group consisting of 0 to 19, and the carboxylate R group is selected from a group consisting of an ester or a pharmaceutically acceptable salt, wherein the R group is selected from a group consisting of hydrogen, methyl, ethyl, alkyl, or a cation selected from a group consisting of: ammonium cation, iminium cation, or a metal cation. Compounds of structure M are di-hydroxylated derivatives of very long chain polyunsaturated fatty acids with a total from 23 to 42 carbon atoms in the carbon chain, two hydroxyl groups at positions ω-6 and ω-13, and 6 carbon-carbon double bonds at positions ω-3, ω-7, ω-9, ω-11, ω-15 and ω-18. Compounds of structure N are di-hydroxylated derivatives of very long chain polyunsaturated fatty acids with a total from 23 to 42 carbon atoms in the carbon chain, two hydroxyl groups at positions ω-6 and ω-13, and 5 carbon-carbon double bonds at positions ω-3, ω-7, ω-9, ω-11 and ω-15. In preferred embodiments, n is a number selected from selected from a group consisting of 1 to 13. In further preferred embodiments, n is a number selected from 1, 3, 5, 7, 9, 11 or 13, and the fatty acid contains a total of 24, 26, 28, 30, 32, 34 or 36 carbon atoms. In other preferred embodiments, n is a number selected from a group consisting of 0, 2, 4, 6, 8, 10 or 12, and the fatty acid contains a total of 23, 25, 27, 19, 31, 33 or 35 carbon atoms. R is selected from a group consisting of methyl, ethyl, alkyl, or a cation selected from a group consisting of: ammonium cation, iminium cation, or a metal cation. In some preferred embodiments the metal cation is selected from a group consisting of sodium, potassium, magnesium, zinc or calcium cation. In some preferred embodiments, the R group is methyl or ethyl, or a metal cation selected from a group consisting of sodium, potassium, magnesium, zinc or calcium cation. In an exemplary preferred embodiment, the disclosure provides compounds of the general formula W or Y, wherein: n is 9 or 11, and the fatty acid chain contains a total of 32 or 34 carbon atoms. In an exemplary preferred embodiment, the present disclosure provides a compound selected from the group consisting of compounds X or Z, wherein R is methyl or sodium: Methods of Preparation and Manufacturing of Provided Compounds The compounds provided by the present disclosure can be prepared from readily available starting materials. For example, the synthesis of compounds of general structure M can be prepared according to the following general Scheme 1, which exemplifies the method of preparation and manufacturing of the provided compounds of this type. Scheme 1 shows the detailed approach for the stereocontrolled total synthesis of compounds of type O, wherein n is 9, and the fatty acid chain contains a total of 32 carbon atoms, and the R group is methyl or sodium cation. In particular, Scheme 1 shows the synthesis of compounds ELV1-Me and ELV1-Na, starting with methyl pentadec-14-ynoate (compound 4). By starting with heptadec-16-ynoate, this process affords compounds ELV2-Me and ELV2-Na. The alkynyl precursors of ELV1 and ELV2, namely 13a, 13b, 15a, and 15b are also among the provided compounds X and Z in this disclosure. Scheme 1 provides the key reagents and conditions for the preparations of the provided compounds, by employing reaction conditions that are typical for this type of reactions. Pharmaceutical Compositions for the Treatment of Diseases In other embodiments the present disclosure provides formulations of pharmaceutical compositions containing therapeutically effective amounts of one or more of compounds provided herein or their salts thereof in a pharmaceutically acceptable carrier. The provided compositions contain one or more compounds provided herein or their salts thereof, and a pharmaceutically acceptable excipient, diluent, carrier and/or adjuvant. The compounds are preferably formulated into suitable pharmaceutical preparations such as solutions, suspensions, tablets, dispersible tablets, pills, capsules, powders, sustained release formulations or elixirs, for oral, buccal, intranasal, vaginal, rectal, ocular administration or in sterile solutions or suspensions for parenteral administration, as well as transdermal patch preparation and dry powder inhalers. The provided formulations may be in the form of a drop, such as an eye drop, and the pharmaceutical formulation may further contain known agents for the treatment of eye diseases. Typically the compounds described above are formulated into pharmaceutical compositions using techniques and procedures well known in the art (see, e.g., Ansel Introduction to Pharmaceutical Dosage Forms, Fourth Edition 1985, 126). Preferred embodiments of the disclosure provides pharmaceutical compositions containing various forms of the provided compounds, as the free carboxylic acids or their pharmaceutically acceptable salts, or as their corresponding esters or their phospholipid derivatives. In other preferred embodiments the disclosure provides pharmaceutical compositions containing provided compounds that contain one or two hydroxyl groups at positions located between ω-3 to ω-18 of the very long chain polyunsaturated fatty acids, as the free carboxylic acids or their pharmaceutically acceptable salts, or as their corresponding esters. In the provided compositions, effective concentrations of one or more compounds or pharmaceutically acceptable derivatives is (are) mixed with a suitable pharmaceutical carrier or vehicle. The compounds may be derivatized as the corresponding salts, esters, enol ethers or esters, acids, bases, solvates, hydrates or prodrugs prior to formulation, as described above. The concentrations of the compounds in the compositions are effective for delivery of an amount, upon administration, that treats, prevents, or ameliorates one or more of the symptoms of a disease, disorder or condition. As described herein, the compositions can be readily prepared by adapting methods known in the art. The compositions can be a component of a pharmaceutical formulation. The pharmaceutical formulation may further contain known agents for the treatment of inflammatory or degenerative diseases, including neurodegenerative diseases. The provided compositions can serve as pro-drug precursors of the fatty acids and can be converted to the free fatty acids upon localization to the site of the disease. The present disclosure also provides packaged composition(s) or pharmaceutical composition(s) for use in treating the disease or condition. Other packaged compositions or pharmaceutical compositions provided by the present disclosure further include indicia including at least one of: instructions for using the composition to treat the disease or condition. The kit can further include appropriate buffers and reagents known in the art for administering various combinations of the components listed above to the host. Pharmaceutical Formulations Embodiments of the present disclosure include a composition or pharmaceutical composition as identified herein and can be formulated with one or more pharmaceutically acceptable excipients, diluents, carriers and/or adjuvants. In addition, embodiments of the present disclosure include a composition or pharmaceutical composition formulated with one or more pharmaceutically acceptable auxiliary substances. In particular the composition or pharmaceutical composition can be formulated with one or more pharmaceutically acceptable excipients, diluents, carriers, and/or adjuvants to provide an embodiment of a composition of the present disclosure. A wide variety of pharmaceutically acceptable excipients are known in the art. Pharmaceutically acceptable excipients have been amply described in a variety of publications, including, for example, A. Gennaro (2000) “Remington: The Science and Practice of Pharmacy,” 20th edition, Lippincott, Williams, & Wilkins; Pharmaceutical Dosage Forms and Drug Delivery Systems (1999) H. C. Ansel et al., eds., 7th ed., Lippincott, Williams, & Wilkins; and Handbook of Pharmaceutical Excipients (2000) A. H. Kibbe et al., eds., 3rd ed. Amer. Pharmaceutical Assoc. The pharmaceutically acceptable excipients, such as vehicles, adjuvants, carriers or diluents, are readily available to the public. Moreover, pharmaceutically acceptable auxiliary substances, such as pH adjusting and buffering agents, tonicity adjusting agents, stabilizers, wetting agents and the like, are readily available to the public. In an embodiment of the present disclosure, the composition or pharmaceutical composition can be administered to the subject using any means capable of resulting in the desired effect. Thus, the composition or pharmaceutical composition can be incorporated into a variety of formulations for therapeutic administration. For example, the composition or pharmaceutical composition can be formulated into pharmaceutical compositions by combination with appropriate, pharmaceutically acceptable carriers or diluents, and may be formulated into preparations in solid, semi-solid, liquid or gaseous forms, such as tablets, capsules, powders, granules, ointments, solutions, suppositories, injections, inhalants and aerosols. Suitable excipient vehicles for the composition or pharmaceutical composition are, for example, water, saline, dextrose, glycerol, ethanol, or the like, and combinations thereof. In addition, if desired, the vehicle may contain minor amounts of auxiliary substances such as wetting or emulsifying agents or pH buffering agents. Methods of preparing such dosage forms are known, or will be apparent upon consideration of this disclosure, to those skilled in the art. See, e.g., Remington's Pharmaceutical Sciences, Mack Publishing Company, Easton, Pennsylvania, 17th edition, 1985. The composition or formulation to be administered will, in any event, contain a quantity of the composition or pharmaceutical composition adequate to achieve the desired state in the subject being treated. Compositions of the present disclosure can include those that comprise a sustained release or controlled release matrix. In addition, embodiments of the present disclosure can be used in conjunction with other treatments that use sustained-release formulations. As used herein, a sustained-release matrix is a matrix made of materials, usually polymers, which are degradable by enzymatic or acid-based hydrolysis or by dissolution. Once inserted into the body, the matrix is acted upon by enzymes and body fluids. A sustained-release matrix desirably is chosen from biocompatible materials such as liposomes, polylactides (polylactic acid), polyglycolide (polymer of glycolic acid), polylactide co-glycolide (copolymers of lactic acid and glycolic acid), polyanhydrides, poly(ortho)esters, polypeptides, hyaluronic acid, collagen, chondroitin sulfate, carboxylic acids, fatty acids, phospholipids, polysaccharides, nucleic acids, polyamino acids, amino acids such as phenylalanine, tyrosine, isoleucine, polynucleotides, polyvinyl propylene, polyvinylpyrrolidone and silicone. Illustrative biodegradable matrices include a polylactide matrix, a polyglycolide matrix, and a polylactide co-glycolide (co-polymers of lactic acid and glycolic acid) matrix. In another embodiment, the pharmaceutical composition of the present disclosure (as well as combination compositions) can be delivered in a controlled release system. For example, the composition or pharmaceutical composition may be administered using intravenous infusion, an implantable osmotic pump, a transdermal patch, liposomes, or other modes of administration. In one embodiment, a pump may be used (Sefton (1987). CRC Crit. Ref. Biomed. Eng. 14:201; Buchwald et al. (1980). Surgery 88:507; Saudek et al. (1989). N. Engl. J. Med. 321:574). In another embodiment, polymeric materials are used. In yet another embodiment a controlled release system is placed in proximity of the therapeutic target thus requiring only a fraction of the systemic dose. In yet another embodiment, a controlled release system is placed in proximity of the therapeutic target, thus requiring only a fraction of the systemic. Other controlled release systems are discussed in the review by Langer (1990). Science 249:1527-1533. In another embodiment, the compositions of the present disclosure (as well as combination compositions separately or together) include those formed by impregnation of the composition or pharmaceutical composition described herein into absorptive materials, such as sutures, bandages, and gauze, or coated onto the surface of solid phase materials, such as surgical staples, zippers and catheters to deliver the compositions. Other delivery systems of this type will be readily apparent to those skilled in the art in view of the instant disclosure. In another embodiment, the compositions or pharmaceutical compositions of the present disclosure (as well as combination compositions separately or together) can be part of a delayed-release formulation. Delayed-release dosage formulations can be prepared as described in standard references such as “Pharmaceutical dosage form tablets”, eds. Liberman et. al. (New York, Marcel Dekker, Inc., 1989), “Remington—The science and practice of pharmacy”, 20th ed., Lippincott Williams & Wilkins, Baltimore, MD, 2000, and “Pharmaceutical dosage forms and drug delivery systems”, 6th Edition, Ansel et al., (Media, PA: Williams and Wilkins, 1995). These references provide information on excipients, materials, equipment and process for preparing tablets and capsules and delayed release dosage forms of tablets, capsules, and granules. These references provide information on carriers, materials, equipment and process for preparing tablets and capsules and delayed release dosage forms of tablets, capsules, and granules. Embodiments of the composition or pharmaceutical composition can be administered to a subject in one or more doses. Those of skill will readily appreciate that dose levels can vary as a function of the specific the composition or pharmaceutical composition administered, the severity of the symptoms and the susceptibility of the subject to side effects. Preferred dosages for a given compound are readily determinable by those of skill in the art by a variety of means. In an embodiment, multiple doses of the composition or pharmaceutical composition are administered. The frequency of administration of the composition or pharmaceutical composition can vary depending on any of a variety of factors, e.g., severity of the symptoms, and the like. For example, in an embodiment, the composition or pharmaceutical composition can be administered once per month, twice per month, three times per month, every other week (qow), once per week (qw), twice per week (biw), three times per week (tiw), four times per week, five times per week, six times per week, every other day (qod), daily (qd), twice a day (qid), three times a day (tid), or four times a day. As discussed above, in an embodiment, the composition or pharmaceutical composition is administered 1 to 4 times a day over a 1 to 10 day time period. The duration of administration of the composition or pharmaceutical composition analogue, e.g., the period of time over which the composition or pharmaceutical composition is administered, can vary, depending on any of a variety of factors, e.g., patient response, etc. For example, the composition or pharmaceutical composition in combination or separately, can be administered over a period of time of about one day to one week, about one day to two weeks. The amount of the compositions and pharmaceutical compositions of the present disclosure that can be effective in treating the condition or disease can be determined by standard clinical techniques. In addition, in vitro or in vivo assays can optionally be employed to help identify optimal dosage ranges. The precise dose to be employed can also depend on the route of administration, and can be decided according to the judgment of the practitioner and each patient's circumstances. Routes of Administration Embodiments of the present disclosure provide methods and compositions for the administration of the active agent(s) to a subject (e.g., a human) using any available method and route suitable for drug delivery, including in vivo and ex vivo methods, as well as systemic and localized routes of administration. Routes of administration include intranasal, intramuscular, intratracheal, subcutaneous, intradermal, topical application, intravenous, rectal, nasal, oral, and other enteral and parenteral routes of administration. Routes of administration may be combined, if desired, or adjusted depending upon the agent and/or the desired effect. An active agent can be administered in a single dose or in multiple doses. The VLC-PUFA and their biogenic derivatives are formed in cells and are not a component of human diet. Possible routes of administration of the novel compounds provided herein will include oral and parenteral administration, including intravitreal and subretinal injection into the eye to by-pass intestinal absorption, the gut-liver, and the blood-ocular barrier. The provided formulations may be delivered in the form of a drop, such as an eye drop, or any other customary method for the treatment of eye diseases. Parenteral routes of administration other than inhalation administration include, but are not limited to, topical, transdermal, subcutaneous, intramuscular, intraorbital, intracapsular, intraspinal, intrasternal, and intravenous routes, i.e., any route of administration other than through the alimentary canal. Parenteral administration can be conducted to effect systemic or local delivery of the composition. Where systemic delivery is desired, administration typically involves invasive or systemically absorbed topical or mucosal administration of pharmaceutical preparations. In an embodiment, the composition or pharmaceutical composition can also be delivered to the subject by enteral administration. Enteral routes of administration include, but are not limited to, oral and rectal (e.g., using a suppository) delivery. Methods of administration of the composition or pharmaceutical composition through the skin or mucosa include, but are not limited to, topical application of a suitable pharmaceutical preparation, transdermal transmission, injection and epidermal administration. For transdermal transmission, absorption promoters or iontophoresis are suitable methods. Iontophoretic transmission may be accomplished using commercially available “patches” that deliver their product continuously via electric pulses through unbroken skin for periods of several days or more. Methods for the Treatment of Diseases, Disorders or Conditions Described herein are methods and compositions for treating and protecting an organ or tissue from the effects of oxidative stress or other homeostatic disruptions associated with a persistent inflammatory condition or a progressive degenerative disease, including a neurodegenerative disease. The provided compounds, compositions, and methods can be used for the preventive and therapeutic treatment of a disease, disorder or condition. The list of diseases that can be treated with the provided compositions and methods include but are not limited to inflammatory diseases, degenerative diseases, including neurodegenerative diseases including, but not limited to the following: (a) Inflammatory diseases, including acute and chronic disorders were homeostasis is disrupted by abnormal or dysregulated inflammatory response. These diseases are initiated and mediated by a number of inflammatory factors, including oxidative stress, chemokines, cytokines, breakage of blood/tissue barriers, autoimmune diseases or other conditions that engage leukocytes, monocytes/macrophages or parenchymal cells that induce excessive amounts of pro-cell injury, pro-inflammatory/disruptors of homeostasis mediators. These diseases occur in a wide range of tissues and organs and are currently treated, by anti-inflammatory agents such as corticosteroids, non-steroidal anti-inflammatory drugs, TNF modulators, COX-2 inhibitors, etc. Representative examples include but are not limited to: rheumatoid arthritis, osteoarthritis, atherosclerosis, cancer, diabetes, intestinal bowel disease, prostatitis, ischemic stroke, traumatic brain damage, spinal cord injury, multiple sclerosis, autism, schizophrenia, depression, traumatic brain injury, status epilepticus, Huntington's disease, Alzheimer's disease, Parkinson's disease, amyotrophic lateral sclerosis, retina degenerative diseases, age-related macular degeneration, inherited retinal degenerative diseases, Stargardt-like macular dystrophy, X-linked juvenile retinoschisis, perioperative hypoxia, retinitis pigmentosa, glaucoma, etc. (b) Degenerative diseases, which include conditions that involve progressive loss of vital cells and tissues that result in progressive impairment of function, such as loss of cartilage in knees, hip joints or other joints such as in osteoarthritis. Other degenerative diseases engages cellular and intercellular homeostasis perturbations and includes heart disease, atherosclerosis, cancer, diabetes, intestinal bowel disease, osteoporosis, prostatitis, rheumatoid arthritis, etc. (c) Neurodegenerative diseases, which include some of the major diseases of the brain, retina, spinal cord and peripheral nerves, whereby a progressive demise of cellular organization leads to impaired function. These are due to immune or inflammatory disorders and/or to inherited conditions or aging. They include ischemic stroke, traumatic brain damage, spinal cord injury, epilepsy, multiple sclerosis, Alzheimer's disease, Parkinson's disease, amyotrophic lateral sclerosis, retina degenerative diseases such as age-related macular degeneration, inherited eye diseases such as retinitis pigmentosa, glaucoma, etc. (d) Retinal degenerative diseases, which are the leading causes of blindness that affects very large numbers of people and involve the deterioration of the retina caused by the progressive and eventual death of the photoreceptor cells of the retina. Examples of common retinal degenerative diseases include but are not limited to: retinitis pigmentosa, age-related macular degeneration, inherited retinal degenerative diseases, Stargardt-like macular dystrophy, X-linked juvenile retinoschisis, perioperative hypoxia, glaucoma, etc. The provided compounds, compositions, and methods can also be used to induce the increased expression of Sirtuin1 (SIRT1) and to treat diseases and conditions that can benefit from an increased expression of SIRT1. Sirtuin1 (SIRT1) belongs to a family of highly conserved proteins associated with aging, modulation of energy metabolism, genomic stability, stress resistance, Alzheimer's and other neurodegenerative diseases. Sirtuin1 is a major therapeutic target in many diseases including cancer, diabetes, inflammatory disorders and neurodegenerative disease, all of which can be treated with the provided compounds, compositions and methods. Also described herein are methods and compositions for treating and protecting the retina of the eye. Specifically, described herein are methods for treating and protecting retinal pigment epithelial cells and photoreceptors of the eye. Generally, compositions as described herein are administered to a subject in any preferred mode of administration. Such modes include in an eye drop. Methods and compositions described herein can be used to treat a diseased eye in a subject. For example, the disease can be a retinal disease, such as retinal degeneration. In this instance, the retinal degeneration can be prevented or delayed. Eye diseases that are particularly suited for methods and compositions as described herein include age-related macular degeneration, retinitis pigmentosa, and Stargardt disease. Methods and compositions described herein can promote the survival of photoreceptors in the retina. Methods and compositions described herein can induce signaling pathways that enhance cell survival in cell specific to the eye, such as retinal pigment epithelial cells and photoreceptors. While embodiments of the present disclosure are described in connection with the Examples and the corresponding text and figures, there is no intent to limit the disclosure to the embodiments in these descriptions. On the contrary, the intent is to cover all alternatives, modifications, and equivalents included within the spirit and scope of embodiments of the present disclosure. EXAMPLES Example 1 Evidence for the formation of hydroxylated VLC-PUFA in cells as postulated inFIG.1, and as documented inFIG.2. The biogenic conversion of the n3 VLC-PUFA (1) to the mono-hydroxylated derivative 2 and the di-hydroxylated derivative 3 demonstrates the ability of VLC-PUFA to generate hydroxylated derivatives with structures analogous to those obtained from other omega-3 PUFA such as DHA. The preferred structures of 2 are 2a and 2b, while the preferred structures of 3 are 3a and 3b. Although these novel findings do not prove that compounds 2 or 3 are naturally occurring in living systems, they provide a design rationale for the provided compounds and their biological activities, as provided in this disclosure. The cell-derived hydroxylated derivatives 2 and 3 were obtained from human retinal pigment epithelial cells in culture. Human retinal pigment epithelial cells (spontaneously transformed ARPE-19 cells) or primary human retinal pigment epithelial cells (HRPE) were incubated with 34:6n3 (100 nM) during 12-16 hours and then the culture media collected, lipid extracted and run in LC-MS/MS. The results suggest that C34:6 with an m/z of 495.5 (FIG.2A) yielded a hydroxylated product analogous to the mono-hydroxylated DHA derivative 17-HDHA having a parent-H m/z of 511.8 and a fragment m/z of 413, which is consistent with the mono-hydroxylated compound 29-hydroxy-34:6 (FIG.2B). The data show that compound C34:6 was also converted to an elongation product analogous to the di-hydroxylated DHA derivative NPD1,(10R,17S-dihydroxy-docosa-4Z,7Z,11E,13E,15Z,19Z-hexaenoic acid) having a parent-H m/z of 527.8, and a fragment m/z of 206 consistent with the NPD1-like di-hydroxylated compound 22,29-dihydroxy-34:6 (FIG.2C). The stereochemistry of the mono- and di-hydroxy compounds were not possible to determine, but they were presumed to be the same as those derived from DHA. Example 2 Representative of experiments used human retinal pigment epithelial (RPE) cells, which are neuroectoderm-derived post-mitotic cells of the retina, an integral part of the central nervous system. These cells are richly endowed with a multitude of mechanisms to protect themselves from injury and to protect other cells, particularly the survival of photoreceptors. They are the most active phagocyte of the human body, critical for the health of photoreceptors and vision, and have the ability to secrete neurotrophins and other beneficial substances. In pathological conditions they recapitulate aspects of Alzheimer's disease by processing amyloid precursor protein and contributing to the formation of Drusen, analogously to the senile amyloid plaques. Thus, these are among the reasons that experimental data included in this disclosure were obtained with RPE cells. Therefore, the data provided herein are representative of the expected activities of the provided compounds in other cells and tissues where VLC-PUFA are known to be generated or be present. Evidence of cytoprotection by 32.6 and 34.6 VLC-PUFA in oxidative-stress induced ARPE-19 cells as detailed in (FIG.4): (A) Cytoprotective effects of NPD1 like compounds on OS induced apoptosis. The results shown in this figure compare the cytoprotective capacities of very long chain polyunsaturated fatty acids (VLC-PUFA), elovanoids ELV1 and ELV2, and neuroprotectin D1 (NPD1) in human retinal pigment epithelial (RPE) cells deficient in 15-LOX-D1 by measuring the protection of cell deaths induced by oxidative stress (OS) by these compounds. The results indicate that NPD1 provided the maximum protection (60%), followed by elovanoids at intermediate level (55%), and VLC-PUFA (50%), the least compared to OS (90%). (B) Elovanoid precursors protect human retinal pigment epithelial cells deficient in 15-LOX-1, unlike DHA, from oxidative stress conditions. This experiment clearly shows that VLC-PUFA, elovanoid precursors 32:6 and 34:6, and NPD1 protect against cell death in 15-LOX-D1 cells under oxidative stress conditions. On the other hand, DHA was unable to do so, as the 15-LOX-D1 cells lack the enzyme required for conversion of DHA to the neuroprotective agent. Example 3 FIG.5—(A) Effect of PD146176 on VLC-PUFA inhibited apoptosis induced by OS in ARPE-19 cells. This experiment demonstrated the effect of 15-lipooxygenese inhibitor PD146176 on the VLC-PUFA-mediated inhibition of cell death in ARPE-19 cells under stressed condition. It is evident that 32:6 and 34:6 LOAF were able to induce a substantial amount (55 and 48% respectively) of neuroprotection compared to PD 146176 (22%) when the stressed cells were treated with 5 μm of 15-LOX-D1 inhibitor. It can be concluded that since PD146176 is the inhibitor of 15-lipooxygenase enzyme, it might be protecting the stressed RPE cells by accumulating neuroprotective agents inside the cells. (B) Comparison of cytoprotective capacities of NPD1, C32:6 and C34:6 VLC-PUFA on oxidative stress-induced apoptosis in 15-LOX-1 cells. Shown here is the comparison of neuroprotection in a 15-LOX-1-deficient cell line under oxidative stress with 32:6 and 34:6 VLC-PUFA along with NPD1. 32:6 and 34:6 VLC-PUFA were able to induce neuroprotection (45% and 40% respectively), as compared to oxidative stress (90%) under this condition. (C) Concentration dependent cytoprotection by C32:6 and C34:6 VLC-PUFA in oxidative-stress induced ARPE-19 cells. A concentration (50-500 nM) kinetic of cytoprotection induced by VLC-PUFA 32:6 and 34:6 in RPE cell culture under OS was shown here. The result indicates that there was a gradual decrease of cell deaths starting from 50 nM concentrations of both 32:6 and 34:6 VLC-PUFA, very good intermediate effect at 250 nM, and maximum effect at 500 nM. We decided to use 250 nM concentrations of 32:6 and 34:6 VLC-PUFA in subsequent experiments. (D) Selected images of alive and dead cells from this study (control, OS, treatment with C32:6). Example 4 FIG.6—(A) VLC-PUFA and elovanoids ELV1 and ELV2 mediated effect on Bid upregulation in ARPE-19 cells under stress. This figure displays the downregulation of the proapoptotic protein of the Bcl2 family Bid by western blot analysis by VLC-PUFA and elovanoids in RPE cells in culture under oxidative-stress. Results indicate that upregulated Bid protein by OS, as evident from the figure, was inhibited by both elovanoids and VLC-PUFA. It is interesting to see that the sodium salts of the elovaniod precursors are more effective than the methyl ester forms. (B) VLC-PUFA and ELV1 and ELV2 compounds mediated upregulation of Bid in ARPE-19 cells under stress. This Figure shows the quantification of Bid downregulation. Example 5 FIG.7—A) VLC-PUFA and ELV1 and ELV2 compounds mediated upregulation of Bim in ARPE-19 cells under stress. Bim, another class of Bcl2 family, has been tested like Bid in this figure to confirm our previous results. VLC-PUFA and elovanoids protected the upregulation of Bim by OS, similar to Bid, in RPE cells under stress. (B) VLC-PUFA and elovanoids mediated effect on Bim upregulation in ARPE-19 cells under stress. This Figure shows the quantification of Bim downregulation. Example 6 FIG.8—(A) Bcl-xL-upregulation by elovanoids ELV1 and ELV2 in ARPE-19 cells under stress. Bcl-xL is the antiapoptotic Bcl2 family protein. Like proapoptotic proteins Bid and Bim, the effect of elovaniod precursors on the antiapoptotic protein Bcl-xL was tested in this figure in RPE cells under OS. Results showed that elovaniod precursors were able to upregulate the Bcl-xL protein in RPE cells under stress, which is the opposite effect of Bid and Bim. (B) Effect of NPD1, ELV1 and ELV2 on Bax expression in LOX-D cells under stress. Proapoptotic Bax was tested in this figure. It is evident that elovaniod precursors downregulated the Bax upregulation by OS in RPE cells under OS, which is consistent with our inhibition of apoptosis experiments, as shown before. C) VLC-PUFA and elovanoids ELV1 and ELV2 mediated effect on Bax upregulation in ARPE-19 cells under stress. In this experiment, elovanoid precursors along with VLC-PUFA were tested on the downregulation of the Bax protein in RPE cells under stress. Example 7 FIG.9—(A) VLC-PUFA and elovanoids ELV1 and ELV2 mediated effect on Bcl2 upregulation in ARPE-19 cells under stress. In this experiment we tested the effect of elovaniod precursors on Blc2 upregulation along with VLC-PUFA in stressed RPE. (B) Quantification of Bcl2 upregulation by NPD1, ELV1 and ELV2 in LOX-D cells. Bcl2 is an important antiapoptotic protein of the Bcl2 family protein. It is evident that elovaniod precursors upregulated the Bcl2 protein in RPE cells under stress. Example 8 FIG.10—(A) Effect of NPD1 and VLC-PUFA C32:6 and C34:6 in mediating upregulation of SIRT1 in ARPE-19 cells. (B) Quantification of SIRT1 upregulation by NPD1, C32:6 and C34:6. SIRT1 (Sirtuin1) belongs to a family of highly conserved proteins linked to caloric restriction beneficial outcomes and aging by regulating energy metabolism, genomic stability and stress resistance. SIRT1 is a potential therapeutic target in several diseases including cancer, diabetes, inflammatory disorders, and neurodegenerative diseases or disorders. Elovanoids induce cell survival involving the upregulation of the Bcl2 class of survival proteins and the downregulation of pro-apoptotic Bad and Bax under oxidative stress (OS) in RPE cells. The data in this Figure suggest that elovanoids upregulate SIRT1 abundance in human RPE cells when confronted with OS. As a consequence, remarkable cell survival takes place. This target of elovanoids might be relevant to counteract consequences of several diseases associated with SIRT1. Example 9 FIG.11—The elovanoid ELV2 in 200 nM concentrations protects neuronal cells in primary cultures from NMDA-induced toxicity (A), and MK-801 potentiates protection as assessed by MTT assay for cell viability (B). In several neurological and neurodegenerative diseases, such as stroke, epilepsy, status epilepticus, traumatic head injury, etc., as well as ophthalmological diseases, such as glaucoma, an excessive presynaptic release of the excitatory neurotransmitter glutamate takes place. As a consequence, glutamate transporters that function to remove extracellular glutamate from astrocytes and neurons are overwhelmed and the NMDA-type glutamate receptor is over-activated. This receptor is a calcium channel that therefore leads to a flooding of calcium into the postsynaptic cell. The overall phenomena is refer to as excitotoxicity that in turn leads to neuronal damage and cell death. MK801 is a known blocker of this receptor used here as a control. The results in this Figure demonstrate that when NMDA in increasing concentrations is added to neuronal cultures it leads to cell death, while the use of ELV2 reduces cell death and increases cell viability. These data support the use of the elovanoids for the treatment of neurodegenerative diseases and conditions involving NMDA-related excitotoxicity, such as: ischemic stroke, Alzheimer's disease, Parkinson's disease, etc. Example 10 FIG.12—Elovanoids ELV2-Na and ELV2-Me are more active than DHA and NPD1 in a model of ischemic stroke after 2 hrs of MCAo (middle cerebral occlusion). To test the novel elovanoids the experimental design consisted injecting the compounds into the right cerebral ventricle (5 μg/per rat, ICV), one hour after two hours of an ischemic stroke in rats and following thereafter the neurological behavior (neurological score) during 7 days. The protocol in brief was as follows. The injection was made through a surgically implanted metal canula (Alzet) into the right lateral ventricle. Two days later the right middle cerebral artery (MCA) was occluded for 2 h by means of an intraluminal nylon filament (Belayev et al, Traslational Stroke Research, 2010). Then one hour after the compounds were injected dissolved in sterile cerebrospinal fluid. The occlusion was transient performed as follows. The right common carotid artery was exposed through an incision in the neck and was isolated from surrounding tissues. The distal external carotid artery and pterygopalatine arteries were tied. A 4-cm of 3-0 monofilament nylon suture coated with poly-Lysine was introduced into the internal carotid artery and MCA. The suture position was confirmed by advancing the suture 20-22 mm from the common carotid artery bifurcation. Then, the rats were allowed to awaken from anesthesia and returned to their cages. The degree of stroke injury was assessed by neurological assessment of each rat at 60 min after onset of MCAo. Rats that do not demonstrate high-grade contralateral deficit (score, 10-11) were excluded from the study. After 2 hours of MCA occlusion, the rats were re-anesthetized temperature probes were reinserted and the intraluminal suture was removed. The neck incision was closed with silk sutures, and the animals were allowed free access to food and water. These results show that the use elovanoids after the ischemic event result in remarkable neuroprotection, suggesting a potential therapeutic benefit for the treatment of ischemic stroke and other neurodegenerative diseases or disorders. The sodium salt ELV2-Na showed a greater potency, presumably because it delivers the active form of ELV2 and has a more immediate effect. The methyl ester ELV2-Me is expected to first be hydrolyzed via the actions of esterases, and it may have a more delayed effect, which may be beneficial for a sustainable long-term treatment. Overall, these data demonstrate the neuroprotective effects of the elovanoids, either as pharmaceutically acceptable salts (e.g. ELV2-Na), or in the form of a prodrug, such as an ester derivative (e.g. ELV2-Me), or as a pharmaceutical composition containing a combination of the two forms that can have both an immediate and a sustainable long-term therapeutic effect. REFERENCES Bazan N G. 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11858889 | DETAILED DESCRIPTION The compounds, compositions, and methods described herein may be understood more readily by reference to the following detailed description of specific aspects of the disclosed subject matter and the Examples included therein. Before the present compounds, compositions, and methods are disclosed and described, it is to be understood that the aspects described below are not limited to specific synthetic methods or specific reagents, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Also, throughout this specification, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which the disclosed matter pertains. The references disclosed are also individually and specifically incorporated by reference herein for the material contained in them that is discussed in the sentence in which the reference is relied upon. General Definitions In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings. Throughout the description and claims of this specification the word “comprise” and other forms of the word, such as “comprising” and “comprises,” means including but not limited to, and is not intended to exclude, for example, other additives, components, integers, or steps. As used in the description and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a composition” includes mixtures of two or more such compositions, reference to “an agent” includes mixtures of two or more such agents, reference to “the component” includes mixtures of two or more such components, and the like. “Optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event or circumstance occurs and instances where it does not. Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. By “about” is meant within 5% of the value, e.g., within 4, 3, 2, or 1% of the value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is understood that throughout this specification the identifiers “first” and “second” are used solely to aid in distinguishing the various components and steps of the disclosed subject matter. The identifiers “first” and “second” are not intended to imply any particular order, amount, preference, or importance to the components or steps modified by these terms. As used herein, by a “subject” is meant an individual. Thus, the “subject” can include domesticated animals (e.g., cats, dogs, etc.), livestock (e.g., cattle, horses, pigs, sheep, goats, etc.), laboratory animals (e.g., mouse, rabbit, rat, guinea pig, etc.), and birds. “Subject” can also include a mammal, such as a primate or a human. Thus, the subject can be a human or veterinary patient. The term “patient” refers to a subject under the treatment of a clinician, e.g., physician. The term “inhibit” refers to a decrease in an activity, response, condition, disease, or other biological parameter. This can include but is not limited to the complete ablation of the activity, response, condition, or disease. This can also include, for example, a 10% reduction in the activity, response, condition, or disease as compared to the native or control level. Thus, the reduction can be a 10, 20, 30, 40, 50, 60, 70, 80, 90, 100%, or any amount of reduction in between as compared to native or control levels. By “reduce” or other forms of the word, such as “reducing” or “reduction,” is meant lowering of an event or characteristic (e.g., DDAH or ADMA). It is understood that this is typically in relation to some standard or expected value, in other words it is relative, but that it is not always necessary for the standard or relative value to be referred to. For example, “reduces AMDA” means reducing the circulating levels of ADMA in a subject relative to a standard or a control. A modulator is a compound that can reduce or increase DDAH in different cells, tissues or in response to different stimulator or inhibitor. A modulator may produce efficacy in certain disease by increasing DDAH such as heart disease or PAH whereas in other disease, it may produce efficacy by reducing DDAH such as pain, eye disease and cancer. By “prevent” or other forms of the word, such as “preventing” or “prevention,” is meant to stop a particular event or characteristic, to stabilize or delay the development or progression of a particular event or characteristic, or to minimize the chances that a particular event or characteristic will occur. Prevent does not require comparison to a control as it is typically more absolute than, for example, reduce. As used herein, something could be reduced but not prevented, but something that is reduced could also be prevented. Likewise, something could be prevented but not reduced, but something that is prevented could also be reduced. It is understood that where reduce or prevent are used, unless specifically indicated otherwise, the use of the other word is also expressly disclosed. For example, the terms “prevent” or “suppress” can refer to a treatment that forestalls or slows the onset of a disease or condition or reduced the severity of the disease or condition. Thus, if a treatment can treat a disease in a subject having symptoms of the disease, it can also prevent or suppress that disease in a subject who has yet to suffer some or all of the symptoms. The term “treatment” refers to the medical management of a patient with the intent to cure, ameliorate, stabilize, or prevent a disease, pathological condition, or disorder. This term includes active treatment, that is, treatment directed specifically toward the improvement of a disease, pathological condition, or disorder, and also includes causal treatment, that is, treatment directed toward removal of the cause of the associated disease, pathological condition, or disorder. In addition, this term includes palliative treatment, that is, treatment designed for the relief of symptoms rather than the curing of the disease, pathological condition, or disorder; preventative treatment, that is, treatment directed to minimizing or partially or completely inhibiting the development of the associated disease, pathological condition, or disorder; and supportive treatment, that is, treatment employed to supplement another specific therapy directed toward the improvement of the associated disease, pathological condition, or disorder. As used herein, “fibrotic condition” refers to a disease or condition involving the formation and/or deposition of fibrous tissue, e.g., excessive connective tissue builds up in a tissue and/or spreads over or replaces normal organ tissue (reviewed in, e.g., Wynn,Nature Reviews4:583-594 (2004) and Abdel-Wahab, O. et al. (2009)Annu. Rev. Med.60:233-45, incorporated herein by reference). In certain embodiments, the fibrotic condition involves excessive collagen mRNA production and deposition. In certain embodiments, the fibrotic condition is caused, at least in part, by injury, e.g., chronic injury (e.g., an insult, a wound, a toxin, a disease). In certain embodiments, the fibrotic condition is associated with an inflammatory, an autoimmune or a connective tissue disorder. For example, chronic inflammation in a tissue can lead to fibrosis in that tissue. Exemplary fibrotic tissues include, but are not limited to, biliary tissue, liver tissue, lung tissue, heart tissue, vascular tissue, kidney tissue, skin tissue, gut tissue, peritoneal tissue, bone marrow, and the like. In certain embodiments, the tissue is epithelial tissue. The term “therapeutically effective” refers to the amount of the composition used is of sufficient quantity to ameliorate one or more causes or symptoms of a disease or disorder. Such amelioration only requires a reduction or alteration, not necessarily elimination. The term “pharmaceutically acceptable” refers to those compounds, materials, compositions, and/or dosage forms which are, within the scope of sound medical judgment, suitable for use in contact with the tissues of human beings and animals without excessive toxicity, irritation, allergic response, or other problems or complications commensurate with a reasonable benefit/risk ratio. The term “prodrug” refers to a compound that, when metabolized in vivo, undergo conversion to a compound having the desired pharmacological activity. Prodrugs can be prepared by replacing appropriate functionalities present in compound of Formula I with “pro-moieties” as described, for example, in H. Bundgaar, Design of Prodrugs (1985). Examples of prodrugs include ester (e.g., alkyl esters, glycyl esters, amino acid esters such as valine esters, PEG esters, glycerol esters, N-methylpiperazino esters, aminocarboxylic acid esters, etc.), ether, amide (e.g., benzamides, carboxamides, amides derived from amino acids residues, etc.), carbonate, carbamate, imine, and phosphate derivatives of the compounds herein, and their pharmaceutically acceptable salts. For further discussions of prodrugs, see, for example, T. Higuchi and V. Stella “Pro-drugs as Novel Delivery Systems,” ACS Symposium Series 14 (1975) and E. B. Roche ed., Bioreversible Carriers in Drug Design (1987); and D. H. Jornada, G. S. dos Santos Fernandes, D. E. Chiba, T. R. F. de Melo, J. L. dos Santos, and M. C. Chung.Molecules,2016, 21, 42. The term “pharmaceutically acceptable salt” refers generally to compounds prepared by reaction of a free acid or base form of a compound described herein with a stoichiometric amount of an appropriate base or acid in water or in an organic solvent, or in a mixture of the two; generally, non-aqueous media like ether, ethyl acetate, ethanol, isopropanol, or acetonitrile are preferred. Lists of suitable salts are found, for example, in Remington's Pharmaceutical Sciences, 20th ed., Lippincott Williams & Wilkins, Baltimore, M D, 2000, p. 704. In some cases, it may be desirable to prepare a salt of a compound described herein due to one or more of the salt's advantageous physical properties, such as enhanced stability or a desirable solubility or dissolution profile. Suitable pharmaceutically acceptable acid addition salts of the compounds of the present invention when possible include those derived from inorganic acids, such as hydrochloric, hydrobromic, hydrofluoric, boric, fluoroboric, phosphoric, metaphosphoric, nitric, carbonic, sulfonic, and sulfuric acids, and organic acids such as acetic, benzenesulfonic, benzoic, citric, ethanesulfonic, fumaric, gluconic, glycolic, isothionic, lactic, lactobionic, maleic, malic, methanesulfonic, trifluoromethanesulfonic, succinic, toluenesulfonic, tartaric, and trifluoroacetic acids. Suitable organic acids generally include, for example, aliphatic, cycloaliphatic, aromatic, araliphatic, heterocyclic, carboxylic, and sulfonic classes of organic acids. Specific examples of suitable organic acids include acetate, trifluoroacetate, formate, propionate, succinate, glycolate, gluconate, digluconate, lactate, malate, tartaric acid, citrate, ascorbate, glucuronate, maleate, fumarate, pyruvate, aspartate, glutamate, benzoate, anthranilic acid, mesylate, stearate, salicylate, p-hydroxybenzoate, phenylacetate, mandelate, embonate (pamoate), methanesulfonate, ethanesulfonate, benzenesulfonate, pantothenate, toluenesulfonate, 2-hydroxyethanesulfonate, sufanilate, cyclohexylaminosulfonate, algenic acid, β-hydroxybutyric acid, galactarate, galacturonate, adipate, alginate, butyrate, camphorate, camphorsulfonate, cyclopentanepropionate, dodecylsulfate, glycoheptanoate, glycerophosphate, heptanoate, hexanoate, nicotinate, 2-naphthalesulfonate, oxalate, palmoate, pectinate, 3-phenylpropionate, picrate, pivalate, thiocyanate, tosylate, and undecanoate. In some cases, the pharmaceutically acceptable salt may include alkali metal salts, including but not limited to sodium or potassium salts; alkaline earth metal salts, e.g., calcium or magnesium salts; and salts formed with suitable organic ligands, e.g., quaternary ammonium salts. In another embodiment, base salts are formed from bases which form non-toxic salts, including aluminum, arginine, benzathine, choline, diethylamine, diolamine, glycine, lysine, meglumine, olamine, tromethamine and zinc salts. Organic salts may be made from secondary, tertiary or quaternary amine salts, such as tromethamine, diethylamine, N,N′-dibenzylethylenediamine, chloroprocaine, choline, diethanolamine, ethylenediamine, meglumine (N-methylglucamine), and procaine. Basic nitrogen-containing groups may be quaternized with agents such as lower alkyl (C1-C6) halides (e.g., methyl, ethyl, propyl, and butyl chlorides, bromides, and iodides), dialkyl sulfates (e.g., dimethyl, diethyl, dibutyl, and diamyl sulfates), long chain halides (e.g., decyl, lauryl, myristyl, and stearyl chlorides, bromides, and iodides), arylalkyl halides (e.g., benzyl and phenethyl bromides), and others. Chemical Definitions Terms used herein will have their customary meaning in the art unless specified otherwise. The organic moieties mentioned when defining variable positions within the general formulae described herein (e.g., the term “halogen”) are collective terms for the individual substituents encompassed by the organic moiety. The prefix Cn-Cmpreceding a group or moiety indicates, in each case, the possible number of carbon atoms in the group or moiety that follows. As used herein, the term “substituted” is contemplated to include all permissible substituents of organic compounds. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents can be one or more and the same or different for appropriate organic compounds. For purposes of this disclosure, heteroatoms present in a compound or moiety, such as nitrogen, can have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valency of the heteroatom. This disclosure is not intended to be limited in any manner by the permissible substituents of organic compounds. Also, the terms “substitution” or “substituted with” include the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc. “Z1,” “Z2,” “Z3,” and “Z4” are used herein as generic symbols to represent various specific substituents. These symbols can be any substituent, not limited to those disclosed herein, and when they are defined to be certain substituents in one instance, they can, in another instance, be defined as some other substituents. As used herein, the term “alkyl” refers to saturated, straight-chained or branched saturated hydrocarbon moieties. Unless otherwise specified, C1-C24(e.g., C1-C22, C1-C20, C1-C18, C1-C16, C1-C14, C1-C12, C1-C10, C1-C8, C1-C6, or C1-C4) alkyl groups are intended. Examples of alkyl groups include methyl, ethyl, propyl, 1-methyl-ethyl, butyl, 1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl-ethyl, pentyl, 1-methyl-butyl, 2-methyl-butyl, 3-methyl-butyl, 2,2-dimethyl-propyl, 1-ethyl-propyl, hexyl, 1,1-dimethyl-propyl, 1,2-dimethyl-propyl, 1-methyl-pentyl, 2-methyl-pentyl, 3-methyl-pentyl, 4-methyl-pentyl, 1,1-dimethyl-butyl, 1,2-dimethyl-butyl, 1,3-dimethyl-butyl, 2,2-dimethyl-butyl, 2,3-dimethyl-butyl, 3,3-dimethyl-butyl, 1-ethyl-butyl, 2-ethyl-butyl, 1,1,2-trimethyl-propyl, 1,2,2-trimethyl-propyl, 1-ethyl-1-methyl-propyl, and 1-ethyl-2-methyl-propyl. Alkyl substituents may be unsubstituted or substituted with one or more chemical moieties. The alkyl group can be substituted with one or more groups including, but not limited to, hydroxy, halogen, acyl, alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, acyl, aldehyde, amino, carboxylic acid, ester, ether, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, as described below, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied. Throughout the specification “alkyl” is generally used to refer to both unsubstituted alkyl groups and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the specific substituent(s) on the alkyl group. For example, the term “halogenated alkyl” specifically refers to an alkyl group that is substituted with one or more halides (halogens; e.g., fluorine, chlorine, bromine, or iodine). The term “alkoxyalkyl” specifically refers to an alkyl group that is substituted with one or more alkoxy groups, as described below. The term “alkylamino” specifically refers to an alkyl group that is substituted with one or more amino groups, as described below, and the like. When “alkyl” is used in one instance and a specific term such as “alkylalcohol” is used in another, it is not meant to imply that the term “alkyl” does not also refer to specific terms such as “alkylalcohol” and the like. This practice is also used for other groups described herein. That is, while a term such as “cycloalkyl” refers to both unsubstituted and substituted cycloalkyl moieties, the substituted moieties can, in addition, be specifically identified herein; for example, a particular substituted cycloalkyl can be referred to as, e.g., an “alkylcycloalkyl.” Similarly, a substituted alkoxy can be specifically referred to as, e.g., a “halogenated alkoxy,” a particular substituted alkenyl can be, e.g., an “alkenylalcohol,” and the like. Again, the practice of using a general term, such as “cycloalkyl,” and a specific term, such as “alkylcycloalkyl,” is not meant to imply that the general term does not also include the specific term. As used herein, the term “alkenyl” refers to unsaturated, straight-chained, or branched hydrocarbon moieties containing a double bond. Unless otherwise specified, C2-C24(e.g., C2-C22, C2-C20, C2-C18, C2-C16, C2-C14, C2-C12, C2-C10, C2-C8, C2-C6, C2-C4) alkenyl groups are intended. Alkenyl groups may contain more than one unsaturated bond. Examples include ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, and 1-ethyl-2-methyl-2-propenyl. The term “vinyl” refers to a group having the structure —CH═CH2; 1-propenyl refers to a group with the structure-CH═CH—CH3; and 2-propenyl refers to a group with the structure —CH2—CH═CH2. Asymmetric structures such as (Z1Z2)C═C(Z3Z4) are intended to include both the E and Z isomers. This can be presumed in structural formulae herein wherein an asymmetric alkene is present, or it can be explicitly indicated by the bond symbol C═C. Alkenyl substituents may be unsubstituted or substituted with one or more chemical moieties. Examples of suitable substituents include, for example, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, acyl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, as described below, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied. As used herein, the term “alkynyl” represents straight-chained or branched hydrocarbon moieties containing a triple bond. Unless otherwise specified, C2-C24(e.g., C2-C22, C2-C20, C2-C18, C2-C16, C2-C14, C2-C12, C2-C10, C2-C8, C2-C6, C2-C4) alkynyl groups are intended. Alkynyl groups may contain more than one unsaturated bond. Examples include C2-C6-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl (or propargyl), 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl-1-butynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 3-methyl-1-pentynyl, 4-methyl-1-pentynyl, 1-methyl-2-pentynyl, 4-methyl-2-pentynyl, 1-methyl-3-pentynyl, 2-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, and 1-ethyl-1-methyl-2-propynyl. Alkynyl substituents may be unsubstituted or substituted with one or more chemical moieties. Examples of suitable substituents include, for example, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, acyl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, as described below. As used herein, the term “aryl,” as well as derivative terms such as aryloxy, refers to groups that include a monovalent aromatic carbocyclic group of from 3 to 20 carbon atoms. Aryl groups can include a single ring or multiple condensed rings. In some embodiments, aryl groups include C6-C10aryl groups. Examples of aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, tetrahydronaphthyl, phenylcyclopropyl, and indanyl. In some embodiments, the aryl group can be a phenyl, indanyl or naphthyl group. The term “heteroaryl” is defined as a group that contains an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. The term “non-heteroaryl,” which is included in the term “aryl,” defines a group that contains an aromatic group that does not contain a heteroatom. The aryl or heteroaryl substituents may be unsubstituted or substituted with one or more chemical moieties. Examples of suitable substituents include, for example, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, acyl, aldehyde, amino, carboxylic acid, cycloalkyl, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol as described herein. The term “biaryl” is a specific type of aryl group and is included in the definition of aryl. Biaryl refers to two aryl groups that are bound together via a fused ring structure, as in naphthalene, or are attached via one or more carbon-carbon bonds, as in biphenyl. The term “cycloalkyl” as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. The term “heterocycloalkyl” is a cycloalkyl group as defined above where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl group and heterocycloalkyl group can be substituted or unsubstituted. The cycloalkyl group and heterocycloalkyl group can be substituted with one or more groups including, but not limited to, alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, acyl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol as described herein. The term “cycloalkenyl” as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms and containing at least one double bound, i.e., C═C. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, and the like. The term “heterocycloalkenyl” is a type of cycloalkenyl group as defined above, and is included within the meaning of the term “cycloalkenyl,” where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkenyl group and heterocycloalkenyl group can be substituted or unsubstituted. The cycloalkenyl group and heterocycloalkenyl group can be substituted with one or more groups including, but not limited to, alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, acyl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol as described herein. The term “cyclic group” is used herein to refer to either aryl groups, non-aryl groups (i.e., cycloalkyl, heterocycloalkyl, cycloalkenyl, and heterocycloalkenyl groups), or both. Cyclic groups have one or more ring systems that can be substituted or unsubstituted. A cyclic group can contain one or more aryl groups, one or more non-aryl groups, or one or more aryl groups and one or more non-aryl groups. The term “acyl” as used herein is represented by the formula —C(O)Z1where Z1can be a hydrogen, hydroxyl, alkoxy, alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above. As used herein, the term “acyl” can be used interchangeably with “carbonyl.” Throughout this specification “C(O)” or “CO” is a short hand notation for C═O. As used herein, the term “alkoxy” refers to a group of the formula Z1—O—, where Z1is unsubstituted or substituted alkyl as defined above. Unless otherwise specified, alkoxy groups wherein Z1is a C1-C24(e.g., C1-C22, C1-C20, C1-C18, C1-C16, C1-C14, C1-C12, C1-C10, C1-C8, C1-C6, C1-C4) alkyl group are intended. Examples include methoxy, ethoxy, propoxy, 1-methyl-ethoxy, butoxy, 1-methyl-propoxy, 2-methyl-propoxy, 1,1-dimethyl-ethoxy, pentoxy, 1-methyl-butyloxy, 2-methyl-butoxy, 3-methyl-butoxy, 2,2-di-methyl-propoxy, 1-ethyl-propoxy, hexoxy, 1,1-dimethyl-propoxy, 1,2-dimethyl-propoxy, 1-methyl-pentoxy, 2-methyl-pentoxy, 3-methyl-pentoxy, 4-methyl-pentoxy, 1,1-dimethyl-butoxy, 1,2-dimethyl-butoxy, 1,3-dimethyl-butoxy, 2,2-dimethyl-butoxy, 2,3-dimethyl-butoxy, 3,3-dimethyl-butoxy, 1-ethyl-butoxy, 2-ethylbutoxy, 1,1,2-trimethyl-propoxy, 1,2,2-trimethyl-propoxy, 1-ethyl-1-methyl-propoxy, and 1-ethyl-2-methyl-propoxy. The term “aldehyde” as used herein is represented by the formula —C(O)H. The terms “amine” or “amino” as used herein are represented by the formula —NZ1Z2, where Z1and Z2can each be substitution group as described herein, such as hydrogen, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above. “Amido” is —C(O)NZ1Z2. The term “carboxylic acid” as used herein is represented by the formula —C(O)OH. A “carboxylate” or “carboxyl” group as used herein is represented by the formula —C(O)O−. The term “ester” as used herein is represented by the formula —OC(O)Z1or —C(O)OZ1, where Z1can be an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above. The term “ether” as used herein is represented by the formula Z1OZ2, where Z1and Z2can be, independently, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above. The term “ketone” as used herein is represented by the formula Z1C(O)Z2, where Z1and Z2can be, independently, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above. The term “halide” or “halogen” or “halo” as used herein refers to fluorine, chlorine, bromine, and iodine. The term “hydroxyl” as used herein is represented by the formula —OH. The term “nitro” as used herein is represented by the formula —NO2. The term “silyl” as used herein is represented by the formula —SiZ1Z2Z3, where Z1, Z2, and Z3can be, independently, hydrogen, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above. The term “sulfonyl” is used herein to refer to the group represented by the formula —S(O)2Z1, where Z1can be hydrogen, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above. The term “sulfonylamino” or “sulfonamide” as used herein is represented by the formula —S(O)2NH—. The term “thiol” as used herein is represented by the formula —SH. The term “thio” as used herein is represented by the formula —S—. As used herein, Me refers to a methyl group; OMe refers to a methoxy group; and i-Pr refers to an isopropyl group. “R1,” “R2,” “R3,” “Rn,” etc., where n is some integer, as used herein can, independently, possess one or more of the groups listed above. For example, if R1is a straight chain alkyl group, one of the hydrogen atoms of the alkyl group can optionally be substituted with a hydroxyl group, an alkoxy group, an amine group, an alkyl group, a halide, and the like. Depending upon the groups that are selected, a first group can be incorporated within second group or, alternatively, the first group can be pendant (i.e., attached) to the second group. For example, with the phrase “an alkyl group comprising an amino group,” the amino group can be incorporated within the backbone of the alkyl group. Alternatively, the amino group can be attached to the backbone of the alkyl group. The nature of the group(s) that is (are) selected will determine if the first group is embedded or attached to the second group. Unless stated to the contrary, a formula with chemical bonds shown only as solid lines and not as wedges or dashed lines contemplates each possible stereoisomer or mixture of stereoisomer (e.g., each enantiomer, each diastereomer, each meso compound, a racemic mixture, or scalemic mixture). Reference will now be made in detail to specific aspects of the disclosed materials, compounds, compositions, and methods, examples of which are illustrated in the accompanying Examples. Compounds Provided herein are compounds that can reduce ADMA levels in a subject. In some embodiments, the compound can be defined by Formula I: or a pharmaceutically acceptable salt or prodrug thereof, whereinrepresents a single, double, or triple bond;X1and X2, as valence permits, are independently absent or selected from C, CH, CH2, O, CO, S, SO2, and NR′; wherein R is independently selected from hydrogen or C1-C6alkyl; or X1and X2together with the bond to which they are attached form a 3 or 4 membered carbocyclic ring;R2is, independently for each occurrence, selected from halogen, cyano, hydroxyl, amino, alkylamino, dialkylamino, alkyl, haloalkyl; alkylthio; haloalkylthio; alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylaminocarbonyl, heteroalkylaminocarbonyl, dialkylaminocarbonyl, and heterodialkylaminocarbonyl; n is an integer from 0 to 4; Y is selected from aryl, heteroaryl, cycloalkyl, and heterocycloalkyl, each optionally substituted with one or more substituents individually selected from R″; and R″ is, independently for each occurrence, selected from halogen, cyano, nitro, hydroxyl, amino, alkylamino, dialkylamino, alkyl, haloalkyl; alkylthio; haloalkylthio; alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylaminocarbonyl, heteroalkylaminocarbonyl, dialkylaminocarbonyl, and heterodialkylaminocarbonyl. In some embodiments, the compound can be defined by Formula IA: wherein, X1, X2, R2, n, Y, R′, and R″ are as defined above with respect to Formula I; and R1is selected from hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, aryl, and alkylaryl. In some embodiments of Formula I and Formula IA, Y can be a substituted or unsubstituted aryl ring (e.g., a substituted or unsubstituted phenyl ring). In certain embodiments, Y can be a substituted phenyl ring. In certain embodiments, Y can be a di-substituted phenyl ring. In other embodiments of Formula I and Formula IA, Y can be a substituted or unsubstituted 5- to 7-membered heteroaryl ring. For example, Y can be an oxazole ring, a pyridinyl ring, a thiazole ring, or a thiophene ring. In some embodiments, the compound of Formula I and Formula IA can be defined by the formula below or a pharmaceutically acceptable salt or prodrug thereof, wherein, X1, X2, R2, n, Y, R′, and R″ are as defined above with respect to Formula I; Z, is S or O; Z2is N or C—R3; and R3R4, and R5, are independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, amino, alkylamino, dialkylamino, alkyl, haloalkyl; alkylthio; haloalkylthio; alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylaminocarbonyl, heteroalkylaminocarbonyl, dialkylaminocarbonyl, and heterodialkylaminocarbonyl. In some embodiments, the compound of Formula I and Formula IA can be defined by the formula below or a pharmaceutically acceptable salt or prodrug thereof, wherein, X1, X2, R2, n, Y, R′, and R″ are as defined above with respect to Formula I; Z1is S or O; Z2is N or C—R4; and R3R4, and R5, are independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, amino, alkylamino, dialkylamino, alkyl, haloalkyl; alkylthio; haloalkylthio; alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylaminocarbonyl, heteroalkylaminocarbonyl, dialkylaminocarbonyl, and heterodialkylaminocarbonyl. In some embodiments, the compound of Formula I and Formula IA can be defined by the formula below or a pharmaceutically acceptable salt or prodrug thereof, wherein, X1, X2, R2, n, Y, R′, and R″ are as defined above with respect to Formula I; and R3R4, and R5, are independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, amino, alkylamino, dialkylamino, alkyl, haloalkyl; alkylthio; haloalkylthio; alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylaminocarbonyl, heteroalkylaminocarbonyl, dialkylaminocarbonyl, and heterodialkylaminocarbonyl. In some embodiments of Formula I and Formula IA, X1and X2are both CH. In some of these embodiments, the stereochemistry of the double bond can be cis. In other cases, the stereochemistry of the double bond can be trans. In other embodiments of Formula I and Formula IA, X1and X2are independently O or CH2. For example, in some embodiments, X1can be CH2and X2can be O. In other embodiments, X2can be CH2and X1can be O. In other embodiments of Formula I and Formula IA, X1and X2together with the bond to which they are attached forms a 3-membered carbocyclic ring. In some embodiments, the compound can be defined by Formula II: or a pharmaceutically acceptable salt or prodrug thereof, whereinis a single, double, or triple bond; X1and X2as valence permits, are independently absent or selected from C, CH, CH2, O, CO, S, SO2, and NR′; wherein R is independently selected from hydrogen or C1-C6alkyl; or X1and X2together with the bond to which they are attached form a 3 or 4 membered carbocyclic ring; and R3R4, R5, R6, and R7are independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, amino, alkylamino, dialkylamino, alkyl, haloalkyl; alkylthio; haloalkylthio; alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylaminocarbonyl, heteroalkylaminocarbonyl, dialkylaminocarbonyl, and heterodialkylaminocarbonyl. In some embodiments, the compound can be a compound defined by Formula IIA: wherein, X1, X2, R′, R3, R4, R5, R6, and R7are as defined above with respect to Formula II; and R1is selected from hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, aryl, and alkylaryl. In some embodiments of Formula II and Formula IIA, X1and X2are both CH. In some of these embodiments, the stereochemistry of the double bond can be cis. In other cases, the stereochemistry of the double bond can be trans. In other embodiments of Formula II and Formula IIA, X1and X2are independently O or CH2. For example, in some embodiments, X1can be CH2and X2can be O. In other embodiments, X2can be CH2and X1can be O. In other embodiments of Formula II and Formula IIA, X1and X2together with the bond to which they are attached forms a 3-membered carbocyclic ring. In some embodiments of Formula II and Formula IIA, R4, R6, and R7are hydrogen. In some embodiments of Formula II and Formula IIA, R3can be a C1-C4alkyl group (e.g., a methyl group). In some embodiments of Formula II and Formula IIA, R5can be selected from hydroxyl and C1-C4alkoxy (e.g., a methoxy group). In some embodiments of Formula II and Formula IIA, R5can hydroxyl. In some embodiments of Formula II and Formula IIA, R5can be C1-C4alkoxy (e.g., a methoxy group). In other examples, the compound can be defined by Formula III: or a pharmaceutically acceptable salt or prodrug thereof, whereinis a single, double, or triple bond; X1and X2as valence permits, are independently absent or selected from C, CH, CH2, O, CO, S, SO2, and NR′; wherein R′ is independently selected from hydrogen or C1-C6alkyl; or X1and X2together with the bond to which they are attached form a 3 or 4 membered carbocyclic ring; R2is, independently for each occurrence, selected from halogen, cyano, hydroxyl, amino, alkylamino, dialkylamino, alkyl, haloalkyl; alkylthio; haloalkylthio; alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylaminocarbonyl, heteroalkylaminocarbonyl, dialkylaminocarbonyl, and heterodialkylaminocarbonyl; n is an integer from 0 to 4; Y is a 5- to 7-membered heteroaryl ring selected from an oxazole ring, a pyridinyl ring, a thiazole ring, and a thiophene ring, each optionally substituted with one or more substituents individually selected from R″; and R″ is, independently for each occurrence, selected from halogen, cyano, nitro, hydroxyl, amino, alkylamino, dialkylamino, alkyl, haloalkyl; alkylthio; haloalkylthio; alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylaminocarbonyl, heteroalkylaminocarbonyl, dialkylaminocarbonyl, and heterodialkylaminocarbonyl. In some embodiments, the compound can be a compound defined by Formula IIIA: wherein, X1, X2, R, R2, and R″ are as defined above with respect to Formula III; and R1is selected from hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, aryl, and alkylaryl. In some embodiments of Formula III and Formula IIIA, Y can be a substituted or unsubstituted oxazole ring. In some embodiments of Formula III and Formula IIIA, Y can be a substituted or unsubstituted pyridinyl ring. In some embodiments of Formula III and Formula IIIA, Y can be a substituted or unsubstituted thiazole ring. In some embodiments of Formula III and Formula IIIA, Y can be a substituted or unsubstituted thiophene ring. In some embodiments of Formula III and Formula IIIA, X1and X2are both CH. In some of these embodiments, the stereochemistry of the double bond can be cis. In other cases, the stereochemistry of the double bond can be trans. In other embodiments of Formula III and Formula IIIA, X1and X2are independently O or CH2. For example, in some embodiments, X1can be CH2and X2can be O. In other embodiments, X2can be CH2and X1can be O. In other embodiments of Formula III and Formula IIIA, X1and X2together with the bond to which they are attached forms a 3-membered carbocyclic ring. Pharmaceutical Compositions Also provided are compositions that include one or more of the compounds described herein. In some embodiments, ADMA-modulating (e.g., increasing or reducing) compositions are provided, comprising a carrier and an effective amount of a compound described herein. In some embodiments, the carrier can be a pharmaceutically acceptable carrier. A “pharmaceutically acceptable carrier” as used herein refers to a carrier that, when combined with a compound described herein, facilitates the application or administration of that compound described herein for its intended purpose (e.g., to modulate DDAH and ADMA levels in a subject, to treat or prevent a disease or condition associated with elevated levels of asymmetric dimethylarginine (ADMA) in a subject, to increase DDAH levels in a subject, to reduce one or more risk factors associated with inhibition of nitric oxide synthase in a subject, or a combination thereof). In other embodiments, the modulator may decrease the levels of DDAH. The compound described herein may be formulated for administration in a pharmaceutically acceptable carrier in accordance with known techniques. See, e.g., Remington, The Science and Practice of Pharmacy (9th Ed. 1995). The pharmaceutically acceptable carrier can, of course, also be acceptable in the sense of being compatible with any other ingredients in the composition. The carrier may be a solid or a liquid, or both, and is preferably formulated with the a compound described herein as a unit-dose composition, for example, a tablet, which may contain from 0.01 or 0.5% to 95% or 99% by weight of the a compound described herein. One or more a compounds described herein can be included in the compositions, which may be prepared by any of the well-known techniques of pharmacy comprising admixing the components, optionally including one or more accessory ingredients. In general, compositions may be prepared by uniformly and intimately admixing a compound described herein with a liquid or finely divided solid carrier, or both, and then, if necessary, shaping the resulting mixture. For example, a tablet may be prepared by compressing or molding a powder or granules containing the a compound described herein, optionally with one or more accessory ingredients. Compressed tablets may be prepared by compressing, in a suitable machine, the compound in a free-flowing form, such as a powder or granules optionally mixed with a binder, lubricant, inert diluent, and/or surface active/dispersing agent(s). Molded tablets may be made by molding, in a suitable machine, the powdered compound moistened with an inert liquid binder. Compositions can be formulated to be suitable for oral, nasal, rectal, topical, buccal (e.g., sub-lingual), vaginal, parenteral (e.g., subcutaneous, intramuscular, intradermal, or intravenous), topical (i.e., both skin and mucosal surfaces, including airway surfaces) or transdermal administration, although the most suitable route in any given case will depend on the nature and severity of the condition being treated and on the nature of the particular compound that is being used. Compositions suitable for oral administration may be presented in discrete units, such as capsules, cachets, lozenges, or tablets, each containing a predetermined amount of the compound; as a powder or granules; as a solution or a suspension in an aqueous or non-aqueous liquid; or as an oil-in-water or water-in-oil emulsion. Such compositions may be prepared by any suitable method of pharmacy, which includes the step of bringing into association the compound and a suitable carrier (which may contain one or more accessory ingredients as noted above). Compositions suitable for buccal (sub-lingual) administration include lozenges comprising the compound in a flavored base, usually sucrose and acacia or tragacanth; and pastilles comprising the compound in an inert base such as gelatin and glycerin or sucrose and acacia. Compositions suitable for parenteral administration comprise sterile aqueous and non-aqueous injection solutions of the compound, which preparations are preferably isotonic with the blood of the intended recipient. These preparations may contain antioxidants, buffers, bacteriostats and solutes that render the composition isotonic with the blood of the intended recipient. Aqueous and non-aqueous sterile suspensions may include suspending agents and thickening agents. The compositions may be presented in unit/dose or multi-dose containers, for example sealed ampoules and vials, and may be stored in a freeze-dried (lyophilized) condition requiring only the addition of the sterile liquid carrier, for example, saline or water-for-injection immediately prior to use. Extemporaneous injection solutions and suspensions may be prepared from sterile powders, granules and tablets of the kind previously described. For example, the composition can be an injectable, stable, sterile composition comprising a compound described herein in a unit dosage form in a sealed container. The composition can be provided in the form of a lyophilizate that can be reconstituted with a suitable pharmaceutically acceptable carrier to form a liquid composition suitable for injection thereof into a subject. The unit dosage form can comprise from about 10 mg to about 10 grams of the compound. When the compound or salt is substantially water-insoluble, a sufficient amount of emulsifying agent that is physiologically acceptable may be employed in sufficient quantity to emulsify the compound or salt in an aqueous carrier. One such useful emulsifying agent is phosphatidyl choline. Compositions suitable for rectal administration can be presented as unit dose suppositories. These may be prepared by mixing the active compound with one or more conventional solid carriers, for example, cocoa butter, and then shaping the resulting mixture. Compositions suitable for topical application to the skin can take the form of an ointment, cream, lotion, paste, gel, spray, aerosol, or oil. Carriers that may be used include petroleum jelly, lanoline, polyethylene glycols, alcohols, transdermal enhancers, and combinations of two or more thereof. Compositions suitable for transdermal administration can be presented as discrete patches adapted to remain in intimate contact with the epidermis of the recipient for a prolonged period of time. Compositions suitable for transdermal administration may also be delivered by iontophoresis and typically take the form of an optionally buffered aqueous solution of the active compound. In some embodiments, the compositions described herein can further include one or more additional active agents. Examples of suitable additional active agents include antidiabetics, hypotensive agents, perfusion-enhancing agents, lipid metabolism modulators, antithrombotic agents, antioxidants, chemokine receptor antagonists, p38-kinase inhibitors, NPY agonists, orexin agonists, anorectics, PAF-AH inhibitors, antiphlogistics, COX inhibitors, LTB4-receptor antagonists, analgesics, prostacyclin analogs, guanylate cyclase stimulators, endothelin receptor antagonists, PDE5 inhibitors, ACE inhibitors, angiotensin receptor antagonists, diuretics, analgesics (e.g., NSAIDs such as aspirin), antidepressants, and other psychopharmaceuticals. Examples of lipid metabolism modulators include HMG-CoA reductase inhibitors, inhibitors of HMG-CoA reductase expression, squalene synthesis inhibitors, ACAT inhibitors, LDL receptor inductors, cholesterol absorption inhibitors, polymeric bile acid adsorbers, bile acid reabsorption inhibitors, MTP inhibitors, lipase inhibitors, LpL activators, fibrates, niacin, CETP inhibitors, PPAR-α, PPAR-γ and/or PPAR-δ agonists, RXR modulators, FXR modulators, LXR modulators, thyroid hormones and/or thyroid mimetics, ATP citrate lyase inhibitors, Lp(a) antagonists, cannabinoid receptor 1 antagonists, leptin receptor agonists, bombesin receptor agonists, histamine receptor agonists, cannabinoid receptor 1 antagonists, and antioxidants/radical scavengers. In some embodiments, the lipid metabolism modulator can comprise a statins, such as, by way of example, lovastatin, simvastatin, pravastatin, fluvastatin, atorvastatin, rosuvastatin, cerivastatin, or pitavastatin. In some embodiments, the lipid metabolism modulator can comprise a squalene synthesis inhibitor, such as, by way of example, BMS-188494 or TAK-475. In some embodiments, the lipid metabolism modulator can comprise an ACAT inhibitor, such as, by way of example, avasimibe, melinamide, pactimibe, eflucimibe or SMP-797. In some embodiments, the lipid metabolism modulator can comprise a cholesterol absorption inhibitor, such as, by way of example, ezetimibe, tiqueside or pamaqueside. In some embodiments, the lipid metabolism modulator can comprise an MTP inhibitor, such as, by way of example, implitapide, BMS-201038, R-103757 or JTT-130. In some embodiments, the lipid metabolism modulator can comprise a lipase inhibitor, such as, by way of example, orlistat. In some embodiments, the lipid metabolism modulator can comprise a thyroid hormone and/or thyroid mimetic, such as, by way of example, D-thyroxine or 3,5,3′-triiodothyronine (T3). In some embodiments, the lipid metabolism modulator can comprise an agonist of the niacin receptor, such as, by way of example, niacin, acipimox, acifran or radecol. In some embodiments, the lipid metabolism modulator can comprise a CETP inhibitor, such as, by way of example, dalcetrapib, BAY 60-5521, anacetrapib or CETP vaccine (CETi-1). In some embodiments, the lipid metabolism modulator can comprise a PPAR-γ agonist, for example from the class of the thiazolidinediones, such as, by way of example, pioglitazone or rosiglitazone. In some embodiments, the lipid metabolism modulator can comprise a PPAR-5 agonist, such as, by way of example, GW-501516 or BAY 68-5042. In some embodiments, the lipid metabolism modulator can comprise a polymeric bile acid adsorber, such as, by way of example, cholestyramine, colestipol, colesolvam, CholestaGel or colestimide. In some embodiments, the lipid metabolism modulator can comprise a bile acid reabsorption inhibitor, such as, by way of example, ASBT (=IBAT) inhibitors, such as, for example, AZD-7806, S-8921, AK-105, BARI-1741, SC-435 or SC-635. In some embodiments, the lipid metabolism modulator can comprise an antioxidant/radical scavenger, such as, by way of example, probucol, AGI-1067, BO-653 or AEOL-10150. In some embodiments, the lipid metabolism modulator can comprise a cannabinoid receptor 1 antagonist, such as, by way of example, rimonabant or SR-147778. Examples of suitable antidiabetics since insulin and insulin derivatives, and also orally effective hypoglycemic active ingredients. Here, insulin and insulin derivatives include both insulins of animal, human or biotechnological origin and also mixtures thereof. The orally effective hypoglycemic active ingredients for example may include sulfonylureas, biguanides, meglitinide derivatives, glucosidase inhibitors and PPAR-gamma agonists. In some embodiments, the antidiabetics can comprise insulin and modified insulins. In some embodiments, the antidiabetics can comprise a sulfonylurea, such as, by way of example, tolbutamide, glibenclamide, glimepiride, glipizide or gliclazide. In some embodiments, the antidiabetics can comprise a biguanide, such as, by way of example, metformin. In some embodiments, the antidiabetics can comprise a meglitinide derivative, such as, by way of example, repaglinide or nateglinide. In some embodiments, the antidiabetics can comprise a glucosidase inhibitor, such as, by way of example, miglitol or acarbose. In some embodiments, the antidiabetics can comprise a DPP-IV inhibitor, such as, by way of example, sitagliptin and vildagliptin. In some embodiments, the antidiabetics can comprise a PPAR-gamma agonist, for example from the class of the thiazolinediones, such as, by way of example, pioglitazone or rosiglitazone. Examples of suitable hypotensive agents include calcium antagonists, angiotensin AII antagonists, ACE inhibitors, beta-receptor blockers, alpha-receptor blockers and diuretics. In some embodiments, the hypotensive agent can comprise a calcium antagonist, such as, by way of example, nifedipine, amlodipine, verapamil or diltiazem. In some embodiments, the hypotensive agent can comprise an angiotensin AII antagonist, such as, by way of example, losartan, valsartan, candesartan, embusartan, olmesartan or telmisartan. In some embodiments, the hypotensive agent can comprise an ACE inhibitor, such as, by way of example, enalapril, captopril, lisinopril, ramipril, delapril, fosinopril, quinopril, perindopril or trandopril. In some embodiments, the hypotensive agent can comprise a beta-receptor blocker, such as, by way of example, propranolol, atenolol, timolol, pindolol, alprenolol, oxprenolol, penbutolol, bupranolol, metipranolol, nadolol, mepindolol, carazalol, sotalol, metoprolol, betaxolol, celiprolol, bisoprolol, carteolol, esmolol, labetalol, carvedilol, adaprolol, landiolol, nebivolol, epanolol or bucindolol. In some embodiments, the hypotensive agent can comprise an alpha-receptor blocker, such as, by way of example, prazosin. In some embodiments, the hypotensive agent can comprise a diuretic, such as, by way of example, furosemide, bumetanide, torsemide, bendroflumethiazide, chlorothiazide, hydrochlorothiazide, hydroflumethiazide, methyclothiazide, polythiazide, trichloromethiazide, chlorothalidone, indapamide, metolazone, quinethazone, acetazolamide, dichlorophenamide, methazolamide, glycerol, isosorbide, mannitol, amiloride or triamteren. In some embodiments, the one or more additional active agents can comprise an aldosterone or mineralocorticoid receptor antagonist, such as, by way of example, spironolactone or eplerenone. In some embodiments, the one or more additional active agents can comprise a vasopressin receptor antagonist, such as, by way of example, conivaptan, tolvaptan, lixivaptan or SR-121463. In some embodiments, the one or more additional active agents can comprise an organic nitrate or NO donor, such as, by way of example, sodium nitroprusside, nitroglycerol, isosorbide mononitrate, isosorbide dinitrate, molsidomin or SIN-1, or in combination with inhalative NO. In some embodiments, the one or more additional active agents can comprise a positive-inotropic compound, such as, by way of example, cardiac glycosides (digoxin), beta-adrenergic and dopaminergic agonists, such as isoproterenol, adrenaline, noradrenaline, dopamine or dobutamine. In some embodiments, the one or more additional active agents can comprise an antisympathotonic, such as reserpine, clonidine or alpha-methyldopa, or a potassium channel agonist, such as minoxidil, diazoxide, dihydralazine or hydralazine, or a substance which releases nitrogen oxide, such as glycerol nitrate or sodium nitroprusside. Examples of antithrombotics include platelet aggregation inhibitors and anticoagulants. In some embodiments, the antithrombotic can comprise a platelet aggregation inhibitor, such as, by way of example, aspirin, clopidogrel, ticlopidine or dipyridamol. In some embodiments, the antithrombotic can comprise a thrombin inhibitor, such as, by way of example, ximelagatran, melagatran, dabigatran, bivalirudin or clexane. In some embodiments, the one or more additional active agents can comprise a GPIIb/IIIa antagonist, such as, by way of example, tirofiban or abciximab. In some embodiments, the one or more additional active agents can comprise a factor Xa inhibitor, such as, by way of example, rivaroxaban (BAY 59-7939), DU-176b, apixaban, otamixaban, fidexaban, razaxaban, fondaparinux, idraparinux, PMD-3112, YM-150, KFA-1982, EMD-503982, MCM-17, MLN-1021, DX 9065a, DPC 906, JTV 803, SSR-126512 or SSR-128428. In some embodiments, the one or more additional active agents can comprise heparin or a low molecular weight (LMW) heparin derivative. In some embodiments, the one or more additional active agents can comprise a vitamin K antagonist, such as, by way of example, coumarin. In some embodiments, the one or more additional active agents can comprise an endothelin receptor antagonist, such as, by way of example, bosentan or ambrisentan. In some embodiments, the one or more additional active agents can comprise a phosphodiesterase type 5 inhibitor, such as, by way of example, sildenafil or tadalafil. In some embodiments, the one or more additional active agents can comprise a prostacyclin analogue, such as, by way of example, epoprostenol, treprostinil or iloprost. Coating compositions are also provided. A “coating” as used herein is generally known. Any of a variety of organic and aqueous coating compositions, with or without pigments, may be modified to contain one or more compounds described herein. Examples of suitable coating compositions include, for example, the coating compositions described in U.S. Pat. Nos. 7,109,262, 6,964,989, 6,835,459, 6,677,035, 6,528,580, and 6,235,812, each incorporated by reference herein in their entirety. In some examples, coating compositions can comprise (in addition to one or more compounds described herein) a film-forming resin, an aqueous or organic solvent that disperses the resin; and, optionally, at least one pigment. Other ingredients such as colorants, secondary pigments, stabilizers and the like can be included if desired. The one or more compounds described herein may be dissolved or dispersed in the solvent and/or resin, so that the compound(s) are dispersed or distributed on an article or substrate coated by the coating composition. The resin may comprise, for example, a polymeric material. A polymeric material is a material that is comprised of large molecules made from associated smaller repeating structural units, often covalently linked. Common examples of polymeric materials are unsaturated polyester resins, and epoxy resins. Any suitable article can be coated, in whole or in part, with the coating compositions described herein. Suitable articles include, but are not limited to, the surface of implantable medical devices such as stents. Coating of the article with the composition can be carried out by any suitable means, such as by brushing, spraying, electrostatic deposition, dip coating, doctor blading, etc. The compositions described herein can include an effective amount of a compound described herein to achieve the intended purpose, e.g. to modulating DDAH and ADMA levels in a subject. The determination of an effective dose is well within the capability of those skilled in the art in view of the present disclosure. For any compound, the therapeutically effective dose can be estimated initially either in in vitro assays, e.g. those described in the Examples herein, or in animal models, usually mice, rabbits, dogs, or pigs. The animal model is also used to achieve a desirable concentration range and route of administration. Such information can then be used to determine useful doses and routes for administration in humans. A therapeutically effective dose refers to that amount of a compound described herein that ameliorates the symptoms or condition. Therapeutic efficacy and toxicity of such compounds can be determined by standard pharmaceutical procedures in vitro or experimental animals, e.g., ED50 (the dose therapeutically effective in 50% of the population) and LD50 (the dose lethal to 50% of the population). The dose ratio between therapeutic and toxic effects is the therapeutic index, and it can be expressed as the ratio, ED50/LD50. Exemplary pharmaceutical compositions exhibit large therapeutic indices. The data obtained from in vitro assays and animal studies are used in formulating a range of dosage for human use. The dosage of such compounds lies for example within a range of circulating concentrations what include the ED50 with little or no toxicity. The dosage varies within this range depending upon the dosage form employed, sensitivity of the patient, and the route of administration. Normal dosage amounts may vary from 0.1 to 1000 milligrams total dose, depending upon the route of administration. Guidance as to particular dosages and methods of delivery is provided in the literature. See U.S. Pat. Nos. 4,657,760; 5,206,344; or 5,225,212. Those skilled in the art will employ different formulations for polynucleotides than for proteins or their inhibitors. Similarly, delivery of polynucleotides or polypeptides will be specific to particular cells, conditions, locations, etc. Methods of Use The compounds described herein can modulate the enzyme dimethylarginine diaminohydrolase (DDAH), modulate ADMA, and/or treat diseases characterized by elevated or low levels of ADMA. The compounds described herein can be administered to a subject in order to modulate tissue or plasma levels of ADMA. ADMA is eliminated from the body through a combination of renal clearance and the enzymatic action of DDAH. It has been shown that there is a direct correlation between renal failure and increased levels of ADMA in patient's blood along with decreased levels of NO. Elevated levels of ADMA have been found in patients with a wide variety of diseases and conditions such as renal disease, coronary artery disease, ischemic heart disease, congestive heart failure, hypertension, lung injury, pulmonary hypertension, hypercholesterolemia, diabetes, atherosclerosis, sepsis, organ failure, surgical trauma, and in particular end stage renal failure. ADMA levels are also increased in patients with acute kidney injury and contrast induced renal injury. In addition, it has been reported that increased ADMA level is an indicator of risk for cardiovascular-related death. Thus, there is an urgent need to develop a means to modulate ADMA or at least reduce ADMA concentration in the blood of patients, in particular patients with chronic kidney disease, organ failure and those who are receiving hemodialysis treatment for kidney related diseases. The ability to reduce ADMA from the blood of end stage renal disease patients in conjunction with hemodialysis treatment by administering the compounds may reduce ADMA-mediated morbidity and extend life. In exemplary embodiments, the DDAH and ADMA-modulating compounds described herein can exhibit activity that is indicative of clinical efficacy, including hydrolyzing ADMA, in vitro or in vivo activity, and efficacy for treatment of cardiac diseases, heart failure, kidney diseases, lung disease, sepsis or in a model thereof. Accordingly, provided herein are methods for modulating DDAH and asymmetric dimethylarginine (ADMA) in a subject, the method comprising administering to the subject a composition comprising a therapeutically effective amount of a compound described herein. Also provided are methods of reducing one or more risk factors associated with inhibition of nitric oxide synthase in a subject. These methods can comprise administering to the subject a therapeutically effective amount of a compound described herein. In some cases, the risk factors can include renal failure, endothelial dysfunction, vascular disease, or a combination thereof. Also provided are methods of treating or preventing a disease or condition associated with elevated levels of asymmetric dimethylarginine (ADMA) in a subject. These methods can comprise administering a therapeutically effective amount of a compound described herein. Administration of the compounds described herein may reduce the concentration of ADMA, and/or increase the levels of citrulline, and/or increase the levels of NO in the subject. The disease can any diseases or conditions associated with elevated ADMA levels, including but not limited to cardiac diseases such as heart failure, or renal diseases. For example, the compounds described herein can be used for the prophylaxis and/or treatment of renal disease, sepsis, sickle cell crisis, severe malaria, Mediterranean fever, trauma, ICU patients, acute kidney injury contrast induced kidney injury, decompensated heart failure, diuretic resistant heart failure, cardiac failure and cardiac insufficiency thromboembolic disorders, reperfusion damage following ischemia, micro- and macrovascular lesions (vasculitis), arterial and venous thromboses, edemas, ischemias such as myocardial infarction, stroke and transient ischemic attacks, for cardio protection in connection with coronary artery bypass operations (coronary artery bypass graft, CABG), primary percutaneous transluminal coronary angioplasties (PTCAs), PTCAs after thrombolysis, rescue PTCA, heart transplants and open-heart operations, and for organ protection in connection with transplants, bypass operations, catheter examinations and other surgical procedures. The compounds described herein can be used for the prophylaxis and/or treatment of respiratory disorders, such as, for example, chronic obstructive pulmonary disease (chronic bronchitis, COPD), asthma, pulmonary emphysema, bronchiectases, lung injury, cystic fibrosis (mucoviscidosis) and pulmonary hypertension, in particular pulmonary arterial hypertension. The compounds described herein can be used for the prophylaxis and/or treatment of kidney diseases, especially of acute and chronic kidney diseases and acute and chronic renal insufficiencies, as well as acute and chronic renal failure, including acute and chronic stages of renal failure with or without the requirement of dialysis, as well as the underlying or related kidney diseases such as renal hypoperfusion, dialysis induced hypotension, glomerulopathies, glomerular and tubular proteinuria, renal edema, hematuria, primary, secondary, as well as acute and chronic glomerulonephritis, membranous and membranoproliferative glomerulonephritis, Alport-Syndrome, glomerulosclerosis, interstistial tubular diseases, nephropathic diseases, such as primary and inborn kidney diseases, renal inflammation, immunological renal diseases like renal transplant rejection, immune complex induced renal diseases, as well as intoxication induced nephropathic diseases, diabetic and non-diabetic renal diseases, pyelonephritis, cystic kidneys, nephrosclerosis, hypertensive nephrosclerosis, nephrotic syndrome, that are characterized and diagnostically associated with an abnormal reduction in creatinine clearance and/or water excretion, abnormal increased blood concentrations of urea, nitrogen, potassium and/or creatinine, alteration in the activity of renal enzymes, such as glutamyl synthetase, urine osmolarity and urine volume, increased microalbuminuria, macroalbuminuria, glomerular and arteriolar lesions, tubular dilation, hyperphosphatemia and/or the requirement of dialysis. The compounds described herein can be used for the prophylaxis and/or treatment of renal carcinomas, after incomplete resection of the kidney, suppression of gastric cancer, dehydration after overuse of diuretics, uncontrolled blood pressure increase with malignant hypertension, urinary tract obstruction and infection, amyloidosis, as well as systemic diseases associated with glomerular damage, such as Lupus erythematosus, and rheumatic immunological systemic diseases, as well as renal artery stenosis, renal artery thrombosis, renal vein thrombosis, analgetics induced nephropathy and renal tubular acidosis. The compounds described herein can be used for the prophylaxis and/or treatment of contrast medium induced and drug induced acute and chronic interstitial kidney diseases, metabolic syndrome and insulin resistance. The compounds described herein can be used for the prophylaxis and/or treatment of aftereffects associated with acute and/or chronic kidney diseases, such as pulmonary edema, heart failure, uremia, anemia, electrolyte disturbances (e.g. hyperkalemia, hyponatremia), as well as bone and carbohydrate metabolism. The compounds described herein can be used for the prophylaxis and/or treatment of coronary heart disease, acute coronary syndrome, heart failure, and myocardial infarction. In therapeutic applications, the compounds described herein are administered to a patient already suffering from a disease, condition or disorder, in an amount sufficient to cure or at least partially arrest the symptoms of the disease, disorder or condition. Such an amount is defined to be a “therapeutically effective amount,” and will depend on the severity and course of the disease, disorder or condition, previous therapy, the patient's health status and response to the drugs, and the judgment of the treating physician. It is considered well within the skill of the art for one to determine such therapeutically effective amounts by routine experimentation (e.g., a dose escalation clinical trial). In prophylactic applications, the compounds described herein are administered to a patient susceptible to or otherwise at risk of a particular disease, disorder or condition. Such an amount is defined to be a “prophylactically effective amount.” In this use, the precise amounts also depend on the patient's state of health, weight, and the like. It is considered well within the skill of the art for one to determine such prophylactically effective amounts by routine experimentation (e.g., a dose escalation clinical trial). The compounds described herein can be used to modulate the concentration of ADMA in a patient. In one embodiment, a subject in need thereof receives a therapeutic amount of a compound described herein that would decrease the subject's ADMA concentration over the baseline of their seeking treatment by 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, more than 100%, 150%, more than 150%, 200%, more than 200%. In another embodiment, provided are methods of treatment of a subject in need thereof to increase the subject's NO production by administering a therapeutically effective amount of a compound described herein to increase NO production by 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, more than 100%, 150%, more than 150%, 200%, more than 200%. The compound described here can reduce DDAH in disease state in certain cells and therefore used for the treatment of pain, eye disease and cancer. The compounds described herein can also be used to treat or prevent fibrotic conditions. Example fibrotic conditions that can be treated or prevented using the compounds described herein include, but are not limited to, a fibrotic condition of the lung, liver, heart, vasculature, kidney, skin, gastrointestinal tract, bone marrow, or a combination thereof. Each of these conditions is described in more detail herein. Fibrosis of the lung (also referred to herein as “pulmonary fibrosis”) is characterized by the formation of scar tissue within the lungs, which results in a decreased function. Pulmonary fibrosis is associated with shortness of breath, which progresses to discomfort in the chest weakness and fatigue, and ultimately to loss of appetite and rapid weight-loss. Approximately 500,000 people in the U.S. and 5 million worldwide suffer from pulmonary fibrosis, and 40,000 people in the U.S. die annually from the disease. Pulmonary fibrosis has a number of causes, including radiation therapy, but can also be due to smoking or hereditary factors (Meltzer, E B et al. (2008)Orphanet J. Rare Dis.3:8). Pulmonary fibrosis can occur as a secondary effect in disease processes such as asbestosis and silicosis, and is known to be more prevalent in certain occupations such as coal miner, ship workers and sand blasters where exposure to environmental pollutants is an occupational hazard (Green, F H et al. (2007)Toxicol Pathol.35:136-47). Other factors that contribute to pulmonary fibrosis include cigarette smoking, and autoimmune connective tissue disorders, like rheumatoid arthritis, scleroderma and systemic lupus erythematosus (SLE) (Leslie, K O et al. (2007)Semin Respir Crit. Care Med.28:369-78; Swigris, J J et al. (2008) Chest. 133:271-80; and Antoniou, K M et al. (2008)Curr Opin Rheumatol.20:686-91). Other connective tissue disorders such as sarcoidosis can include pulmonary fibrosis as part of the disease (Paramothayan, S et al. (2008)Respir Med.102:1-9), and infectious diseases of the lung can cause fibrosis as a long term consequence of infection, particularly chronic infections. Pulmonary fibrosis can also be a side effect of certain medical treatments, particularly radiation therapy to the chest and certain medicines like bleomycin, methotrexate, amiodarone, busulfan, and nitrofurantoin (Catane, R et al. (1979)Int J Radiat Oncol Biol Phys.5:1513-8; Zisman, D A et al. (2001)Sarcoidosis Vasc Diffuse Lung Dis.18:243-52; Rakita, L et al. (1983)Am Heart J.106:906-16; Twohig, K J et al. (1990)Clin Chest Med.11:31-54; and Witten C M. (1989)Arch Phys Med. Rehabil.70:55-7). In other embodiments, idiopathic pulmonary fibrosis can occur where no clear causal agent or disease can be identified. Increasingly, it appears that genetic factors can play a significant role in these cases of pulmonary fibrosis (Steele, M P et al. (2007) Respiration 74:601-8; Brass, D M et al. (2007)Proc Am Thorac Soc.4:92-100 and du Bois R M. (2006)Semin Respir Crit. Care Med.27:581-8). In some examples, the fibrotic condition of the lung can be chosen from one or more of: pulmonary fibrosis, idiopathic pulmonary fibrosis (IPF), usual interstitial pneumonitis (UIP), interstitial lung disease, cryptogenic fibrosing alveolitis (CFA), or bronchiectasis. In other examples, the pulmonary fibrosis can include, but is not limited to, pulmonary fibrosis associated with chronic obstructive pulmonary disease (COPD), scleroderma, pleural fibrosis, chronic asthma, acute lung syndrome, amyloidosis, bronchopulmonary dysplasia, Caplan's disease, Dressler's syndrome, histiocytosis X, idiopathic pulmonary haemosiderosis, lymphangiomyomatosis, mitral valve stenosis, polymyositis, pulmonary edema, pulmonary hypertension (e.g., idiopathic pulmonary hypertension (IPH)), pneumoconiosis, radiotherapy (e.g., radiation induced fibrosis), rheumatoid disease, Shaver's disease, systemic lupus erythematosus, systemic sclerosis, tropical pulmonary eosinophilia, tuberous sclerosis, Weber-Christian disease, Wegener's granulomatosis, Whipple's disease, or exposure to toxins or irritants (e.g., pharmaceutical drugs such as amiodarone, bleomycin, busulphan, carmustine, chloramphenicol, hexamethonium, methotrexate, methysergide, mitomycin C, nitrofurantoin, penicillamine, peplomycin, and practolol; inhalation of talc or dust, e.g., coal dust, silica). In certain embodiments, the pulmonary fibrosis is associated with an inflammatory disorder of the lung, e.g., asthma, COPD. In some embodiments, the fibrotic condition can be a fibrotic condition of the liver (also referred to herein as “hepatic fibrosis”), such as fatty liver disease e.g., steatosis such as nonalcoholic steatohepatitis (NASH), biliary fibrosis, cholestatic liver disease (e.g., primary biliary cirrhosis (PBC), and cholangiopathies (e.g., chronic cholangiopathies)). In certain embodiments, the fibrotic of the liver or hepatic fibrosis can be chosen from one or more of: fatty liver disease, steatosis (e.g., nonalcoholic steatohepatitis (NASH), cholestatic liver disease, primary biliary cirrhosis (PBC), biliary fibrosis, cirrhosis, alcohol induced liver fibrosis, biliary duct injury, infection or viral induced liver fibrosis, congenital hepatic fibrosis, autoimmune hepatitis, or cholangiopathies (e.g., chronic cholangiopathies). In certain embodiments, hepatic or liver fibrosis includes, but is not limited to, hepatic fibrosis associated with alcoholism, viral infection, e.g., hepatitis (e.g., hepatitis C, B or D), autoimmune hepatitis, non-alcoholic fatty liver disease (NAFLD), progressive massive fibrosis, exposure to toxins or irritants (e.g., alcohol, pharmaceutical drugs and environmental toxins such as arsenic), alpha-1 antitrypsin deficiency, hemochromatosis, Wilson's disease, galactosemia, or glycogen storage disease. In certain embodiments, the hepatic fibrosis is associated with an inflammatory disorder of the liver. In some embodiments, the fibrotic condition can be a fibrotic condition of the heart or vasculature, such as myocardial fibrosis. Fibrotic conditions of the heart or vasculature can include, but are not limited to, myocardial fibrosis (e.g., myocardial fibrosis associated with radiation myocarditis, a surgical procedure complication (e.g., myocardial post-operative fibrosis), vascular restenosis, atherosclerosis, cerebral disease, peripheral vascular disease, infectious diseases (e.g., Chagas disease, bacterial, trichinosis or fungal myocarditis)); granulomatous, metabolic storage disorders (e.g., cardiomyopathy, hemochromatosis); developmental disorders (e.g., endocardial fibroelastosis); arteriosclerotic, or exposure to toxins or irritants (e.g., drug induced cardiomyopathy, drug induced cardiotoxicity, alcoholic cardiomyopathy, cobalt poisoning or exposure). In certain embodiments, the myocardial fibrosis is associated with an inflammatory disorder of cardiac tissue (e.g., myocardial sarcoidosis). In some embodiments, the fibrotic condition can be a fibrotic condition of the kidney, such as renal fibrosis (e.g., chronic kidney fibrosis). Renal fibrosis can include, but is not limited to, nephropathies associated with injury/fibrosis (e.g., chronic nephropathies associated with diabetes (e.g., diabetic nephropathy)), lupus, scleroderma of the kidney, glomerular nephritis, focal segmental glomerular sclerosis, IgA nephropathyrenal fibrosis associated with human chronic kidney disease (CKD), chronic kidney fibrosis, nephrogenic systemic fibrosis, chronic progressive nephropathy (CPN), tubulointerstitial fibrosis, ureteral obstruction (e.g., fetal partial urethral obstruction), chronic uremia, chronic interstitial nephritis, radiation nephropathy, glomerulosclerosis (e.g., focal segmental glomerulosclerosis (FSGS)), progressive glomerulonephrosis (PGN), endothelial/thrombotic microangiopathy injury, scleroderma of the kidney, HIV-associated nephropathy (HIVVAN), or exposure to toxins, irritants, chemotherapeutic agents. In one embodiment, the kidney fibrosis is mediated by a bone morphogeneic protein (BMP). In certain embodiments, the renal fibrosis is a result of an inflammatory disorder of the kidney. In some embodiments, the fibrotic condition can be a fibrotic condition of the bone marrow. In certain embodiments, the fibrotic condition of the bone marrow is myelofibrosis (e.g., primary myelofibrosis (PMF)), myeloid metaplasia, chronic idiopathic myelofibrosis, or primary myelofibrosis. In other embodiments, bone marrow fibrosis is associated with a hematologic disorder chosen from one or more of hairy cell leukemia, lymphoma, or multiple myeloma. In other embodiments, the bone marrow fibrosis can be associated with one or more myeloproliferative neoplasms (MPN) chosen from: essential thrombocythemia (ET), polycythemia vera (PV), mastocytosis, chronic eosinophilic leukemia, chronic neutrophilic leukemia, or other MPN. In some examples, the fibrotic condition can be primary myelofibrosis. Primary myelofibrosis (PMF) (also referred to in the literature as idiopathic myeloid metaplasia, and Agnogenic myeloid metaplasia) is a clonal disorder of multipotent hematopoietic progenitor cells (reviewed in Abdel-Wahab, O. et al. (2009)Annu. Rev. Med.60:233-45; Varicchio, L. et al. (2009)Expert Rev. Hematol.2(3):315-334; Agrawal, M. et al. (2010)Cancer1-15). The disease is characterized by anemia, splenomegaly and extramedullary hematopoiesis, and is marked by progressive marrow fibrosis and atypical megakaryocytic hyperplasia. CD34+ stem/progenitor cells abnormally traffic in the peripheral blood and multi organ extramedullary erythropoiesis is a hallmark of the disease, especially in the spleen and liver. The bone marrow structure is altered due to progressive fibrosis, neoangiogenesis, and increased bone deposits. A significant percentage of patients with PMF have gain-of-function mutations in genes that regulate hematopoiesis, including Janus kinase 2 (JAK2) (˜50%) (e.g., JAK2V617F) or the thrombopoietin receptor (MPL) (5-10%), resulting in abnormal megakaryocyte growth and differentiation. Studies have suggested that the clonal hematopoietic disorder leads to secondary proliferation of fibroblasts and excessive collagen deposition. Decreased bone marrow fibrosis can improve clinical signs and symptoms, including anemia, abnormal leukocyte counts, and splenomegaly. Bone marrow fibrosis can be observed in several other hematologic disorders including, but not limited to hairy cell leukemia, lymphoma, and multiple myeloma. However, each of these conditions is characterized by a constellation of clinical, pathologic, and molecular findings not characteristic of PMF (see Abdel-Wahab, O. et al. (2009) supra at page 235). In other embodiments, the bone marrow fibrosis can be secondary to non-hematologic disorders, including but not limited to, solid tumor metastases to bone marrow, autoimmune disorders (systemic lupus erythematosus, scleroderma, mixed connective tissue disorder, polymyositis), and secondary hyperparathyroidism associated with vitamin D deficiency (see Abdel-Wahab, O. et al. (2009) supra at page 235). In most cases, it is possible to distinguish between these disorders and PMF, although in rare cases the presence of the JAK2V617F or MPLW515L/K mutation can be used to demonstrate the presence of a clonal MPN and to exclude the possibility of reactive fibrosis. Optionally, monitoring a clinical improvement in a subject with bone marrow fibrosis can be evaluated by one or more of: monitoring peripheral blood counts (e.g., red blood cells, white blood cells, platelets), wherein an increase in peripheral blood counts is indicative of an improved outcome. In other embodiments, clinical improvement in a subject with bone marrow fibrosis can be evaluated by monitoring one or more of: spleen size, liver size, and size of extramedullary hematopoiesis, wherein a decrease in one or more of these parameters is indicative of an improved outcome. In other embodiments, the fibrotic condition can be a fibrotic condition of the skin. In certain embodiments, the fibrotic condition is chosen from one or more of: skin fibrosis and/or scarring, post-surgical adhesions, scleroderma (e.g., systemic scleroderma), or skin lesions such as keloids. In certain embodiments, the fibrotic condition can be a fibrotic condition of the gastrointestinal tract. Such fibrotic conditions can be associated with an inflammatory disorder of the gastrointestinal tract, e.g., fibrosis associated with scleroderma; radiation induced gut fibrosis; fibrosis associated with a foregut inflammatory disorder such as Barrett's esophagus and chronic gastritis, and/or fibrosis associated with a hindgut inflammatory disorder, such as inflammatory bowel disease (IBD), ulcerative colitis and Crohn's disease. In certain embodiments, the fibrotic condition can be diffuse scleroderma. Fibrotic conditions can further include diseases that have as a manifestation fibrotic disease of the penis, including Peyronie's disease (fibrosis of the cavernous sheaths leading to contracture of the investing fascia of the corpora, resulting in a deviated and painful erection). In certain embodiments, the fibrotic condition can be selected from pulmonary fibrosis, bronchiectasis, interstitial lung disease; fatty liver disease; cholestatic liver disease, biliary fibrosis, hepatic fibrosis; myocardial fibrosis; and renal fibrosis. In certain embodiments, the fibrotic condition can be selected from biliary fibrosis, hepatic fibrosis, pulmonary fibrosis, myocardial fibrosis and renal fibrosis In certain embodiments, the fibrotic condition can be selected from nonalcoholic fatty liver disease (NAFLD) and nonalcoholic steatohepatitis (NASH). Other fibrotic conditions that can be treated with the methods and compositions of the invention include cystic fibrosis, endomyocardial fibrosis, mediastinal fibrosis, sarcoidosis, scleroderma, spinal cord injury/fibrosis. A number of models in which fibrosis is induced are available in the art. Administration of ERβ agonists can be readily used to evaluate whether fibrosis is ameliorated in such models. Examples of such models, include but are not limited to, the unilateral ureteral obstruction model of renal fibrosis (see Chevalier et al., “Ureteral Obstruction as a Model of Renal Interstitial Fibrosis and Obstructive Nephropathy”Kidney International(2009) 75:1145-1152), the bleomycin induced model of pulmonary fibrosis (see Moore and Hogaboam “Murine Models of Pulmonary Fibrosis”Am. J. Physiol. Lung. Cell. Mol. Physiol. (2008) 294:L152-L160), a variety of liver/biliary fibrosis models (see Chuang et al., “Animal Models of Primary Biliary Cirrhosis”Clin Liver Dis(2008) 12:333-347; Omenetti, A. et al. (2007)Laboratory Investigation87:499-514 (biliary duct-ligated model); or a number of myelofibrosis mouse models as described in Varicchio, L. (2009) supra. Regardless of the model, ERβ agonists can be evaluated in essentially three paradigms: 1) test whether ERβ agonists can inhibit the fibrotic state; 2) test whether ERβ agonists can stop fibrotic progression once initiated; and/or 3) test whether ERβ agonists can reverse the fibrotic state once initiated. In certain embodiments, the fibrotic condition is provided in a tissue (e.g., biliary tissue, liver tissue, lung tissue, heart tissue, kidney tissue, skin tissue, gut tissue, or neural tissue). In certain embodiments, the tissue is biliary tissue. In certain embodiments, the tissue is liver tissue. In certain embodiments the tissue is lung tissue. In certain embodiments, the tissue is heart tissue. In certain embodiments, the tissue is kidney tissue. In certain embodiments, the tissue is skin tissue. In certain embodiments, the tissue is gut tissue. In certain embodiments, the tissue is bone marrow tissue. In certain embodiments, the tissue is epithelial tissue. In certain embodiments, the tissue is neural tissue. Also provided are composition for use, and use of, an compound described herein, alone or in combination with another agent, for preparation of one or more medicaments for use in reducing fibrosis, or treatment of a fibrotic condition. By way of non-limiting illustration, examples of certain embodiments of the present disclosure are given below. EXAMPLES Materials and Methods DDAH Assay. DDAH activity is determined by modification of method published in the art (M. Knipp and M. Vasak Analytical Biochemistry 286, 257-264 (2000). The enzyme activity in cell or tissue extracts generated by homogenization in 0.1 M sodium phosphate buffer pH 6.2 will be determined by L-citrulline generation from ADMA. A 100 μl of sample will be transferred to a tube and 400 μl of 1 mM ADMA in sodium phosphate buffer will be added and incubated at 37° C. for 45 min. The reaction will be terminated by addition of 500 μl of 4% sulfosalicyclic acid. The mixture will be centrifuged at 3000 g for 10 minutes. A 60 μl of supernatant will be transferred to NUNC 96 well plate in triplicates. A 200 μl of COLDER (color development regent) will be added. COLDER is prepared by mixing 1 volume of solution A [80 mM DAMO (diacetyl monoxime) and 2.0 mM TSC (thiosemicarbazide)] and 3 volume of solution B [3 M H3PO4, 6 M H2SO4, and 2 mM NH4Fe(SO4)2]. The plates will be sealed and heated at 95° C. for 20 minutes. After cooling, they will be read at 530 nM. DDAH activity will be expressed as μM citrulline produced per gram protein per minute at 37° C. DDAH promoter activation assay. Activation of DDAH promoter was determined using a DDAH promoter-Luciferase reporter assay. DDAH promoter DNA sequence was cloned in pGL4.10 luciferase reporter plasmid. For transfection of HEK-293 cells, the cells were seeded in six well plates at a density of 2.0×105cells/well. After 24 hours, the cells were transfected with the DDAH promoter plasmid by adding 200 ng DNA/well and incubated for 24 hours. Transfected cells were then transferred to 96 well plates at 50,000 cells/well and incubated overnight with various concentrations of the test compounds. The medium was removed from the wells and 20 μL of lysis reagent was added. After 5 min, 100 μL Luciferase assay reagent was added, and luminescence was measured. DDAH and Collagen western blot analysis. Human umbilical vein endothelial cells (HUVEC), retinal endothelial cells and vascular smooth muscle cells from Lonza were transferred to 6 well plates at a density of 4.0×105/well and incubated overnight. Various concentrations of test compounds were then added. After 24 hours, medium was removed, the cells were scraped and collected in 50 μL of lysis buffer containing 50 mM Tris-HCl, 0.25% deoxycholic acid, 1% NP-40, 1 mM EDTA and protease inhibitor cocktails. Cell extract was subjected to SDS polyacrylamide gel electrophoresis. Proteins from the 12% polyacrylamide gels were transferred to PVDF membranes for westerns and blotted with DDAH or collagen 1 antibodies from Abcam. Determination of Pharmacokinetic Properties. PK of compounds will be determined following both i.v. (1 mg/kg) and s.c. (1 mg/kg) administration. Three rats are bled at each time point and serum samples are analyzed by compound level using LC or LC-MS. Two monkeys will be bled at each time point and serum samples will be analyzed compound level using LC or LC-MS. In beagle dogs, the PK of the compound will be determined following both i.v. (1 mg/kg) and s.c. (1 mg/kg) administration. Two dogs will be bled at each time point after i.v. dosing and one dog per dose group will be bled after s.c. dosing. Serum samples will be analyzed compound level using LC or LC-MS. Following collection, blood samples will be centrifuged at 10,000 rpm for 10 min at 4° C. to obtain serum and serum samples are stored at −20° C. until analysis. Pharmacokinetic parameters will be estimated using non-compartmental analysis by Kinetica software (Thermo Fisher Scientific Corporation, version 5.0). The peak concentration (Cmax) and time for Cmax(Tmax) are recorded directly from experimental observations. The area under the curve from time zero to the last sampling time [AUClast] and the area under the curve from time zero to infinity [AUCtotal] will be calculated using a combination of linear and log trapezoidal summations. The total plasma clearance, steady-state volume of distribution (Vss), apparent elimination half-life (thalf), and mean residence time (MRT) will be estimated after i.v. administration. Estimations of AUC and thalfwill be made using a minimum of 3 time points with quantifiable concentrations. The absolute s.c. bioavailability (F) will be estimated as the ratio of dose-normalized AUC values following s.c. and i.v. doses. The PK parameters will be calculated when applicable. Synthesis of DDAH-ADMA-Modulating Compounds Preparation of VN-317. The synthetic strategy for preparing VN-317 is detailed in the scheme below. Step-1: Synthesis of (4-methoxy-2-methylphenyl)methanol (2). To a stirred solution of 4-methoxy-2-methylbenzaldehyde 1 (10 g, 66.67 mmol) in isopropanol (100 mL) was added sodium borohydride (1.52 g, 40.0 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 3 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (100 mL) and extracted with EtOAc (2×100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 2 (10 g, 65.71 mmol) as colorless syrup. The crude material was taken to next step without further purification.1H NMR (500 MHz, CDCl3): δ 7.23 (d, J=8.1 Hz, 1H), 6.76-6.70 (m, 2H), 4.64 (s, 2H), 3.80 (s, 3H), 2.37 (s, 3H), 1.40 (br s, 1H). Step-2: Synthesis of 1-(bromomethyl)-4-methoxy-2-methylbenzene (3). To a stirred solution of compound 2 (10 g, crude) in CH2Cl2(100 mL) was added phosphorous tribromide (18.7 mL, 197.37 mmol) at 0-5° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was diluted with CH2Cl2(100 mL), washed with water (100 mL) and saturated NaHCO3solution (100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 3 (14.2 g, 66.02 mmol) as colorless syrup. The crude material was taken to next step without further purification. Step-3: Synthesis of (4-methoxy-2-methylbenzyl)triphenylphosphonium bromide (4). To a stirred solution of compound 3 (5 g, crude) in toluene (50 mL) was added triphenylphosphine (6.12 g, 23.36 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 16 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 4 (4.2 g, 8.8 mmol, 38%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.96-7.89 (m, 3H), 7.77-7.71 (m, 6H), 7.67-7.59 (m, 6H), 6.85 (dd, J=8.5, 2.6 Hz, 1H), 6.70-6.61 (m, 2H), 4.99-4.93 (m, 2H), 3.69 (s, 3H), 1.58 (s, 3H). Step-4: Synthesis of Methyl (E)-3-(4-methoxy-2-methylstyryl)benzoate (6). To a stirred solution of compound 4 (4.6 g, 9.64 mmol) in THF (46 mL) was added n-BuLi (2.5 M in hexanes, 4.63 mL, 11.57 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of methyl 3-formylbenzoate 5 (1.9 g, 11.57 mmol) in THF (13.8 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 2 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with saturated NH4Cl solution (50 mL) and extracted with EtOAc (2×70 mL). The combined organic extracts were washed with brine (30 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 10% EtOAc/n-hexanes) to afford compound 6 (1.8 g, 6.37 mmol, 66%) as a mixture of cis and trans-isomers as colorless syrup.1H NMR (500 MHz, CDCl3): δ 8.18 (s, 1H), 7.92 (d, J=7.8 Hz, 1H), 7.87 (s, 1H), 7.82 (d, J=7.7 Hz, 1H), 7.69 (d, J=7.8 Hz, 1H), 7.56 (d, J=8.5 Hz, 1H), 7.44 (t, J=7.7 Hz, 1H), 7.36 (d, J=16.1 Hz, 1H), 7.30 (s, 1H), 7.23-7.17 (m, 1H), 7.02 (d, J=8.4 Hz, 1H), 6.94 (d, J=16.1 Hz, 1H), 6.82-6.75 (m, 3H), 6.71-6.66 (m, 1H), 6.63-6.57 (m, 2H), 3.96 (s, 3H), 3.89 (s, 3H), 3.84 (s, 3H), 3.80 (s, 3H), 2.45 (s, 3H), 2.27 (s, 3H). Step-5: Synthesis of (E)-3-(4-hydroxy-2-methylstyryl)benzoic acid (VN-317). To a stirred solution of compound 6 (1 g, 3.55 mmol) in CH2Cl2(20 mL) was added boron tribromide (1M in CH2Cl2, 10.64 mL, 10.64 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (30 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by reverse phase preparative HPLC followed by normal phase prep-HPLC (Methods N & J) to afford VN-317 (25 mg, 0.1 mmol, 3%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 12.99 (br s, 1H), 9.45 (br s, 1H), 8.07 (s, 1H), 7.88-7.76 (m, 2H), 7.55-7.45 (m, 2H), 7.36 (d, J=16.3 Hz, 1H), 7.01 (d, J=16.2 Hz, 1H), 6.66-6.60 (m, 2H), 2.34 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.04 (s, 1H), 7.83-7.76 (m, 2H), 7.54-7.45 (m, 2H), 7.33 (d, J=16.3 Hz, 1H), 6.98 (d, J=16.2 Hz, 1H), 6.65-6.60 (m, 2H), 2.31 (s, 3H). LC-MS: m/z 252.8 [M−H]−at 2.57 RT (98.77% purity). HPLC: 97.35%. Preparation of VN-318. The synthetic strategy for preparing VN-318 is detailed in the scheme below. Step-1: Synthesis of (4-methoxy-2-methylphenyl)methanol (2). To a stirred solution of 4-methoxy-2-methylbenzaldehyde 1 (10 g, 66.67 mmol) in isopropanol (100 mL) was added sodium borohydride (1.52 g, 40.0 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 3 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (100 mL) and extracted with EtOAc (2×100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 2 (10 g, 65.71 mmol) as colorless syrup. The crude material was taken to next step without further purification.1H NMR (500 MHz, CDCl3): δ 7.23 (d, J=8.1 Hz, 1H), 6.76-6.70 (m, 2H), 4.64 (s, 2H), 3.80 (s, 3H), 2.37 (s, 3H), 1.40 (br s, 1H). Step-2: Synthesis of 1-(bromomethyl)-4-methoxy-2-methylbenzene (3). To a stirred solution of compound 2 (10 g, crude) in CH2Cl2(100 mL) was added phosphorous tribromide (18.7 mL, 197.37 mmol) at 0-5° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was diluted with CH2Cl2(100 mL), washed with water (100 mL) and saturated NaHCO3solution (100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 3 (14.2 g, 66.02 mmol) as colorless syrup. The crude material was taken to next step without further purification. Step-3: Synthesis of (4-methoxy-2-methylbenzyl)triphenylphosphonium bromide (4). To a stirred solution of compound 3 (5 g, crude) in toluene (50 mL) was added triphenylphosphine (6.12 g, 23.36 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 16 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 4 (4.2 g, 8.8 mmol, 38%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.96-7.89 (m, 3H), 7.77-7.71 (m, 6H), 7.67-7.59 (m, 6H), 6.85 (dd, J=8.5, 2.6 Hz, 1H), 6.70-6.61 (m, 2H), 4.99-4.93 (m, 2H), 3.69 (s, 3H), 1.58 (s, 3H). Step-4: Synthesis of Methyl (E)-3-(4-methoxy-2-methylstyryl)benzoate (6). To a stirred solution of compound 4 (4.6 g, 9.64 mmol) in THE (46 mL) was added n-BuLi (2.5 M in hexanes, 4.63 mL, 11.57 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of methyl 3-formylbenzoate 5 (1.9 g, 11.57 mmol) in THF (13.8 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 2 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with saturated NH4Cl solution (50 mL) and extracted with EtOAc (2×70 mL). The combined organic extracts were washed with brine (30 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 10% EtOAc/n-hexanes) to afford compound 6 (1.8 g, 6.37 mmol, 66%) as a mixture of cis and trans-isomers as colorless syrup.1H NMR (500 MHz, CDCl3): δ 8.18 (s, 1H), 7.92 (d, J=7.8 Hz, 1H), 7.87 (s, 1H), 7.82 (d, J=7.7 Hz, 1H), 7.69 (d, J=7.8 Hz, 1H), 7.56 (d, J=8.5 Hz, 1H), 7.44 (t, J=7.7 Hz, 1H), 7.36 (d, J=16.1 Hz, 1H), 7.30 (s, 1H), 7.23-7.17 (m, 1H), 7.02 (d, J=8.4 Hz, 1H), 6.94 (d, J=16.1 Hz, 1H), 6.82-6.75 (m, 3H), 6.71-6.66 (m, 1H), 6.63-6.57 (m, 2H), 3.96 (s, 3H), 3.89 (s, 3H), 3.84 (s, 3H), 3.80 (s, 3H), 2.45 (s, 3H), 2.27 (s, 3H). Step-5: Synthesis of Methyl 3-(4-methoxy-2-methylphenethyl)benzoate (7). To a stirred solution of compound 6 (400 mg, mixture) in ethylacetate (10 mL) was added 10% Pd/C (160 mg) at RT under inert atmosphere. The reaction mixture was evacuated and stirred at RT under hydrogen atmosphere (balloon pressure) for 6 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was filtered through a pad of celite and the celite bed was washed with EtOAc (15 mL). The filtrate was concentrated under reduced pressure. The combined organic extracts were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 15% EtOAc/n-hexanes) to afford compound 7 (230 mg, 0.81 mmol, 57%) as colorless syrup.1H NMR (400 MHz, CDCl3): δ 7.91-7.86 (m, 2H), 7.36-7.32 (m, 2H), 7.02 (d, J=8.3 Hz, 1H), 6.74-6.65 (m, 2H), 3.92 (s, 3H), 3.78 (s, 3H), 2.92-2.81 (m, 4H), 2.28 (s, 3H). LC-MS: m/z 285.2 [M+H]+at 3.02 RT (91.48% purity). Step-6: Synthesis of 3-(4-hydroxy-2-methylphenethyl)benzoic acid (VN-318). To a stirred solution of compound 7 (230 mg, 0.81 mmol) in CH2Cl2(6 mL) was added boron tribromide (1 M in CH2Cl2, 2.83 mL, 2.83 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (15 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by preparative HPLC (Method J) to afford VN-319 (40 mg, 0.16 mmol, 20%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 12.86 (br s, 1H), 9.00 (s, 1H), 7.83-7.73 (m, 2H), 7.49-7.35 (m, 2H), 6.92 (d, J=8.2 Hz, 1H), 6.57-6.46 (m, 2H), 2.86-2.69 (m, 4H), 2.17 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.77-7.71 (m, 2H), 7.45-7.35 (m, 2H), 6.88 (d, J=8.2 Hz, 1H), 6.55-6.43 (m, 2H), 2.83-2.67 (m, 4H), 2.12 (s, 3H). LC-MS: m/z 254.9 [M−H]−at 2.31 RT (98.01% purity). HPLC: 99.50%. Preparation of VN-319. The synthetic strategy for preparing VN-319 is detailed in the scheme below. Step-1: Synthesis of 4-ethynyl-3-methylphenol (2). To a stirred solution of 1-ethynyl-4-methoxy-2-methylbenzene 1 (1 g, 6.85 mmol) in CH2Cl2(40 mL) was added boron tribromide (1 M in CH2Cl2, 20.55 mL, 20.55 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 2 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (50 mL) and extracted with EtOAc (2×50 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 2 (1 g) as brown syrup. The crude material was taken to next step without further purification. LC-MS: m/z 130.9 [M−H]−at 2.96 RT (10.01% purity). Step-2: Synthesis of Methyl 3-((4-hydroxy-2-methylphenyl)ethynyl)benzoate (4). To a stirred solution of compound 2 (500 mg, crude) in DMF (10 mL) were added methyl 3-iodobenzoate 3 (1.09 g, 4.17 mmol), copper(l) iodide (72 mg, 0.38 mmol) followed by triethylamine (2.64 mL, 18.94 mmol) in a sealed tube at RT under inert atmosphere and purged under argon for 15 min. To this reaction mixture was added Pd(PPh3)2Cl2(266 mg, 0.38 mmol) at RT. The vessel was sealed and heated to 80° C. and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was diluted with water (20 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 15% EtOAc/n-hexanes) to afford compound 4 (300 mg, 1.13 mmol, 30%) as an off white solid.1H NMR (500 MHz, CDCl3): δ 8.17 (s, 1H), 7.97 (d, J=7.8 Hz, 1H), 7.68 (br d, J=7.5 Hz, 1H), 7.45-7.37 (m, 2H), 6.73 (d, J=2.0 Hz, 1H), 6.66 (dd, J=8.3, 2.5 Hz, 1H), 5.10 (br s, 1H), 3.94 (s, 3H), 2.48 (s, 3H). LC-MS: m/z 265.1 [M−H]−at 3.26 RT (93.70% purity). Step-3: Synthesis of Methyl 3-((4-hydroxy-2-methylphenyl)ethynyl)benzoate VN-319. To a stirred solution of compound 4 (150 mg, 0.56 mmol) in a mixture of THF/water (3:1, 4 mL) was added lithium hydroxide monohydride (71 mg, 1.69 mmol) at RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was acidified with 1N HCl solution to pH ˜2-3. The precipitated solid was filtered, washed with 30% Et2O/n-pentane (10 mL) and dried under vacuum to afford VN-320 (70 mg, 0.28 mmol, 49%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 9.84 (br s, 1H), 7.99 (br s, 1H), 7.92 (br d, J=7.5 Hz, 1H), 7.74 (d, J=7.7 Hz, 1H), 7.60-7.50 (m, 1H), 7.35 (d, J=8.4 Hz, 1H), 6.72 (d, J=2.1 Hz, 1H), 6.64 (dd, J=8.3, 2.4 Hz, 1H), 2.40 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.97 (br s, 1H), 7.90 (br d, J=7.4 Hz, 1H), 7.72 (d, J=7.7 Hz, 1H), 7.58-7.51 (m, 1H), 7.34 (d, J=8.4 Hz, 1H), 6.71 (d, J=2.1 Hz, 1H), 6.63 (dd, J=8.3, 2.4 Hz, 1H), 2.37 (s, 3H). LC-MS: m/z 250.8 [M−H]−at 2.34 RT (96.53% purity). HPLC: 99.66%. Preparation of VN-321. The synthetic strategy for preparing VN-321 is detailed in the scheme below. Step-1: Synthesis of 4-((tert-butyldimethylsilyl)oxy)-2-methylphenol (2). To a stirred solution of 2-methylbenzene-1,4-diol 1 (1 g, 8.06 mmol) in CH2Cl2(20 mL) were added imidazole (822 mg, 12.1 mmol) and tert-butyldimethylchlorosilane (1.21 g, 8.06 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was diluted with water (30 mL) and extracted with CH2Cl2(2×50 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 5% EtOAc/n-hexanes) to afford compound 2 (500 mg, 2.1 mmol, 26%) as pale yellow liquid.1H NMR (400 MHz, CDCl3): δ 6.65-6.60 (m, 2H), 6.56-6.50 (m, 1H), 4.43-4.38 (m, 1H), 2.20-2.15 (m, 3H), 1.02-0.95 (m, 9H), 0.19-0.15 (m, 6H) (NMR not clean because of close running impurity like positional isomers). Step-2: Synthesis of Methyl 3-((4-((tert-butyldimethylsilyl)oxy)-2-methylphenoxy)methyl)benzoate (4). To a stirred solution of compound 2 (400 mg, 1.68 mmol) in acetonitrile (10 mL) were added methyl 3-(bromomethyl)benzoate 3 (381 mg, 1.68 mmol) and potassium carbonate (464 mg, 3.36 mmol) at RT under inert atmosphere. The reaction mixture was heated to 60° C. and stirred for 6 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with water (20 mL) and extracted with EtOAc (2×25 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 5-10% EtOAc/n-hexanes) to afford compound 4 (450 mg, 1.16 mmol, 69%) as colorless liquid.1H NMR (400 MHz, CDCl3): δ 8.11-8.10 (m, 1H), 7.99 (dt, J=7.8, 1.4 Hz, 1H), 7.69-7.62 (m, 1H), 7.49-7.41 (m, 1H), 6.72 (d, J=8.7 Hz, 1H), 6.68-6.66 (m, 1H), 6.62-6.56 (m, 1H), 5.06-5.00 (m, 2H), 3.93-3.92 (m, 3H), 2.25-2.13 (m, 3H), 1.02-0.96 (m, 9H), 0.20-0.15 (m, 6H). NMR not clean Step-3: Synthesis of Methyl 3-((4-hydroxy-2-methylphenoxy)methyl)benzoate (5). To a stirred solution of compound 4 (400 mg, 1.04 mmol) in THF (8 mL) was added tetra-n-butylammonium fluoride (1M in THF, 1.24 mL, 1.24 mmol) at RT under inert atmosphere and stirred for 1 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with water (20 mL) and extracted with EtOAc (2×25 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 30% EtOAc/n-hexanes) to afford compound 5 (210 mg, 0.77 mmol, 75%) as pale yellow liquid.1H NMR (400 MHz, CDCl3): δ 8.10 (s, 1H), 7.99 (d, J=7.8 Hz, 1H), 7.66-7.61 (m, 1H), 7.49-7.41 (m, 1H), 6.74 (d, J=8.7 Hz, 1H), 6.70-6.66 (m, 1H), 6.59 (dd, J=8.7, 3.1 Hz, 1H), 5.04 (s, 2H), 4.52 (br s, 1H), 3.93 (s, 3H), 2.25 (s, 3H). LC-MS: m/z 273.4 [M+H]+at 3.64 RT (85.23% purity). Step-4: Synthesis of 3-((4-hydroxy-2-methylphenoxy)methyl)benzoic acid (VN-321). To a stirred solution of compound 5 (200 mg, 0.73 mmol) in a mixture of THF/water (4:1, 5 mL) was added lithium hydroxide monohydride (93 mg, 2.2 mmol) at RT under inert atmosphere and stirred for 2 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was acidified with 6N HCl to pH ˜2-3 and extracted with EtOAc (2×25 mL). The combined organic extracts were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by normal phase preparative HPLC (Method G) to afford VN-322 (50 mg, 0.19 mmol, 26%) as brown solid. The structure was confirmed by 2 D NMR (NOESY, gDQFCOSY) studies.1H NMR (500 MHz, DMSO-d6): δ 12.96 (br s, 1H), 8.80 (s, 1H), 8.00 (s, 1H), 7.87 (d, J=7.5 Hz, 1H), 7.66 (d, J=8.1 Hz, 1H), 7.50 (t, J=7.8 Hz, 1H), 6.79 (d, J=8.7 Hz, 1H), 6.56 (d, J=2.9 Hz, 1H), 6.49 (dd, J=8.7, 2.9 Hz, 1H), 5.05 (s, 2H), 2.12 (s, 3H);1H NMR (500 MHz, DMSO-d6, D2O Exc.): δ 7.98 (s, 1H), 7.86 (d, J=7.5 Hz, 1H), 7.65 (d, J=8.1 Hz, 1H), 7.50 (t, J=7.5 Hz, 1H), 6.79 (d, J=8.7 Hz, 1H), 6.57 (d, J=2.3 Hz, 1H), 6.49 (dd, J=8.7, 2.9 Hz, 1H), 5.04 (s, 2H), 2.10 (s, 3H). LC-MS: m/z 256.8 [M−H]−at 1.83 RT (92.45% purity). HPLC: 96.21%. Preparation of VN-378. The synthetic strategy for preparing VN-378 is detailed in the scheme below. Step-1: Synthesis of (4-methoxy-2-methylphenyl)methanol (2). To a stirred solution of 4-methoxy-2-methylbenzaldehyde 1 (10 g, 66.67 mmol) in isopropanol (100 mL) was added sodium borohydride (1.52 g, 40.0 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 3 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (100 mL) and extracted with EtOAc (2×100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 2 (10 g, 65.71 mmol) as colorless syrup. The crude material was taken to next step without further purification.1H NMR (500 MHz, CDCl3): δ 7.23 (d, J=8.1 Hz, 1H), 6.76-6.70 (m, 2H), 4.64 (s, 2H), 3.80 (s, 3H), 2.37 (s, 3H), 1.40 (br s, 1H). Step-2: Synthesis of 1-(bromomethyl)-4-methoxy-2-methylbenzene (3). To a stirred solution of compound 2 (10 g, crude) in CH2Cl2(100 mL) was added phosphorous tribromide (18.7 mL, 197.37 mmol) at 0-5° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was diluted with CH2Cl2(100 mL), washed with water (100 mL) and saturated NaHCO3solution (100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 3 (14.2 g, 66.02 mmol) as colorless syrup. The crude material was taken to next step without further purification. Step-3: Synthesis of (4-methoxy-2-methylbenzyl)triphenylphosphonium bromide (4). To a stirred solution of compound 3 (5 g, crude) in toluene (50 mL) was added triphenylphosphine (6.12 g, 23.36 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 16 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 4 (4.2 g, 8.8 mmol, 38%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.96-7.89 (m, 3H), 7.77-7.71 (m, 6H), 7.67-7.59 (m, 6H), 6.85 (dd, J=8.5, 2.6 Hz, 1H), 6.70-6.61 (m, 2H), 4.99-4.93 (m, 2H), 3.69 (s, 3H), 1.58 (s, 3H). Step-4: Synthesis of Methyl (E)-3-(4-methoxy-2-methylstyryl)benzoate (6) & Methyl (Z)-3-(4-methoxy-2-methylstyryl)benzoate (7). To a stirred solution of compound 4 (4 g, 8.38 mmol) in THF (30 mL) was added n-BuLi (2.5 M in hexanes, 4.02 mL, 10.06 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 1 h. Then a solution of methyl 3-formylbenzoate 5 (2.06 g, 12.58 mmol) in THF (10 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with saturated NH4Cl solution (50 mL) and extracted with EtOAc (2×70 mL). The combined organic extracts were washed with brine (30 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 10% EtOAc/n-hexanes) followed by normal phase preparative HPLC (Method H) to afford trans compound 6 (300 mg, 1.06 mmol, 13%) & cis compound 7 (500 mg, 1.77 mmol, 21%) as colorless liquids respectively. Analytical data of compound 6 (trans):1H NMR (500 MHz, CDCl3): δ 8.17 (s, 1H), 7.90 (d, J=7.5 Hz, 1H), 7.67 (d, J=7.5 Hz, 1H), 7.54 (d, J=8.7 Hz, 1H), 7.42 (t, J=7.5 Hz, 1H), 7.34 (d, J=16.2 Hz, 1H), 6.92 (d, J=16.2 Hz, 1H), 6.78 (dd, J=8.4, 2.6 Hz, 1H), 6.74 (d, J=2.3 Hz, 1H), 3.95 (s, 3H), 3.82 (s, 3H), 2.44 (s, 3H). LC-MS: m/z 283.2 [M+H]+at 4.58 RT (98.78% purity). Analytical data of compound 7 (cis):1H NMR (500 MHz, CDCl3): δ 7.85 (s, 1H), 7.80 (br d, J=7.5 Hz, 1H), 7.29-7.25 (m, 2H), 7.21-7.16 (m, 1H), 7.01 (d, J=8.7 Hz, 1H), 6.75 (d, J=1.7 Hz, 1H), 6.69-6.65 (m, 1H), 6.61-6.56 (m, 2H), 3.87 (s, 3H), 3.79 (s, 3H), 2.25 (s, 3H). LC-MS: m/z 283.2 [M+H]+at 4.67 RT (98.13% purity). Step-5: Synthesis of Methyl 3-((1R,2S)-2-(4-methoxy-2-methylphenyl)cyclopropyl)benzoate (8). To a stirred solution of compound 7 (cis) (400 mg, 1.42 mmol) in diethylether (20 mL) was added palladium(II) acetate (127 mg, 0.57 mmol) at RT under inert atmosphere. Then a solution of freshly prepared diazomethane (15 mL) was added at −50° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with water (20 mL) and extracted with EtOAc (2×25 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 8 (400 mg, 1.35 mmol) as brown syrup. The crude material was taken to next step without further purification. LC-MS: m/z 297.3 [M+H]+at 4.37 RT (75.19% purity). Step-6: Synthesis of 3-((1R,2S)-2-(4-hydroxy-2-methylphenyl)cyclopropyl)benzoic acid (VN-378). To a stirred solution of compound 8 (300 mg, 1.01 mmol) in CH2Cl2(15 mL) was added boron tribromide (1 M in CH2Cl2, 4.05 mL, 4.05 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 3 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (20 mL) and extracted with CH2Cl2(2×20 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by preparative HPLC (Method I) to afford VN-378 (30 mg, 0.11 mmol) as an off white solid. The compound was highly hygroscopic.1H NMR (400 MHz, DMSO-d6): δ 7.57-7.48 (m, 2H), 7.04-6.94 (m, 2H), 6.80 (br d, J=7.8 Hz, 1H), 6.42 (dd, J=8.2, 2.4 Hz, 1H), 6.33 (d, J=2.3 Hz, 1H), 2.48-2.43 (m, 1H), 2.35-2.27 (m, 1H), 1.98 (s, 3H), 1.49-1.34 (m, 2H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.54-7.45 (m, 2H), 7.03-6.92 (m, 2H), 6.79 (br d, J=7.7 Hz, 1H), 6.41 (dd, J=8.2, 2.5 Hz, 1H), 6.33 (d, J=2.4 Hz, 1H), 2.48-2.40 (m, 1H), 2.36-2.24 (m, 1H), 1.97 (s, 3H), 1.46-1.32 (m, 2H). LC-MS: m/z 266.9 [M−H]−at 2.38 RT (96.39% purity). HPLC: 86.80%. HPLC: 87.75%. Preparation of VN-323. The synthetic strategy for preparing VN-323 is detailed in the scheme below. Step-1: Synthesis of Methyl 3-(4-methoxy-2-methylbenzamido)benzoate (3). To a stirred solution of 4-methoxy-2-methylbenzoic acid 1 (1 g, 6.02 mVN-324 mol) in CH2Cl2(15 mL) were added methyl 3-aminobenzoate 2 (909 mg, 6.01 mmol), HATU (2.74 g, 7.22 mmol) and ethyldiisopropylamine (2.62 mL, 15.04 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was diluted with water (30 mL) and extracted with CH2Cl2(2×40 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 40% EtOAc/n-hexanes) to afford compound 3 (500 mg, 1.67 mmol, 28%) as an off white solid.1H NMR (400 MHz, CDCl3): δ 8.09 (s, 1H), 8.01 (br d, J=7.7 Hz, 1H), 7.81 (d, J=7.8 Hz, 1H), 7.58 (br s, 1H), 7.47 (t, J=8.0 Hz, 2H), 6.82-6.74 (m, 2H), 3.91 (s, 3H), 3.84 (s, 3H), 2.53 (s, 3H). LC-MS: m/z 299.9 [M+H]+at 2.90 RT (88.64% purity); m/z 300.0 [M+H]+at 3.03 RT (11.35% purity). Step-2: Synthesis of 3-(4-hydroxy-2-methylbenzamido)benzoic acid (VN-323). To a stirred solution of compound 3 (300 mg, 1.0 mmol) in CH2Cl2(15 mL) was added boron tribromide (1 M in CH2Cl2, 6.02 mL, 6.02 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (20 mL) and extracted with CH2Cl2(2×20 mL). The combined organic extracts were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 100% EtOAc) followed by preparative HPLC (Method P) to afford VN-324 (40 mg, 0.15 mmol, 15%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 12.92 (br s, 1H), 10.23 (s, 1H), 9.77 (s, 1H), 8.40 (t, J=1.8 Hz, 1H), 7.94-7.89 (m, 1H), 7.64 (dt, J=7.8, 1.3 Hz, 1H), 7.47-7.36 (m, 2H), 6.70-6.65 (m, 2H), 2.35 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.37 (t, J=1.8 Hz, 1H), 7.89-7.85 (m, 1H), 7.64 (dt, J=7.8, 1.3 Hz, 1H), 7.44 (t, J=7.9 Hz, 1H), 7.35 (d, J=8.2 Hz, 1H), 6.69-6.63 (m, 2H), 2.32 (s, 3H). LC-MS: m/z 270.0 [M−H]+at 6.14 RT (99.89% purity). HPLC: 99.83%. Preparation of VN-324. The synthetic strategy for preparing VN-324 is detailed in the scheme below. Step-1: Synthesis of Methyl 3-((4-methoxy-2-methylphenyl)carbamoyl)benzoate (3). To a stirred solution of 3-(methoxycarbonyl)benzoic acid 2 (1 g, 5.55 mmol) in CH2Cl2(15 mL) were added 4-methoxy-2-methylaniline 1 (0.71 mL, 5.55 mmol), HATU (2.53 g, 6.66 mmol) and ethyldiisopropylamine (2.42 mL, 13.87 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was diluted with water (30 mL) and extracted with CH2Cl2(2×40 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 40% EtOAc/n-hexanes) to afford compound 3 (1.5 g, 5.01 mmol, 90%) as an off white solid.1H NMR (500 MHz, CDCl3): δ 8.50 (br s, 1H), 8.21 (br d, J=7.8 Hz, 1H), 8.13 (br d, J=7.3 Hz, 1H), 7.66 (br s, 1H), 7.61-7.55 (m, 2H), 6.82-6.76 (m, 2H), 3.96 (s, 3H), 3.81 (s, 3H), 2.31 (s, 3H). Step-2: Synthesis of 3-((4-hydroxy-2-methylphenyl)carbamoyl)benzoic acid (VN-325). To a stirred solution of compound 3 (200 mg, 0.67 mmol) in CH2Cl2(15 mL) was added boron tribromide (1 M in CH2Cl2, 4.01 mL, 4.01 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (20 mL) and extracted with CH2Cl2(2×20 mL). The combined organic extracts were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 100% EtOAc) to afford VN-324 (40 mg, 0.15 mmol, 22%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 13.25 (br s, 1H), 9.88 (s, 1H), 9.31 (br s, 1H), 8.52 (s, 1H), 8.22-8.07 (m, 2H), 7.64 (t, J=7.7 Hz, 1H), 7.05 (d, J=8.4 Hz, 1H), 6.66 (d, J=2.5 Hz, 1H), 6.60 (dd, J=8.4, 2.5 Hz, 1H), 2.13 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.47 (s, 1H), 8.13 (br t, J=9.2 Hz, 2H), 7.64 (t, J=7.7 Hz, 1H), 7.04 (d, J=8.4 Hz, 1H), 6.67 (d, J=2.5 Hz, 1H), 6.61 (dd, J=8.4, 2.6 Hz, 1H), 2.11 (s, 3H). LC-MS: m/z 270.1 [M−H]+at 5.89 RT (97.19% purity). HPLC: 96.95%. Preparation of VN-325. The synthetic strategy for preparing VN-325 is detailed in the scheme below. Step-1: Synthesis of Methyl 3-(4-methoxy-2-methylbenzamido)benzoate (3). To a stirred solution of 4-methoxy-2-methylbenzoic acid 1 (1 g, 6.02 mmol) in CH2Cl2(15 mL) were added methyl 3-aminobenzoate 2 (909 mg, 6.02 mmol), HATU (2.74 g, 7.22 mmol) and ethyldiisopropylamine (2.62 mL, 15.04 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was diluted with water (30 mL) and extracted with CH2Cl2(2×40 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 40% EtOAc/n-hexanes) to afford compound 3 (500 mg, 1.67 mmol, 28%) as an off white solid.1H NMR (400 MHz, CDCl3): δ 8.09 (s, 1H), 8.01 (br d, J=7.7 Hz, 1H), 7.81 (d, J=7.8 Hz, 1H), 7.58 (br s, 1H), 7.47 (t, J=8.0 Hz, 2H), 6.82-6.74 (m, 2H), 3.91 (s, 3H), 3.84 (s, 3H), 2.53 (s, 3H). LC-MS: m/z 299.9 [M+H]+at 2.90 RT (88.64% purity); m/z 300.0 [M+H]+at 3.03 RT (11.35% purity). Step-2: Synthesis of Methyl 3-(4-methoxy-N,2-dimethylbenzamido)benzoate (4). To a stirred solution of compound 3 (300 mg, 1.0 mmol) in THF (6 mL) was added sodium hydride (60% in mineral oil, 52 mg, 1.3 mmol) at 0° C. under inert atmosphere and stirred for 10 min. Then iodomethane (0.09 mL, 1.5 mmol) was added at 0° C.; warmed to RT and stirred for 3 h. The progress of the reaction was monitored by TLC & LCMS; after the completion, the reaction mixture was quenched with ice cold water (20 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 20% EtOAc/n-hexanes) to afford compound 4 (200 mg, 0.64 mmol, 64%) as brown syrup.1H NMR (400 MHz, DMSO-d6): δ 7.78-7.69 (m, 2H), 7.44-7.36 (m, 2H), 7.02 (br d, J=8.3 Hz, 1H), 6.69 (d, J=1.9 Hz, 1H), 6.59 (br d, J=8.2 Hz, 1H), 3.83 (s, 3H), 3.67 (s, 3H), 3.34 (s, 3H), 2.24 (s, 3H). LC-MS: m/z 313.9 [M+H]+at 2.77 RT (92.87% purity). Step-3: Synthesis of 3-(4-hydroxy-N,2-dimethylbenzamido)benzoic acid (VN-325). To a stirred solution of compound 4 (200 mg, 0.64 mmol) in CH2Cl2(15 mL) was added boron tribromide (1 M in CH2Cl2, 3.83 mL, 3.83 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (15 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 2% MeOH/CH2Cl2) to afford VN-326 (40 mg, 0.14 mmol, 22%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 13.08 (br s, 1H), 9.47 (br s, 1H), 7.71-7.67 (m, 2H), 7.40-7.34 (m, 2H), 6.87 (d, J=8.3 Hz, 1H), 6.48 (d, J=1.9 Hz, 1H), 6.39 (dd, J=8.3, 1.8 Hz, 1H), 3.33 (s, 3H), 2.17 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.70-7.65 (m, 1H), 7.61 (s, 1H), 7.39-7.33 (m, 2H), 6.85 (br d, J=8.0 Hz, 1H), 6.46 (d, J=1.6 Hz, 1H), 6.37 (br d, J=8.2 Hz, 1H), 3.30 (s, 3H), 2.13 (s, 3H). LC-MS: m/z 286.1 [M+H]+at 2.72 RT (98.64% purity). HPLC: 98.76%. Preparation of VN-326. The synthetic strategy for preparing VN-326 is detailed in the scheme below. Step-1: Synthesis of Methyl 3-((4-methoxy-2-methylphenyl)carbamoyl)benzoate (3). To a stirred solution of 3-(methoxycarbonyl)benzoic acid 2 (1 g, 5.55 mmol) in CH2Cl2(15 mL) were added 4-methoxy-2-methylaniline 1 (0.71 mL, 5.55 mmol), HATU (2.53 g, 6.66 mmol) and ethyldiisopropylamine (2.42 mL, 13.87 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was diluted with water (30 mL) and extracted with CH2Cl2(2×40 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 40% EtOAc/n-hexanes) to afford compound 3 (1.5 g, 5.01 mmol, 90%) as an off white solid.1H NMR (500 MHz, CDCl3): δ 8.50 (br s, 1H), 8.21 (br d, J=7.8 Hz, 1H), 8.13 (br d, J=7.3 Hz, 1H), 7.66 (br s, 1H), 7.61-7.55 (m, 2H), 6.82-6.76 (m, 2H), 3.96 (s, 3H), 3.81 (s, 3H), 2.31 (s, 3H). Step-2: Synthesis of 3-((4-methoxy-2-methylphenyl)(methyl)carbamoyl)benzoic acid (4). To a stirred solution of compound 3 (300 mg, 1.0 mmol) in THF (12 mL) was added sodium hydride (60% in mineral oil, 52 mg, 1.3 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 20 min. Then iodomethane (0.09 mL, 1.5 mmol) was added at 0° C.; warmed to RT and stirred for 3 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was diluted with ice cold water (20 mL) and extracted with EtOAc (2×50 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 5% MeOH/CH2Cl2) to afford compound 4 (300 mg, impure) as pale yellow sticky liquid.1H NMR (400 MHz, DMSO-d6): δ 13.15 (br s, 1H), 7.86-7.76 (m, 2H), 7.39 (d, J=7.8 Hz, 1H), 7.32-7.25 (m, 1H), 7.13 (d, J=8.5 Hz, 1H), 6.73-6.64 (m, 2H), 3.66 (s, 3H), 3.17 (s, 3H), 2.12 (s, 3H). LC-MS: m/z 299.9 [M+H]+at 1.57 RT (80.28% purity). Step-3: Synthesis of 3-((4-hydroxy-2-methylphenyl)(methyl)carbamoyl)benzoic acid (VN-326). To a stirred solution of compound 4 (300 mg, 1.0 mmol) in CH2Cl2(6 mL) was added boron tribromide (1 M in CH2Cl2, 6.02 mL, 6.02 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (20 mL) and the organic layer was separated. The aqueous layer was extracted with EtOAc (2×50 mL). The combined organic extracts (DCM & EtOAc layers) were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was triturated with EtOAc/MeOH (20 mL/1 mL) followed by washings with Et2O (2×10 mL), n-pentane (2×10 mL) and dried under vacuum to afford VN-337 (80 mg, 0.28 mmol, 28%) as an off white solid.1H NMR (500 MHz, DMSO-d6): δ 12.99 (br s, 1H), 9.39 (s, 1H), 7.83-7.76 (m, 2H), 7.40 (d, J=7.5 Hz, 1H), 7.32-7.27 (m, 1H), 6.98 (d, J=8.4 Hz, 1H), 6.51-6.44 (m, 2H), 3.20 (s, 3H), 2.04 (s, 3H);1H NMR (500 MHz, DMSO-d6, D2O Exc.): δ 7.82-7.74 (m, 2H), 7.41 (d, J=7.8 Hz, 1H), 7.34-7.27 (m, 1H), 6.97 (d, J=8.4 Hz, 1H), 6.50-6.42 (m, 2H), 3.18 (s, 3H), 2.00 (s, 3H). LC-MS: m/z 286.2 [M+H]+at 1.80 RT (99.16% purity). HPLC: 98.82%. Preparation of VN-327. The synthetic strategy for preparing VN-327 is detailed in the scheme below. Step-1: Synthesis of (4-methoxy-2-methylphenyl)methanol (2). To a stirred solution of 4-methoxy-2-methylbenzaldehyde 1 (10 g, 66.67 mmol) in isopropanol (100 mL) was added sodium borohydride (1.52 g, 40.0 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 3 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (100 mL) and extracted with EtOAc (2×100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 2 (10 g, 65.71 mmol) as colorless syrup. The crude material was taken to next step without further purification.1H NMR (500 MHz, CDCl3): δ 7.23 (d, J=8.1 Hz, 1H), 6.76-6.70 (m, 2H), 4.64 (s, 2H), 3.80 (s, 3H), 2.37 (s, 3H), 1.40 (br s, 1H). Step-2: Synthesis of 1-(bromomethyl)-4-methoxy-2-methylbenzene (3). To a stirred solution of compound 2 (10 g, crude) in CH2Cl2(100 mL) was added phosphorous tribromide (18.7 mL, 197.37 mmol) at 0-5° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was diluted with CH2Cl2(100 mL), washed with water (100 mL) and saturated NaHCO3solution (100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 3 (14.2 g, 66.02 mmol) as colorless syrup. The crude material was taken to next step without further purification. Step-3: Synthesis of (4-methoxy-2-methylbenzyl)triphenylphosphonium bromide (4). To a stirred solution of compound 3 (5 g, crude) in toluene (50 mL) was added triphenylphosphine (6.12 g, 23.36 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 16 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 4 (4.2 g, 8.8 mmol, 38%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.96-7.89 (m, 3H), 7.77-7.71 (m, 6H), 7.67-7.59 (m, 6H), 6.85 (dd, J=8.5, 2.6 Hz, 1H), 6.70-6.61 (m, 2H), 4.99-4.93 (m, 2H), 3.69 (s, 3H), 1.58 (s, 3H). Step-4: Synthesis of Methyl (E)-3-(4-methoxy-2-methylstyryl)benzoate (6). To a stirred solution of compound 4 (4.6 g, 9.64 mmol) in THF (46 mL) was added n-BuLi (2.5 M in hexanes, 4.63 mL, 11.57 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of methyl 3-formylbenzoate 5 (1.9 g, 11.57 mmol) in THF (13.8 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 2 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was cooled to 0° C.; quenched with saturated NH4Cl solution (50 mL) and extracted with EtOAc (2×70 mL). The combined organic extracts were washed with brine (30 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 10% EtOAc/n-hexanes) to afford compound 6 (1.8 g, 6.37 mmol, 66%) as a mixture of cis and trans-isomers as colorless syrup.1H NMR (500 MHz, CDCl3): δ 8.18 (s, 1H), 7.92 (d, J=7.8 Hz, 1H), 7.87 (s, 1H), 7.82 (d, J=7.7 Hz, 1H), 7.69 (d, J=7.8 Hz, 1H), 7.56 (d, J=8.5 Hz, 1H), 7.44 (t, J=7.7 Hz, 1H), 7.36 (d, J=16.1 Hz, 1H), 7.30 (s, 1H), 7.23-7.17 (m, 1H), 7.02 (d, J=8.4 Hz, 1H), 6.94 (d, J=16.1 Hz, 1H), 6.82-6.75 (m, 3H), 6.71-6.66 (m, 1H), 6.63-6.57 (m, 2H), 3.96 (s, 3H), 3.89 (s, 3H), 3.84 (s, 3H), 3.80 (s, 3H), 2.45 (s, 3H), 2.27 (s, 3H). Step-5: Synthesis of (E)-3-(4-methoxy-2-methylstyryl)benzamide (7). To compound 6 (600 mg, 2.13 mmol) was added methanolic ammonia (10 mL) in a sealed tube at RT under inert atmosphere. The sealed tube was sealed and the reaction mixture was heated to 90° C. and stirred for 24 h. The progress of the reaction was monitored by TLC & LCMS, after the completion, the reaction mixture was concentrated under reduced pressure to obtain the crude. The crude material was purified by silica gel column chromatography (eluent: 30% EtOAc/n-hexanes) to afford compound 7 (200 mg, 0.75 mmol, 35%) as a mixture of cis and trans-isomers as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 8.11-8.02 (m, 2H), 7.88 (br s, 1H), 7.77-7.69 (m, 3H), 7.66-7.59 (m, 2H), 7.47-7.39 (m, 3H), 7.31 (br s, 1H), 7.26-7.18 (m, 1H), 7.17-7.13 (m, 1H), 7.04 (d, J=16.3 Hz, 1H), 6.93 (d, J=8.4 Hz, 1H), 6.84-6.78 (m, 3H), 6.70-6.58 (m, 3H), 3.76 (s, 3H), 3.72 (s, 3H), 2.41 (s, 3H), 2.21 (s, 3H). LC-MS: m/z 308.9 [M+ACN]+at 2.80 RT (93.84% purity). Step-6: Synthesis of (E)-3-(4-hydroxy-2-methylstyryl)benzamide (VN-327). To a stirred solution of compound 7 (200 mg, 0.75 mmol) in DMF (2 mL) was added sodium thioethoxide (503 mg, 6.0 mmol) in a microwave vessel at RT. The vessel was sealed and the reaction mixture was irradiated to 120° C. and stirred for 3 h. The progress of the reaction was monitored by TLC & LC-MS; after the completion, the reaction mixture was diluted with water (20 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 2% MeOH/CH2Cl2) to afford VN-327 (25 mg, 0.1 mmol, 13%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 9.45 (s, 1H), 8.08-8.00 (m, 2H), 7.74-7.66 (m, 2H), 7.51 (d, J=8.2 Hz, 1H), 7.45-7.35 (m, 3H), 6.97 (d, J=16.3 Hz, 1H), 6.66-6.61 (m, 2H), 2.35 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.02 (s, 1H), 7.73-7.66 (m, 2H), 7.51 (d, J=8.2 Hz, 1H), 7.45-7.33 (m, 2H), 6.96 (d, J=16.2 Hz, 1H), 6.66-6.60 (m, 2H), 2.33 (s, 3H). LC-MS: m/z 254.0 [M+H]+at 2.96 RT (94.04% purity). HPLC: 99.42%. Preparation of VN-328. The synthetic strategy for preparing VN-328 is detailed in the scheme below. Step-1: Synthesis of (4-methoxybenzyl)triphenylphosphonium bromide (2). To a stirred solution of 1-(bromomethyl)-4-methoxybenzene 1 (500 mg, 2.49 mmol) in toluene (5 mL) was added triphenylphosphine (652 mg, 2.49 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 12 h. Then the solid was filtered, washed with toluene (2×10 mL), n-hexanes (2×10 mL) and dried under vacuum to afford compound 2 (950 mg, 2.05 mmol, 83%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.87 (m, 3H), 7.78-7.71 (m, 6H), 7.69-7.61 (m, 6H), 6.91-6.85 (m, 2H), 6.83-6.77 (m, 2H), 5.07 (d, J=14.9 Hz, 2H), 3.69 (s, 3H). Step-2: Synthesis of Methyl (E)-3-(4-methoxystyryl)benzoate (4). To a stirred solution of compound 2 (1 g, 2.16 mmol) in THF (10 mL) was added n-BuLi (2.5 M in hexanes, 0.95 mL, 2.37 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of methyl 3-formylbenzoate 3 (354 mg, 2.16 mmol) in THF (2 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with saturated NH4Cl solution (30 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 10% EtOAc/n-hexanes) to afford compound 4 (400 mg, 1.49 mmol, 70%) as a mixture of cis and trans-isomers as an off white semi solid.1H NMR (500 MHz, DMSO-d6): δ 8.12 (s, 1H), 7.90-7.77 (m, 3H), 7.59 (d, J=8.5 Hz, 1H), 7.54-7.46 (m, 2H), 7.45-7.39 (m, 1H), 7.33-7.18 (m, 2H), 7.13 (d, J=8.7 Hz, 2H), 6.96 (d, J=8.7 Hz, 1H), 6.82 (d, J=8.7 Hz, 2H), 6.67-6.56 (m, 2H), 3.88 (s, 2H), 3.81 (s, 3H), 3.78 (s, 2H), 3.73 (s, 3H). LC-MS: m/z 269.1 [M+H]+at 4.51 RT (96.39% purity). Step-3: Synthesis of (E)-3-(4-hydroxystyryl)benzoic acid (VN-328). To a stirred solution of compound 4 (100 mg, 0.37 mmol) in DMF (2 mL) was added sodium thioethoxide (188 mg, 2.24 mmol) in a microwave vessel at RT. The vessel was sealed and the reaction mixture was irradiated to 120° C. and stirred for 2 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with 2N HCl (20 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to obtain the crude. The above lot was combined with two other lots (200 mg) and was purified by reverse phase preparative HPLC (Method K) to afford VN-329 (43 mg, 0.18 mmol, 16% for three batches) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 12.97 (br s, 1H), 9.60 (s, 1H), 8.08 (s, 1H), 7.83-7.75 (m, 2H), 7.51-7.43 (m, 3H), 7.23 (d, J=16.1 Hz, 1H), 7.10 (d, J=16.2 Hz, 1H), 6.78 (d, J=8.7 Hz, 2H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.04 (s, 1H), 7.80-7.74 (m, 2H), 7.50-7.42 (m, 3H), 7.18 (d, J=16.4 Hz, 1H), 7.06 (d, J=16.3 Hz, 1H), 6.77 (d, J=8.7 Hz, 2H). LC-MS: m/z 238.8 [M−H]−at 2.14 RT (98.79% purity). HPLC: 97.92%. Preparation of VN-329& VN-338. The synthetic strategy for preparing VN-329 and VN-338 is detailed in the scheme below. Step-1: Synthesis of (2-methylbenzyl)triphenylphosphonium bromide (2). To a stirred solution of 1-(bromomethyl)-2-methylbenzene 1 (2 g, 10.81 mmol) in toluene (20 mL) was added triphenylphosphine (2.83 g, 10.81 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 12 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×15 mL) and dried under vacuum to afford compound 2 (3.5 g, 7.82 mmol, 73%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.96-7.89 (m, 3H), 7.78-7.69 (m, 6H), 7.67-7.58 (m, 6H), 7.27-7.19 (m, 1H), 7.11 (d, J=7.4 Hz, 1H), 7.04 (t, J=7.5 Hz, 1H), 6.96-6.92 (m, 1H), 5.06-5.02 (m, 2H), 3.32 (s, 3H). Step-2: Synthesis of Methyl (E)-3-(2-methylstyryl)benzoate (4). To a stirred solution of compound 2 (1 g, 2.24 mmol) in THF (3.5 mL) was added n-BuLi (2.5M in hexanes, 0.98 mL, 2.46 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then methyl 3-formylbenzoate 3 (367 mg, 2.24 mmol) in THF (1 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 1 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with saturated NH4Cl solution (30 mL) at 0° C. and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 10% EtOAc/n-hexanes) to afford compound 4 (330 mg, 1.31 mmol, 57%) as a mixture of cis and trans-isomers as colorless liquid.1H NMR (400 MHz, DMSO-d6): δ 8.15 (s, 1H), 7.98-7.94 (m, 1H), 7.90-7.84 (m, 1H), 7.77-7.66 (m, 3H), 7.59-7.46 (m, 2H), 7.36-7.29 (m, 2H), 7.28-7.15 (m, 5H), 7.10-6.99 (m, 2H), 6.83-6.72 (m, 2H), 3.88 (s, 3H), 3.77 (s, 3H), 2.43 (s, 3H), 2.22 (s, 3H). LC-MS: m/z 253.8 [M+H]+at 4.73 RT (98.87% purity). Step-3: Synthesis of (E)-3-(2-methylstyryl)benzoic acid (VN-329) & (Z)-3-(2-methylstyryl)benzoic acid (VN-338). To a stirred solution of compound 4 (320 mg, mixture) in a mixture of methanol (0.7 mL), THF (1 mL) and water (0.7 mL) was added lithium hydroxide monohydride (80 mg, 1.9 mmol) at 0-5° C. The reaction mixture was gradually warmed to RT and stirred for 6 h. The progress of the reaction was monitored by TLC; after the completion, the volatiles were removed under reduced pressure. The residue was acidified with 2N HCl to pH ˜2-3 and extracted with EtOAc (2×25 mL). The combined organic extracts were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by normal phase preparative HPLC (Method N) to afford VN-329 (35 mg, 0.15 mmol, 11%) & VN-338 (35 mg, 0.15 mmol, 11%) as off white solids respectively. Analytical data of VN-329:1H NMR (400 MHz, DMSO-d6): δ 13.06 (br s, 1H), 8.13 (t, J=1.6 Hz, 1H), 7.94-7.92 (m, 1H), 7.84 (dt, J=7.7, 1.3 Hz, 1H), 7.72-7.67 (m, 1H), 7.54-7.45 (m, 2H), 7.26-7.19 (m, 4H), 2.42 (s, 3H);1H NMR (500 MHz, DMSO-d6, D2O Exc.): δ 8.09 (s, 1H), 7.91-7.79 (m, 2H), 7.66 (br d, J=7.1 Hz, 1H), 7.51 (t, J=7.7 Hz, 1H), 7.44 (d, J=16.2 Hz, 1H), 7.24-7.15 (m, 4H), 2.38 (s, 3H). LC-MS: m/z 236.9 [M−H]+at 2.89 RT (99.97% purity). HPLC: 99.20%. Analytical data of VN-3338:1H NMR (400 MHz, DMSO-d6): δ 12.88 (br s, 1H), 7.76-7.69 (m, 2H), 7.32-7.23 (m, 3H), 7.18 (td, J=7.3, 1.6 Hz, 1H), 7.09-7.00 (m, 2H), 6.81-6.72 (m, 2H), 2.23 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.75-7.65 (m, 2H), 7.32-7.26 (m, 2H), 7.26-7.21 (m, 1H), 7.16 (td, J=7.3, 1.5 Hz, 1H), 7.06-6.97 (m, 2H), 6.80-6.69 (m, 2H), 2.19 (s, 3H). LC-MS: m/z 236.9 [M−H]+at 2.90 RT (99.93% purity). HPLC: 98.29%. Preparation of VN-330 & VN-339. The synthetic strategy for preparing VN-330 and VN-339 are detailed in the scheme below. Step-1: Synthesis of Benzyltriphenylphosphonium bromide (2). To a stirred solution of (bromomethyl)benzene 1 (1.39 mL, 11.69 mmol) in toluene (20 mL) was added triphenylphosphine (3.06 g, 11.69 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 16 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×15 mL) and dried under vacuum to afford compound 2 (4.7 g, 10.85 mmol, 97%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.86 (m, 3H), 7.79-7.63 (m, 12H), 7.33-7.26 (m, 1H), 7.26-7.20 (m, 2H), 7.00-6.96 (m, 2H), 5.22-5.16 (m, 2H). Step-2: Synthesis of Methyl (E)-3-styrylbenzoate (4). To a stirred solution of compound 2 (500 mg, 1.21 mmol) in THF (3.5 mL) was added n-BuLi (2.5 M in hexanes, 0.53 mL, 1.33 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 20 min. Then methyl 3-formylbenzoate 3 (198 mg, 1.21 mmol) in THF (0.7 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 30 min. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with saturated NH4Cl solution (30 mL) at 0° C. and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by combi flash column chromatography (eluent: 10% EtOAc/n-hexanes) to afford compound 4 (250 mg, 1.05 mmol, 97%) as a mixture of cis and trans-isomers as colorless liquid.1H NMR (400 MHz, CDCl3): δ 8.20 (t, J=1.8 Hz, 1H), 7.94-7.91 (m, 2H), 7.86 (dt, J=7.7, 1.3 Hz, 1H), 7.68 (dt, J=7.7, 1.3 Hz, 1H), 7.55-7.51 (m, 2H), 7.45-7.35 (m, 4H), 7.31-7.27 (m, 1H), 7.25-7.19 (m, 6H), 7.16 (d, J=11.4 Hz, 2H), 6.70-6.65 (m, 1H), 6.64-6.58 (m, 1H), 3.95 (s, 3H), 3.87 (s, 3H). LC-MS: m/z 239.2 [M+H]+at 4.52 RT (98.96% purity). Step-3: Synthesis of (E)-3-styrylbenzoic acid (VN-330) & (Z)-3-styrylbenzoic acid (VN-339). To a stirred solution of compound 4 (200 mg, mixture) in methanol/THF/water (1:1:1, 1.5 mL) was added lithium hydroxide monohydride (53 mg, 1.26 mmol) at 0° C. The reaction mixture was gradually warmed to RT and stirred for 5 h. The progress of the reaction was monitored by TLC; after the completion, the volatiles were removed under reduced pressure. The residue was acidified with 5N HCl to pH ˜2-3 and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by preparative HPLC (Method F & M) to afford VN-330 (20 mg, 0.09 mmol, 11%) & VN-339 (60 mg, 0.27 mmol, 32%) as off white solids respectively. Analytical data of VN-330:1H NMR (500 MHz, DMSO-d6): δ 13.03 (br s, 1H), 8.15 (s, 1H), 7.85 (br dd, J=12.9, 7.7 Hz, 2H), 7.65 (d, J=7.2 Hz, 2H), 7.51 (t, J=7.7 Hz, 1H), 7.39 (t, J=7.7 Hz, 2H), 7.36-7.34 (m, 2H), 7.32-7.27 (m, 1H);1H NMR (500 MHz, DMSO-d6, D2O Exc.): δ 8.10 (s, 1H), 7.83 (br dd, J=14.6, 7.7 Hz, 2H), 7.61 (d, J=7.2 Hz, 2H), 7.50 (t, J=7.5 Hz, 1H), 7.37 (t, J=7.5 Hz, 2H), 7.31-7.24 (m, 3H). LC-MS: m/z 222.8 [M−H]+at 2.78 RT (99.73% purity). HPLC: 100.00%. Analytical data of VN-339:1H NMR (500 MHz, DMSO-d6): δ 12.88 (s, 1H), 7.84-7.76 (m, 2H), 7.45-7.35 (m, 2H), 7.29-7.19 (m, 5H), 6.74-6.68 (m, 2H);1H NMR (500 MHz, DMSO-d6, D2O Exc.): δ 7.79-7.74 (m, 2H), 7.45-7.35 (m, 2H), 7.26-7.14 (m, 5H), 6.73-6.63 (m, 2H). LC-MS: m/z 222.8 [M−H]+at 2.72 RT (99.60% purity). HPLC: 98.31%. Preparation of VN-331. The synthetic strategy for preparing VN-381 is detailed in the scheme below. Step-1: Synthesis of 4-((tert-butyldimethylsilyl)oxy)-2-methylbenzaldehyde (2). To a stirred solution of 4-hydroxy-2-methylbenzaldehyde 1 (2 g, 14.7 mmol) in DMF (14 mL) were added imidazole (2.5 g, 36.76 mmol) and tert-butyldimethylchlorosilane (3.32 g, 22.06 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 6 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was diluted with water (50 mL) and extracted with EtOAc (2×50 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 5% EtOAc/n-hexanes) to afford compound 2 (2.1 g, 8.39 mmol, 57%) as colorless liquid.1H NMR (400 MHz, CDCl3): δ 10.12 (s, 1H), 7.70 (d, J=8.4 Hz, 1H), 6.78 (dd, J=8.4, 2.4 Hz, 1H), 6.69 (d, J=2.3 Hz, 1H), 2.62 (s, 3H), 0.99 (s, 9H), 0.24 (s, 6H). LC-MS: m/z 251.2 [M+H]+at 3.31 RT (98.30% purity). Step-2: Synthesis of (4-((tert-butyldimethylsilyl)oxy)-2-methylphenyl)methanol (3). To a stirred solution of compound 2 (1 g, 4.0 mmol) in isopropanol (10 mL) was added sodium borohydride (91 mg, 2.4 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 2 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice pieces and extracted with EtOAc (2×40 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 3 (1 g) as colorless syrup. The crude material was taken to next step without further purification.1H NMR (500 MHz, CDCl3): δ 7.16 (d, J=8.1 Hz, 1H), 6.70-6.63 (m, 2H), 4.62 (s, 2H), 2.33 (s, 3H), 0.98 (s, 9H), 0.19 (s, 6H). LC-MS: m/z 235.2 [M-17]+at 3.02 RT (82.70% purity). Step-3: Synthesis of (4-(bromomethyl)-3-methylphenoxy)(tert-butyl)dimethylsilane (4). To a stirred solution of compound 3 (500 mg, crude) in diethylether (10 mL) were added pyridine (0.03 mL, 0.4 mmol) followed by phosphorus tribromide (0.21 mL, 2.18 mmol) drop wise at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 6 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with water (20 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 4 (440 mg) as pale yellow syrup. The crude material was taken to next step without further purification. Step-4: Synthesis of (4-((tert-butyldimethylsilyl)oxy)-2-methylbenzyl)triphenylphosphonium bromide (5). To a stirred solution of compound 4 (480 mg, crude) in toluene (20 mL) was added triphenylphosphine (399 mg, 1.52 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 6 h. Then the precipitated solid was filtered, washed with toluene (2×10 mL), n-hexanes (2×10 mL) and dried under vacuum to afford compound 5 (680 mg, 1.18 mmol, 77%) as white solid. LC-MS: m/z 497.4 [(M-Br)+H]+at 2.74 RT (57.03% purity). Step-5: Synthesis of Methyl (E)-2-(4-((tert-butyldimethylsilyl)oxy)-2-methylstyryl)benzoate (7). To a stirred solution of compound 5 (1 g, 1.73 mmol) in THE (8 mL) was added n-BuLi (2.5 M in hexanes, 0.83 mL, 2.08 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of methyl 2-formylbenzoate 6 (313 mg, 1.91 mmol) in THF (2 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with saturated NH4Cl solution (30 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 3-5% EtOAc/n-hexanes) to afford compound 7 (400 mg, 1.04 mmol, 60%) as a mixture of cis and trans-isomers as colorless semi solid. LC-MS: m/z 383.3 [M+H]+at 6.01 RT (49.99% purity) & m/z 383.3 [M+H]+at 6.14 RT (44.12% purity). Step-6: Synthesis of Methyl (E)-2-(4-hydroxy-2-methylstyryl)benzoate (8). To a stirred solution of compound 7 (430 mg, 1.12 mmol) in THF (5 mL) was added tetra-n-butylammonium fluoride (1 M in THF, 1.35 mL, 1.35 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 6 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with water (20 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by combi flash column chromatography (eluent: 30% EtOAc/n-hexanes) followed by preparative HPLC (Method D) to afford compound 8 (100 mg, 0.37 mmol, 33%) as colorless semi solid.1H NMR (400 MHz, CDCl3): δ 7.92 (dd, J=7.8, 1.2 Hz, 1H), 7.77-7.68 (m, 2H), 7.56-7.48 (m, 2H), 7.30 (td, J=7.6, 1.1 Hz, 1H), 7.15 (d, J=15.9 Hz, 1H), 6.72-6.66 (m, 2H), 3.92 (s, 3H), 2.38 (s, 3H). Step-7: Synthesis of (E)-2-(4-hydroxy-2-methylstyryl)benzoic acid (VN-331). To a stirred solution of compound 8 (100 mg, 0.37 mmol) in a mixture of THF/methanol/water (1:1:1, 6 mL) was added lithium hydroxide monohydride (23 mg, 0.56 mmol) at 0° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the volatiles were removed under reduced pressure. The residue was diluted with water (5 mL) and extracted with EtOAc (2×5 mL). The organic layer was separated; the aqueous layer was acidified with 6N HCl to pH ˜2 and extracted with EtOAc (2×20 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford VN-331 (50 mg, 0.2 mmol, 52%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 12.94 (br s, 1H), 9.46 (s, 1H), 7.81 (d, J=7.9 Hz, 2H), 7.62 (d, J=16.2 Hz, 1H), 7.54 (td, J=7.7, 1.0 Hz, 1H), 7.40 (d, J=8.3 Hz, 1H), 7.37-7.31 (m, 1H), 7.20 (d, J=16.2 Hz, 1H), 6.67-6.60 (m, 2H), 2.32 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.82-7.76 (m, 2H), 7.60-7.51 (m, 2H), 7.41-7.31 (m, 2H), 7.18 (d, J=16.2 Hz, 1H), 6.68-6.61 (m, 2H), 2.30 (s, 3H). LC-MS: m/z 255.2 [M+H]+at 2.11 RT (96.10% purity). HPLC: 99.11%. Preparation of VN-322. The synthetic strategy for preparing VN-322 is detailed in the scheme below. Step-1: Synthesis of (4-methoxy-2-methylphenyl)methanol (2). To a stirred solution of 4-methoxy-2-methylbenzaldehyde 1 (10 g, 66.67 mmol) in isopropanol (100 mL) was added sodium borohydride (1.52 g, 40.0 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 3 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (100 mL) and extracted with EtOAc (2×100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 2 (10 g, 65.71 mmol) as colorless syrup. The crude material was taken to next step without further purification.1H NMR (500 MHz, CDCl3): δ 7.23 (d, J=8.1 Hz, 1H), 6.76-6.70 (m, 2H), 4.64 (s, 2H), 3.80 (s, 3H), 2.37 (s, 3H), 1.40 (br s, 1H). Step-2: Synthesis of 1-(bromomethyl)-4-methoxy-2-methylbenzene (3). To a stirred solution of compound 2 (10 g, crude) in CH2Cl2(100 mL) was added phosphorous tribromide (18.7 mL, 197.37 mmol) at 0-5° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was diluted with CH2Cl2(100 mL), washed with water (100 mL) and saturated NaHCO3solution (100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 3 (14.2 g, 66.02 mmol) as colorless syrup. The crude material was taken to next step without further purification. Step-3: Synthesis of (4-methoxy-2-methylbenzyl)triphenylphosphonium bromide (4). To a stirred solution of compound 3 (5 g, crude) in toluene (50 mL) was added triphenylphosphine (6.12 g, 23.36 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 16 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 4 (4.2 g, 8.8 mmol, 38%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.96-7.89 (m, 3H), 7.77-7.71 (m, 6H), 7.67-7.59 (m, 6H), 6.85 (dd, J=8.5, 2.6 Hz, 1H), 6.70-6.61 (m, 2H), 4.99-4.93 (m, 2H), 3.69 (s, 3H), 1.58 (s, 3H). Step-4: Synthesis of Methyl (E)-4-(4-methoxy-2-methylstyryl)benzoate (6). To a stirred solution of compound 4 (800 mg, 1.68 mmol) in THF (10 mL) was added n-BuLi (2.5 M in hexanes, 0.8 mL, 2.01 mmol) at −78° C. under inert atmosphere. The reaction mixture was stirred at the same temperature for 20 min. and at RT for 30 min. Then a solution of methyl 4-formylbenzoate 5 (275 mg, 1.68 mmol) in THF (5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with saturated NH4Cl solution (20 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 20% EtOAc/n-hexanes) to afford compound 6 (400 mg, 1.42 mmol, 84%) as a mixture of cis and trans-isomers as pale yellow liquid.1H NMR (500 MHz, DMSO-d6): δ 7.94 (d, J=8.4 Hz, 2H), 7.80-7.71 (m, 4H), 7.68-7.64 (m, 1H), 7.50 (d, J=16.5 Hz, 1H), 7.24 (d, J=8.1 Hz, 2H), 7.09 (d, J=16.2 Hz, 1H), 6.92 (d, J=8.4 Hz, 1H), 6.85-6.74 (m, 4H), 6.69-6.60 (m, 2H), 3.85 (s, 3H), 3.81 (s, 3H), 3.77 (s, 3H), 3.73 (s, 3H), 2.41 (s, 3H), 2.21 (s, 3H). LC-MS: m/z 283.2 [M+H]+at 4.74 RT (91.09% purity). Step-5: Synthesis of (E)-4-(4-hydroxy-2-methylstyryl)benzoic acid (VN-322). To a stirred solution of compound 6 (400 mg, 1.42 mmol) in CH2Cl2(8 mL) was added boron tribromide (1 M in CH2Cl2, 8.51 mL, 8.51 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (20 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by preparative HPLC (reverse phase followed by normal phase) (Methods J & N) to afford VN-322 (26 mg, 0.1 mmol, 7%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 12.85 (br s, 1H), 9.52 (br s, 1H), 7.90 (d, J=8.4 Hz, 2H), 7.67 (d, J=8.4 Hz, 2H), 7.54 (d, J=8.2 Hz, 1H), 7.45 (d, J=16.3 Hz, 1H), 7.01 (d, J=16.2 Hz, 1H), 6.66-6.61 (m, 2H), 2.35 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.89 (d, J=8.4 Hz, 2H), 7.65 (d, J=8.5 Hz, 2H), 7.53 (d, J=8.2 Hz, 1H), 7.42 (d, J=16.2 Hz, 1H), 6.98 (d, J=16.3 Hz, 1H), 6.66-6.59 (m, 2H), 2.31 (s, 3H). LC-MS: m/z 252.8 [M−H]−at 2.11 RT (96.79% purity). HPLC: 98.11%. Preparation of VN-333 & VN-342. The synthetic strategy for preparing VN-334 and VN-343 is detailed in the scheme below. Step-1: Synthesis of (4-methoxy-2-methylphenyl)methanol (2). To a stirred solution of 4-methoxy-2-methylbenzaldehyde 1 (10 g, 66.67 mmol) in isopropanol (100 mL) was added sodium borohydride (1.52 g, 40.0 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 3 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (100 mL) and extracted with EtOAc (2×100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 2 (10 g, 65.71 mmol) as colorless syrup. The crude material was taken to next step without further purification.1H NMR (500 MHz, CDCl3): δ 7.23 (d, J=8.1 Hz, 1H), 6.76-6.70 (m, 2H), 4.64 (s, 2H), 3.80 (s, 3H), 2.37 (s, 3H), 1.40 (br s, 1H). Step-2: Synthesis of 1-(bromomethyl)-4-methoxy-2-methylbenzene (3). To a stirred solution of compound 2 (10 g, crude) in CH2Cl2(100 mL) was added phosphorous tribromide (18.7 mL, 197.37 mmol) at 0-5° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was diluted with CH2Cl2(100 mL), washed with water (100 mL) and saturated NaHCO3solution (100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 3 (14.2 g, 66.02 mmol) as colorless syrup. The crude material was taken to next step without further purification. Step-3: Synthesis of (4-methoxy-2-methylbenzyl)triphenylphosphonium bromide (4). To a stirred solution of compound 3 (5 g, crude) in toluene (50 mL) was added triphenylphosphine (6.12 g, 23.36 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 16 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 4 (4.2 g, 8.8 mmol, 38%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.96-7.89 (m, 3H), 7.77-7.71 (m, 6H), 7.67-7.59 (m, 6H), 6.85 (dd, J=8.5, 2.6 Hz, 1H), 6.70-6.61 (m, 2H), 4.99-4.93 (m, 2H), 3.69 (s, 3H), 1.58 (s, 3H). Step-4: Synthesis of Methyl (E)-3-(4-methoxy-2-methylstyryl)benzoate (6). To a stirred solution of compound 4 (4.6 g, 9.64 mmol) in THE (46 mL) was added n-BuLi (2.5 M in hexanes, 4.63 mL, 11.57 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of methyl 3-formylbenzoate 5 (1.9 g, 11.57 mmol) in THF (13.8 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 2 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with saturated NH4Cl solution (50 mL) and extracted with EtOAc (2×70 mL). The combined organic extracts were washed with brine (30 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 10% EtOAc/n-hexanes) to afford compound 6 (1.8 g, 6.37 mmol, 66%) as a mixture of cis and trans-isomers as colorless syrup.1H NMR (500 MHz, CDCl3): δ 8.18 (s, 1H), 7.92 (d, J=7.8 Hz, 1H), 7.87 (s, 1H), 7.82 (d, J=7.7 Hz, 1H), 7.69 (d, J=7.8 Hz, 1H), 7.56 (d, J=8.5 Hz, 1H), 7.44 (t, J=7.7 Hz, 1H), 7.36 (d, J=16.1 Hz, 1H), 7.30 (s, 1H), 7.23-7.17 (m, 1H), 7.02 (d, J=8.4 Hz, 1H), 6.94 (d, J=16.1 Hz, 1H), 6.82-6.75 (m, 3H), 6.71-6.66 (m, 1H), 6.63-6.57 (m, 2H), 3.96 (s, 3H), 3.89 (s, 3H), 3.84 (s, 3H), 3.80 (s, 3H), 2.45 (s, 3H), 2.27 (s, 3H). Step-5: Synthesis of (E)-3-(4-methoxy-2-methylstyryl)benzoic acid (VN-333) & (Z)-3-(4-methoxy-2-methylstyryl)benzoic acid (VN-342). To a stirred solution of compound 6 (250 mg, mixture) in a mixture of methanol (0.5 mL), THE (1 mL) and water (0.5 mL) was added lithium hydroxide monohydride (56 mg, 1.33 mmol) at 0-5° C. The reaction mixture was gradually warmed to RT and stirred for 5 h. The progress of the reaction was monitored by TLC; after the completion, the volatiles were removed under reduced pressure. The residue was diluted with water (10 mL), acidified with 1N HCl to pH ˜2-3 and extracted with EtOAc (2×25 mL). The combined organic extracts were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by normal phase preparative HPLC (Method F) to afford VN-333 (40 mg, 0.15 mmol, 17%) & VN-342 (40 mg, 0.15 mmol, 17%) as white solids respectively. Analytical data of VN-333:1H NMR (400 MHz, DMSO-d6): δ 13.00 (br s, 1H), 8.09 (s, 1H), 7.89-7.85 (m, 1H), 7.81 (dt, J=7.7, 1.3 Hz, 1H), 7.65-7.62 (m, 1H), 7.49 (t, J=7.7 Hz, 1H), 7.40 (d, J=16.3 Hz, 1H), 7.09 (d, J=16.2 Hz, 11H), 6.83-6.79 (m, 2H), 3.76 (s, 3H), 2.41 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.06 (s, 1H), 7.87-7.82 (m, 1H), 7.79 (dt, J=7.7, 1.3 Hz, 1H), 7.64-7.60 (m, 1H), 7.48 (t, J=7.7 Hz, 1H), 7.36 (d, J=16.3 Hz, 1H), 7.05 (d, J=16.3 Hz, 1H), 6.81-6.77 (m, 2H), 3.73 (s, 3H), 2.37 (s, 3H). LC-MS: m/z 266.9 [M−H] at 2.82 RT (97.22% purity). HPLC: 98.77%. Analytical data of VN-342:1H NMR (400 MHz, DMSO-d6): δ 12.84 (br s, 1H), 7.78-7.70 (m, 2H), 7.35-7.28 (m, 2H), 6.94 (d, J=8.4 Hz, 1H), 6.83 (d, J=2.6 Hz, 1H), 6.73-6.61 (m, 3H), 3.73 (s, 3H), 2.21 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.72-7.62 (m, 2H), 7.30 (d, J=4.9 Hz, 2H), 6.89 (d, J=8.5 Hz, 1H), 6.78 (d, J=2.5 Hz, 1H), 6.69-6.54 (m, 3H), 3.67 (s, 3H), 2.15 (s, 3H). LC-MS: m/z 266.9 [M−H]−at 2.88 RT (99.43% purity). HPLC: 99.35%. Preparation of VN-314. The synthetic strategy for preparing VN-314 is detailed in the scheme below. Step-1: Synthesis of (4-methoxy-2-methylphenyl)methanol (2). To a stirred solution of 4-methoxy-2-methylbenzaldehyde 1 (10 g, 66.67 mmol) in isopropanol (100 mL) was added sodium borohydride (1.52 g, 40.0 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 3 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (100 mL) and extracted with EtOAc (2×100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 2 (10 g, 65.71 mmol) as colorless syrup. The crude material was taken to next step without further purification.1H NMR (500 MHz, CDCl3): δ 7.23 (d, J=8.1 Hz, 1H), 6.76-6.70 (m, 2H), 4.64 (s, 2H), 3.80 (s, 3H), 2.37 (s, 3H), 1.40 (br s, 1H). Step-2: Synthesis of 1-(bromomethyl)-4-methoxy-2-methylbenzene (3). To a stirred solution of compound 2 (10 g, crude) in CH2Cl2(100 mL) was added phosphorous tribromide (18.7 mL, 197.37 mmol) at 0-5° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was diluted with CH2Cl2(100 mL), washed with water (100 mL) and saturated NaHCO3solution (100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 3 (14.2 g, 66.02 mmol) as colorless syrup. This material was taken to next step without further purification. Step-3: Synthesis of (4-methoxy-2-methylbenzyl)triphenylphosphonium bromide (4). To a stirred solution of compound 3 (5 g, crude) in toluene (50 mL) was added triphenylphosphine (6.12 g, 23.36 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 16 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 4 (4.2 g, 8.8 mmol, 38%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.96-7.89 (m, 3H), 7.77-7.71 (m, 6H), 7.67-7.59 (m, 6H), 6.85 (dd, J=8.5, 2.6 Hz, 1H), 6.70-6.61 (m, 2H), 4.99-4.93 (m, 2H), 3.69 (s, 3H), 1.58 (s, 3H). Step-4: Synthesis of (E)-3-(4-methoxy-2-methylstyryl)benzonitrile (6). To a stirred solution of compound 4 (1 g, 2.1 mmol) in THF (8 mL) was added n-BuLi (2.5 M in hexanes, 1.57 mL, 2.51 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of 3-formylbenzonitrile 5 (412 mg, 3.14 mmol) in THF (2 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with saturated NH4Cl solution (30 mL) and extracted with EtOAc (2×50 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 10% EtOAc/n-hexanes) to afford compound 6 (500 mg, 2.0 mmol, 96%) as a mixture of cis and trans-isomers as an off white solid.1H NMR (500 MHz, CDCl3): δ 7.76 (s, 1H), 7.69 (d, J=7.8 Hz, 1H), 7.56-7.48 (m, 2H), 7.47-7.39 (m, 2H), 7.36-7.30 (m, 2H), 7.25-7.23 (m, 1H), 6.96 (d, J=8.7 Hz, 1H), 6.85 (d, J=16.2 Hz, 1H), 6.81-6.70 (m, 4H), 6.58 (dd, J=8.4, 2.6 Hz, 1H), 6.51 (d, J=11.9 Hz, 1H), 3.83 (s, 3H), 3.79 (s, 3H), 2.43 (s, 3H), 2.25 (s, 3H). Step-5: Synthesis of (E)-3-(4-hydroxy-2-methylstyryl)benzonitrile (VN-340). To a stirred solution of compound 6 (500 mg, 2.01 mmol) in CH2Cl2(20 mL) was added boron tribromide (1 M in CH2Cl2, 6.02 mL, 6.02 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (20 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 30% EtOAc/n-hexanes) to afford VN-340 (200 mg, 0.85 mmol, 42%) as a brown solid.1H NMR (500 MHz, CDCl3): δ 7.77 (s, 1H), 7.70 (d, J=7.8 Hz, 1H), 7.54-7.44 (m, 3H), 7.32 (d, J=16.2 Hz, 1H), 6.86 (d, J=16.2 Hz, 1H), 6.75-6.69 (m, 2H), 2.42 (s, 3H). LC-MS: m/z 234.0 [M−H]−at 3.06 RT (98.54% purity). Step-6: Synthesis of (E)-4-(3-(2H-tetrazol-5-yl)styryl)-3-methylphenol (VN-314). To a stirred solution of VN-340 (200 mg, 0.85 mmol) in DMF (2 mL) were added sodium azide (166 mg, 2.55 mmol) and ammonium chloride (135 mg, 2.55 mmol) in a microwave vessel at RT under inert atmosphere. The vessel was sealed and the reaction mixture was irradiated to 120° C. and stirred for 2 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with 1N HCl solution (20 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by preparative HPLC (Method O) to afford VN-314 (70 mg, 0.25 mmol, 30%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 9.49 (s, 1H), 8.21 (s, 1H), 7.88 (d, J=7.9 Hz, 1H), 7.78 (d, J=7.9 Hz, 1H), 7.62-7.53 (m, 2H), 7.44 (d, J=16.2 Hz, 1H), 7.04 (d, J=16.2 Hz, 1H), 6.69-6.61 (m, 2H), 2.37 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.19 (s, 1H), 7.87 (d, J=7.8 Hz, 1H), 7.77 (d, J=7.9 Hz, 1H), 7.60-7.53 (m, 2H), 7.42 (d, J=16.3 Hz, 1H), 7.02 (d, J=16.2 Hz, 1H), 6.68-6.62 (m, 2H), 2.35 (s, 3H). LC-MS: m/z 279.1 [M+H]+at 2.41 RT (96.98% purity). HPLC: 98.97%. Preparation of VN-335. The synthetic strategy for preparing VN-335 is detailed in the scheme below. Step-1: Synthesis of (4-methoxy-2-methylphenyl)methanol (2). To a stirred solution of 4-methoxy-2-methylbenzaldehyde 1 (10 g, 66.67 mmol) in isopropanol (100 mL) was added sodium borohydride (1.52 g, 40.0 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 3 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (100 mL) and extracted with EtOAc (2×100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 2 (10 g, 65.71 mmol) as colorless syrup. The crude material was taken to next step without further purification.1H NMR (500 MHz, CDCl3): δ 7.23 (d, J=8.1 Hz, 1H), 6.76-6.70 (m, 2H), 4.64 (s, 2H), 3.80 (s, 3H), 2.37 (s, 3H), 1.40 (br s, 1H). Step-2: Synthesis of 1-(bromomethyl)-4-methoxy-2-methylbenzene (3). To a stirred solution of compound 2 (10 g, crude) in CH2Cl2(100 mL) was added phosphorous tribromide (18.7 mL, 197.37 mmol) at 0-5° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was diluted with CH2Cl2(100 mL), washed with water (100 mL) and saturated NaHCO3solution (100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 3 (14.2 g, 66.02 mmol) as colorless syrup. The crude material was taken to next step without further purification. Step-3: Synthesis of (4-methoxy-2-methylbenzyl)triphenylphosphonium bromide (4). To a stirred solution of compound 3 (5 g, crude) in toluene (50 mL) was added triphenylphosphine (6.12 g, 23.36 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 16 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 4 (4.2 g, 8.8 mmol, 38%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.96-7.89 (m, 3H), 7.77-7.71 (m, 6H), 7.67-7.59 (m, 6H), 6.85 (dd, J=8.5, 2.6 Hz, 1H), 6.70-6.61 (m, 2H), 4.99-4.93 (m, 2H), 3.69 (s, 3H), 1.58 (s, 3H). Step-4: Synthesis of (E)-3-(4-methoxy-2-methylstyryl)benzenesulfonamide (6). To a stirred solution of compound 4 (200 mg, 0.42 mmol) in anhydrous THF (1.5 mL) was added n-BuLi (2.5 M in hexanes, 0.18 mL, 0.46 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of 3-formylbenzenesulfonamide 5 (77 mg, 0.42 mmol) in THF (0.5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with saturated NH4Cl solution (20 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 10% EtOAc/n-hexanes) to afford compound 6 (100 mg, 0.33 mmol, 83%) as yellow syrup.1H NMR (500 MHz, DMSO-d6): δ 8.01 (s, 1H), 7.81 (d, J=7.8 Hz, 1H), 7.70-7.52 (m, 4H), 7.45-7.20 (m, 5H), 7.10 (d, J=16.2 Hz, 1H), 6.93 (d, J=8.4 Hz, 1H), 6.85-6.79 (m, 2H), 6.76-6.60 (m, 2H), 3.77 (s, 3H), 3.73 (s, 2H), 2.41 (s, 3H), 2.22 (s, 2H). LC-MS: m/z 301.9 [M−H]−at 2.98 RT (95.58% purity). Step-5: Synthesis of (E)-3-(4-hydroxy-2-methylstyryl)benzenesulfonamide (VN-335). To a stirred solution of compound 6 (150 mg, 0.49 mmol) in DMF (1.5 mL) was added sodium thioethoxide (208 mg, 2.47 mmol) in a microwave vessel at RT. The vessel was sealed and the reaction mixture was irradiated to 120° C. and stirred for 1 h. The progress of the reaction was monitored by LC-MS; after the completion, the reaction mixture was combined with another lot (SMB-MA1704-035, 150 mg), diluted with water (30 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by preparative HPLC (Method L) to afford VN-335 (28 mg, 0.1 mmol, 10% for two batches) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 9.50 (s, 1H), 7.99 (s, 1H), 7.80-7.76 (m, 1H), 7.68-7.64 (m, 1H), 7.57-7.51 (m, 2H), 7.42-7.35 (m, 3H), 7.03 (d, J=16.3 Hz, 1H), 6.67-6.61 (m, 2H), 2.35 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.94 (s, 1H), 7.78-7.72 (m, 1H), 7.67-7.61 (m, 1H), 7.55-7.50 (m, 2H), 7.35 (d, J=16.2 Hz, 1H), 6.98 (d, J=16.2 Hz, 1H), 6.65-6.61 (m, 2H), 2.30 (s, 3H). LC-MS: m/z 287.9 [M−H]−at 3.11 RT (94.06% purity). HPLC: 95.59%. Preparation of VN-336. The synthetic strategy for preparing VN-336 is detailed in the scheme below. Step-1: Synthesis of Methyl 3-((4-methoxy-2-methylphenyl)amino)benzoate (3). To a stirred solution of 1-bromo-4-methoxy-2-methylbenzene 1 (1 g, 4.97 mmol) and methyl 3-aminobenzoate 2 (901 mg, 5.97 mmol) in toluene (10 mL) were added cesium carbonate (2.43 g, 7.46 mmol) and BINAP (247 mg, 0.4 mmol) in a sealed tube at RT and purged under argon for 10 min. Then Pd(OAc)2(56 mg, 0.25 mmol) was added and again purged under argon for 5 min. The reaction mixture was heated to 120° C. and stirred for 8 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was filtered through a pad of celite and the celite bed was washed with EtOAc (15 mL). The filtrate was washed with water (20 mL) and extracted with EtOAc (2×40 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 30% EtOAc/n-hexanes) to afford compound 3 (700 mg, 2.58 mmol, 52%) as yellow sticky liquid.1H NMR (400 MHz, DMSO-d6): δ 7.58 (s, 1H), 7.24-7.19 (m, 3H), 7.07 (d, J=8.7 Hz, 1H), 6.88-6.84 (m, 2H), 6.77 (dd, J=8.6, 2.9 Hz, 1H), 3.78 (s, 3H), 3.74 (s, 3H), 2.13 (s, 3H). LC-MS: m/z 271.9 [M+H]+at 3.35 RT (92.41% purity). Step-2: Synthesis of 3-((4-hydroxy-2-methylphenyl)amino)benzoic acid (VN-336). To a stirred solution of compound 3 (300 mg, 1.11 mmol) in CH2Cl2(6 mL) was added boron tribromide (1 M in CH2Cl2, 6.64 mL, 6.64 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (30 mL) and the organic layer was separated. The aqueous layer was extracted with EtOAc (2×30 mL). The combined organic extracts (CH2Cl2and EtOAc layers) were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by reverse phase preparative HPLC (Method J) followed by lyophilization to afford VN-336 (30 mg, 0.12 mmol, 11%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 12.63 (br s, 1H), 9.15 (br s, 1H), 7.42 (br s, 1H), 7.19-7.12 (m, 3H), 6.94 (d, J=8.4 Hz, 1H), 6.80-6.75 (m, 1H), 6.67 (d, J=2.6 Hz, 1H), 6.59 (dd, J=8.3, 2.8 Hz, 1H), 2.06 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.22-7.14 (m, 2H), 7.06-7.04 (m, 1H), 6.93 (d, J=8.5 Hz, 1H), 6.83-6.78 (m, 1H), 6.68 (d, J=2.8 Hz, 1H), 6.59 (dd, J=8.4, 2.9 Hz, 1H), 2.03 (s, 3H). LC-MS: m/z 244.2 [M+H]+at 2.00 RT (97.06% purity). HPLC: 99.50%. Preparation of VN-337. The synthetic strategy for preparing VN-337 is detailed in the scheme below. Step-1: Synthesis of 3-((4-methoxy-2-methylphenyl)thio)benzoic acid (3). To a stirred solution of 3-mercaptobenzoic acid 1 (200 mg, 1.3 mmol) in 1,4-dioxane (8 mL) were added 1-bromo-4-methoxy-2-methylbenzene 2 (0.21 mL, 1.56 mmol), N,N-diisopropylethylamine (0.68 mL, 3.9 mmol) followed by Xantphos (150 mg, 0.26 mmol) in a sealed tube at RT under inert atmosphere and purged under argon for 15 min. To this reaction mixture was added Pd2(dba)3(238 mg, 0.26 mmol) at RT. The vessel was sealed and heated to 90° C. and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was filtered through a pad of celite and the celite bed was washed with EtOAc (20 mL). The filtrate was concentrated under reduced pressure to obtain the crude. The crude material was purified by silica gel column chromatography (eluent: 2% MeOH/CH2Cl2) to afford compound 3 (130 mg, impure) as brown syrup. This material was taken to next step without further purification. LC-MS: m/z 272.9 [M−H]−at 2.63 RT (29.28% purity). Step-2: Synthesis of 3-((4-hydroxy-2-methylphenyl)thio)benzoic acid (VN-337). To a stirred solution of compound 3 (100 mg, 0.36 mmol) in CH2Cl2(5 mL) was added boron tribromide (1 M in CH2Cl2, 1.09 mL, 1.09 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 3 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (15 mL) and extracted with EtOAc (2×15 mL). The combined organic extracts were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 3-4% MeOH/CH2Cl2) followed by normal phase preparative HPLC to afford VN-337 (15 mg, 0.06 mmol, 16%) as an off white solid.1H NMR (400 MHz, CD3OD): δ 7.72 (dt, J=7.7, 1.4 Hz, 1H), 7.62 (t, J=1.6 Hz, 1H), 7.37 (d, J=8.4 Hz, 1H), 7.30 (t, J=7.8 Hz, 1H), 7.18-7.14 (m, 1H), 6.81 (d, J=2.8 Hz, 1H), 6.70 (dd, J=8.3, 2.8 Hz, 1H), 2.28 (s, 3H). LC-MS: m/z 258.9 [M−H−at 2.31 RT (95.69% purity). HPLC: 99.06%. Preparation of VN-340. The synthetic strategy for preparing VN-340 is detailed in the scheme below. Step-1: Synthesis of (4-methoxy-2-methylphenyl)methanol (2). To a stirred solution of 4-methoxy-2-methylbenzaldehyde 1 (10 g, 66.67 mmol) in isopropanol (100 mL) was added sodium borohydride (1.52 g, 40.0 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 3 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with ice cold water (100 mL) and extracted with EtOAc (2×100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 2 (10 g, 65.71 mmol) as colorless syrup. The crude material was taken to next step without further purification.1H NMR (500 MHz, CDCl3): δ 7.23 (d, J=8.1 Hz, 1H), 6.76-6.70 (m, 2H), 4.64 (s, 2H), 3.80 (s, 3H), 2.37 (s, 3H), 1.40 (br s, 1H). Step-2: Synthesis of 1-(bromomethyl)-4-methoxy-2-methylbenzene (3). To a stirred solution of compound 2 (10 g, crude) in CH2Cl2(100 mL) was added phosphorous tribromide (18.7 mL, 197.37 mmol) at 0-5° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was diluted with CH2Cl2(100 mL), washed with water (100 mL) and saturated NaHCO3solution (100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 3 (14.2 g, 66.02 mmol) as colorless syrup. The crude material was taken to next step without further purification. Step-3: Synthesis of (4-methoxy-2-methylbenzyl)triphenylphosphonium bromide (4). To a stirred solution of compound 3 (5 g, crude) in toluene (50 mL) was added triphenylphosphine (6.12 g, 23.36 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 16 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 4 (4.2 g, 8.8 mmol, 38%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.96-7.89 (m, 3H), 7.77-7.71 (m, 6H), 7.67-7.59 (m, 6H), 6.85 (dd, J=8.5, 2.6 Hz, 1H), 6.70-6.61 (m, 2H), 4.99-4.93 (m, 2H), 3.69 (s, 3H), 1.58 (s, 3H). Step-4: Synthesis of (E)-3-(4-methoxy-2-methylstyryl)benzonitrile (6). To a stirred solution of compound 4 (1.5 g, 3.14 mmol) in THE (11 mL) was added n-BuLi (2.5 M in hexanes, 1.51 mL, 3.77 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of 3-formylbenzonitrile (618 mg, 4.72 mmol) in THF (5 mL) was added at −78° C. and allowed to stir at the same temperature for 1 h. Then the reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC & LCMS, after the completion, the reaction mixture was quenched with saturated NH4Cl solution (30 mL) and extracted with EtOAc (2×50 mL). The combined organic extracts were washed with brine (30 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 10% EtOAc/n-hexanes) to afford compound 6 (700 mg, 2.81 mmol, 89%) as a mixture of cis and trans-isomers as an off white solid.1H NMR (500 MHz, CDCl3): δ 7.76 (s, 1H), 7.69 (d, J=7.8 Hz, 1H), 7.56-7.49 (m, 2H), 7.47-7.40 (m, 2H), 7.35-7.30 (m, 2H), 7.26-7.23 (m, 0.5H), 6.96 (d, J=8.4 Hz, 0.5H), 6.85 (d, J=16.2 Hz, 1H), 6.80-6.70 (m, 3H), 6.59 (dd, J=8.4, 2.3 Hz, 0.5H), 6.51 (d, J=11.9 Hz, 0.5H), 3.83 (s, 3H), 3.80 (s, 2H), 2.43 (s, 3H), 2.26 (s, 2H). LC-MS: m/z 250.0 [M+H]+at 4.52 RT (95.06% purity). Step-5: Synthesis of (E)-3-(4-hydroxy-2-methylstyryl)benzonitrile (VN-340). To a stirred solution of compound 6 (200 mg, 0.8 mmol) in CH2Cl2(15 mL) was added boron tribromide (1 M in CH2Cl2, 2.41 mL, 2.41 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC & LCMS, after the completion, the reaction mixture was quenched with ice cold water (20 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 25% EtOAc/n-hexanes) to afford VN-340 (100 mg, 0.42 mmol, 53%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 9.51 (s, 1H), 8.09 (s, 1H), 7.88 (d, J=7.9 Hz, 1H), 7.66 (d, J=7.7 Hz, 1H), 7.57-7.44 (m, 3H), 6.97 (d, J=16.2 Hz, 1H), 6.67-6.60 (m, 2H), 2.35 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.01 (s, 1H), 7.87 (d, J=7.9 Hz, 1H), 7.61 (d, J=7.7 Hz, 1H), 7.55-7.48 (m, 2H), 7.42 (d, J=16.2 Hz, 1H), 6.94 (d, J=16.2 Hz, 1H), 6.65-6.59 (m, 2H), 2.31 (s, 3H). LC-MS: m/z 233.9 [M−H]−at 3.08 RT (98.90% purity). HPLC: 99.87%. Preparation of VN-341. The synthetic strategy for preparing VN-341 is detailed in the scheme below. Step-1: Synthesis of Methyl 3-((4-hydroxy-2-methylphenoxy)methyl)benzoate (3). To a stirred solution of 2-methylbenzene-1,4-diol 1 (500 mg, 4.03 mmol) in acetonitrile (10 mL) were added methyl 3-(bromomethyl)benzoate 2 (915 mg, 4.03 mmol) and potassium carbonate (1.11 g, 8.06 mmol) at RT under inert atmosphere and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with water (20 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford a mixture of mono and dialkylated compounds 3, 4 & 5 (500 mg) as colorless liquid. The mixture was taken to next step without further purification. LC-MS: m/z 271.2 [M−H]−at 3.61 RT (28.34% purity). Step-2: Synthesis of 3-((4-hydroxy-3-methylphenoxy)methyl)benzoic acid (VN-341). To a stirred solution of mixture of mono and dialkylated compounds 3, 4 & 5 (500 mg) in a mixture of THF/water (4:1, 5 mL) was added lithium hydroxide monohydride (300 mg) at RT under inert atmosphere and stirred for 2 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was acidified with 6 N HCl to pH ˜2-3 and extracted with EtOAc (2×25 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by reverse phase followed by normal phase preparative HPLC (Method G) to afford VN-341 (12 mg, 0.05 mmol) as brown solid. The structure was confirmed by 2 D NMR (NOESY, DQFCOSY and HMBC) studies.1H NMR (400 MHz, DMSO-d6): δ 12.99 (br s, 1H), 8.79 (s, 1H), 7.99 (s, 1H), 7.88 (d, J=7.8 Hz, 1H), 7.66 (d, J=7.7 Hz, 1H), 7.54-7.48 (m, 1H), 6.77 (d, J=2.1 Hz, 1H), 6.68-6.64 (m, 2H), 5.05 (s, 2H), 2.09 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.94 (s, 1H), 7.85 (br d, J=7.7 Hz, 1H), 7.63 (br d, J=7.7 Hz, 1H), 7.54-7.46 (m, 1H), 6.73 (s, 1H), 6.67-6.58 (m, 2H), 5.02 (s, 2H), 2.05 (s, 3H).13C NMR (101 MHz, DMSO-d6): δ 167.17, 150.80, 149.48, 138.26, 131.76, 130.87, 128.65, 128.48, 128.09, 124.74, 118.93, 117.35, 114.95, 112.56, 69.05, 16.17. LC-MS: m/z 256.8 [M−H]−at 1.79 RT (91.16% purity). HPLC: 96.45%. Preparation of VN-343. The synthetic strategy for preparing VN-343 is detailed in the scheme below. Step-1: Synthesis of Methyl 3-((4-methoxy-2-methylphenyl)ethynyl)benzoate (3). To a stirred solution of 1-ethynyl-4-methoxy-2-methylbenzene 1 (500 mg, 3.42 mmol) in DMF (10 mL) were added methyl 3-iodobenzoate 2 (983 mg, 3.77 mmol), copper(I) iodide (65 mg, 0.34 mmol) followed by triethylamine (2.38 mL, 17.12 mmol) at RT under inert atmosphere and purged under argon for 10 min. Then Pd(PPh3)2Cl2(240 mg, 0.34 mmol) was added and again purged under argon for 10 min. The reaction mixture was heated to 80° C. and stirred for 8 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was diluted with water (20 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 20% EtOAc/n-hexanes) to afford compound 3 (600 mg, 2.14 mmol, 63%) as pale yellow liquid.1H NMR (400 MHz, CDCl3): δ 8.18-8.16 (m, 1H), 7.99-7.95 (m, 1H), 7.70-7.66 (m, 1H), 7.45-7.41 (m, 2H), 6.80-6.67 (m, 2H), 3.94 (s, 3H), 3.82 (s, 3H), 2.50 (s, 3H). Step-2: Synthesis of 3-(2-(4-hydroxy-2-methylphenyl)-2-oxoethyl) benzoic acid (VN-343). To a stirred solution of compound 3 (300 mg, 1.07 mmol) in CH2Cl2(15 mL) was added boron tribromide (1 M in CH2Cl2, 4.28 mL, 4.28 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with ice cold water (20 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by preparative HPLC (Method J) to afford VN-343 (30 mg, 0.11 mmol, 10%) as an off white solid. The structure was confirmed by 2 D NMR (NOESY, COSY and HMBC) studies.1H NMR (400 MHz, DMSO-d6): δ 12.88 (br s, 1H), 10.14 (s, 1H), 7.94 (d, J=8.7 Hz, 1H), 7.83-7.78 (m, 2H), 7.50-7.39 (m, 2H), 6.73-6.64 (m, 2H), 4.33 (s, 2H), 2.37 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.88 (d, J=8.5 Hz, 1H), 7.81-7.72 (m, 2H), 7.46-7.39 (m, 2H), 6.70-6.62 (m, 2H), 4.26 (s, 2H), 2.31 (s, 3H).13C NMR (101 MHz, DMSO-d6): δ 198.28, 167.29, 160.43, 141.54, 136.37, 134.22, 132.73, 130.63, 130.55, 128.38, 127.64, 127.27, 118.60, 112.41, 46.19, 21.90. LC-MS: m/z 271.2 [M+H]+at 2.01 RT (98.53% purity). HPLC: 99.31%. Preparation of VN-344. The synthetic strategy for preparing VN-344 is detailed in the scheme below. Step-1: Synthesis of (4-methoxy-2-methylphenyl)methanol (2)). To a stirred solution of 4-methoxy-2-methylbenzaldehyde 1 (10 g, 66.67 mmol) in isopropanol (100 mL) was added sodium borohydride (1.52 g, 40.0 mmol) at 0° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 3 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with ice cold water (100 mL) and extracted with EtOAc (2×100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 2 (10 g, 65.71 mmol) as colorless syrup. The crude material was taken to next step without further purification.1H NMR (500 MHz, CDCl3): δ 7.23 (d, J=8.1 Hz, 1H), 6.76-6.70 (m, 2H), 4.64 (s, 2H), 3.80 (s, 3H), 2.37 (s, 3H), 1.40 (br s, 1H). Step-2: Synthesis of 1-(bromomethyl)-4-methoxy-2-methylbenzene (3). To a stirred solution of compound 2 (10 g, crude) in CH2Cl2(100 mL) was added phosphorous tribromide (18.7 mL, 197.37 mmol) at 0-5° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was diluted with CH2Cl2(100 mL), washed with water (100 mL) and saturated NaHCO3solution (100 mL). The combined organic extracts were washed with brine (50 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 3 (14.2 g, 66.02 mmol) as colorless syrup. The crude material was taken to next step without further purification. Step-3: Synthesis of (4-methoxy-2-methylbenzyl)triphenylphosphonium bromide (4). To a stirred solution of compound 3 (5 g, crude) in toluene (50 mL) was added triphenylphosphine (6.12 g, 23.36 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 16 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 4 (4.2 g, 8.8 mmol, 38%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.96-7.89 (m, 3H), 7.77-7.71 (m, 6H), 7.67-7.59 (m, 6H), 6.85 (dd, J=8.5, 2.6 Hz, 1H), 6.70-6.61 (m, 2H), 4.99-4.93 (m, 2H), 3.69 (s, 3H), 1.58 (s, 3H). Step-4: Synthesis of Methyl (E)-2-(4-methoxy-2-methylstyryl)benzoate (6). To a stirred solution of compound 4 (1.5 g, 3.14 mmol) in THF (10 mL) was added n-BuLi (2.5 M in hexanes, 1.38 mL, 3.46 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of methyl 2-formylbenzoate 5 (516 mg, 3.14 mmol) in THF (5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 12 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with saturated NH4Cl solution (50 mL) and extracted with EtOAc (2×50 mL). The combined organic extracts were washed with brine (30 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 20% EtOAc/n-hexanes) to afford compound 6 (730 mg, 2.58 mmol, 83%) as a mixture of cis and trans-isomers as colorless syrup. LC-MS: m/z 283.2 [M+H]+at 4.47 RT (43.24% purity) & m/z 283.2 [M+H]+at 4.58 RT (43.82% purity). Step-5: Synthesis of 2-(4-hydroxy-2-methylphenyl)-1H-inden-1-one (VN-344). To a stirred solution of compound 6 (600 mg, 2.13 mmol) in CH2Cl2(15 mL) was added boron tribromide (1 M in CH2Cl2, 12.76 mL, 12.76 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 4 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with ice cold water (30 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by preparative HPLC (Method M) to afford VN-344 (40 mg, 0.17 mmol, 8%) as brown solid. The structure was confirmed by 2 D NMR (NOESY, DQFCOSY, HMBC and HSQC) studies.1H NMR (400 MHz, DMSO-d6): δ 9.51 (s, 1H), 7.65 (s, 1H), 7.48-7.42 (m, 1H), 7.39 (d, J=6.9 Hz, 1H), 7.28-7.19 (m, 2H), 7.12 (d, J=8.3 Hz, 1H), 6.68 (d, J=2.4 Hz, 1H), 6.63 (dd, J=8.3, 2.4 Hz, 1H), 2.22 (s, 3H).13C NMR (101 MHz, DMSO-d6): δ 197.01, 157.32, 144.85, 144.31, 137.99, 137.04, 134.50, 131.07, 129.54, 128.55, 122.53, 122.23, 121.54, 117.22, 112.54, 20.81. LC-MS: m/z 234.8 [M−H]−at 3.67 RT (90.90% purity). HPLC: 97.43%. Preparation of VN-346 & VN-377. The synthetic strategy for preparing VN-346 and VN-377 is detailed in the scheme below. Step-1: Synthesis of (3-(methoxycarbonyl)benzyl)triphenylphosphonium bromide (2). To a stirred solution of methyl 3-(bromomethyl)benzoate 1 (5 g, 21.83 mmol) in toluene (50 mL) was added triphenylphosphine (5.72 g, 21.83 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 6 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 2 (8.8 g, 17.91 mmol, 83%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.84 (m, 4H), 7.79-7.72 (m, 6H), 7.71-7.64 (m, 6H), 7.54-7.52 (m, 1H), 7.41 (t, J=7.8 Hz, 1H), 7.31-7.27 (m, 1H), 5.29-5.23 (m, 2H), 3.77 (s, 3H). Step-2: Synthesis of Methyl (E)-3-(2-cyclohexylvinyl)benzoate (4). To a stirred solution of compound 2 (2 g, 4.08 mmol) in THF (25 mL) was added n-BuLi (2.0 M in hexanes, 2.24 mL, 4.49 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of cyclohexanecarbaldehyde 3 (457 mg, 4.08 mmol) in THF (5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with saturated NH4Cl solution (30 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 5% EtOAc/n-hexanes) to afford compound 4 (800 mg, 3.27 mmol, 80%) as a mixture of cis and trans-isomers as colorless syrup. The mixture was taken to next step without further purification. LC-MS: m/z 245.2 [M+H]+at 5.37 RT (57.23% purity). Step-3: Synthesis of (E)-3-(2-cyclohexylvinyl)benzoic acid (VN-346) & (Z)-3-(2-cyclohexylvinyl)benzoic acid (VN-377). To a stirred solution of compound 4 (800 mg, mixture) in a mixture of THF/methanol (1:1, 6 mL) was added a solution of lithium hydroxide monohydride (413 mg, 9.84 mmol) in water (2 mL) at RT and stirred for 5 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (15 mL) and extracted with ether (2×10 mL). The organic layer was separated and the aqueous layer was acidified with 2 N HCl solutions to pH ˜3-4 and extracted with EtOAc (2×30 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to obtain the crude. The crude material was purified by normal phase preparative HPLC (Method A) to afford VN-346 (30 mg, 0.13 mmol) & VN-377 (25 mg, 0.11 mmol) as off white solids respectively. Analytical data of VN-367:1H NMR (400 MHz, DMSO-d6): δ 12.94 (br s, 1H), 7.92 (t, J=1.6 Hz, 1H), 7.76 (dt, J=7.7, 1.3 Hz, 1H), 7.65-7.61 (m, 1H), 7.42 (t, J=7.7 Hz, 1H), 6.47-6.41 (m, 1H), 6.36-6.28 (m, 1H), 2.19-2.09 (m, 1H), 1.82-1.69 (m, 4H), 1.68-1.61 (m, 1H), 1.36-1.11 (m, 5H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.87 (s, 1H), 7.77-7.71 (m, 1H), 7.62-7.58 (m, 1H), 7.42 (t, J=7.4 Hz, 1H), 6.42-6.36 (m, 1H), 6.32-6.24 (m, 1H), 2.17-2.05 (m, 1H), 1.76-1.55 (m, 5H), 1.32-1.06 (m, 5H). LC-MS: m/z 228.8 [M−H]−at 2.72 RT (99.57% purity). HPLC: 99.28%. Analytical data of VN-377:1H NMR (400 MHz, DMSO-d6): 12.96 (br s, 1H), 7.85-7.79 (m, 2H), 7.49 (d, J=4.9 Hz, 2H), 6.37 (d, J=11.7 Hz, 1H), 5.57 (dd, J=11.7, 10.2 Hz, 1H), 2.48-2.46 (m, 1H), 1.75-1.59 (m, 5H), 1.31-1.13 (m, 5H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.84-7.76 (m, 2H), 7.52-7.44 (m, 2H), 6.35 (d, J=11.8 Hz, 1H), 5.57 (dd, J=11.7, 10.2 Hz, 1H), 2.46-2.44 (m, 1H), 1.72-1.54 (m, 5H), 1.25-1.11 (m, 5H). LC-MS: m/z 228.8 [M−H]−at 2.66 RT (99.48% purity). HPLC: 99.19%. Preparation of VN-347 & VN-376. The synthetic strategy for preparing VN-347 and VN-376 is detailed in the scheme below. Step-1: Synthesis of Benzyltriphenylphosphonium bromide (2). To a stirred solution of (bromomethyl)benzene 1 (5 g, 29.07 mmol) in toluene (50 mL) was added triphenylphosphine (7.62 g, 29.07 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 6 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 2 (11 g, 25.38 mmol, 88%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.86 (m, 3H), 7.79-7.63 (m, 12H), 7.33-7.26 (m, 1H), 7.26-7.20 (m, 2H), 7.00-6.96 (m, 2H), 5.22-5.16 (m, 2H). Step-2: Synthesis of Methyl 3-styrylbenzoate (4). To a stirred solution of compound 2 (1.5 g, 3.47 mmol) in THF (10 mL) was added n-BuLi (2.5 M in hexanes, 1.53 mL, 3.82 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of methyl 3-formylbenzoate 3 (569 mg, 3.47 mmol) in THF (5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with saturated NH4Cl solution (30 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 10% EtOAc/n-hexanes) to afford compound 4 (650 mg, 2.73 mmol, 79%) as a mixture of cis and trans-isomers as white solid. This mixture (650 mg) was further purified by normal phase preparative HPLC (Method B) to afford 4E (200 mg) & 4Z (250 mg) as white solids respectively. Analytical data of 4E:1H NMR (400 MHz, CDCl3): δ 8.20 (t, J=1.8 Hz, 1H), 7.92 (dt, J=7.7, 1.4 Hz, 1H), 7.69 (dt, J=7.7, 1.3 Hz, 1H), 7.55-7.51 (m, 2H), 7.43 (t, J=7.7 Hz, 1H), 7.40-7.35 (m, 2H), 7.31-7.26 (m, 1H), 7.22-7.10 (m, 2H), 3.95 (s, 3H). LC-MS: m/z 239.2 [M+H]+at 4.63 RT (99.70% purity). Analytical data of 4Z:1H NMR (400 MHz, DMSO-d6): δ 7.86-7.76 (m, 2H), 7.48-7.38 (m, 2H), 7.30-7.22 (m, 3H), 7.21-7.17 (m, 2H), 6.77-6.66 (m, 2H), 3.80 (s, 3H). LC-MS: m/z 239.1 [M+H]+at 4.60 RT (97.98% purity). Step-3: Synthesis of Methyl 3-((1S,2S)-2-phenylcyclopropyl)benzoate (5E). To a stirred solution of compound 4E (150 mg, 0.63 mmol) in diethylether (10 mL) were added Pd(OAc)2(56 mg, 0.25 mmol) followed by diazomethane (20 mL) drop wise at −50° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was filtered through a pad of celite and the celite bed was washed with EtOAc (20 mL). The filtrate was concentrated under reduced pressure to obtain the crude. The crude material was purified by silica gel column chromatography (eluent: 5% EtOAc/n-hexanes) to afford compound 5E (130 mg, 0.51 mmol, 86%) as colorless syrup.1H NMR (400 MHz, DMSO-d6): δ 7.79-7.73 (m, 2H), 7.50-7.41 (m, 2H), 7.32-7.25 (m, 2H), 7.22-7.14 (m, 3H), 3.85 (s, 3H), 2.38-2.30 (m, 1H), 2.32-2.21 (m, 1H), 1.53-1.47 (m, 2H). LC-MS: m/z 253.3 [M+H]+at 4.70 RT (91.86% purity). Step-4: Synthesis of 3-((1S,2S)-2-phenylcyclopropyl)benzoic acid (VN-347). To a stirred solution of compound 5E (160 mg, 0.63 mmol) in a mixture of THF/methanol (1:1, 2 mL) was added a solution of lithium hydroxide monohydride (80 mg, 1.9 mmol) in water (1 mL) at RT and stirred for 6 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (15 mL) and extracted with ether (2×10 mL). The organic layer was separated and the aqueous layer was acidified with 2 N HCl solutions to pH ˜3-4 and extracted with EtOAc (2×20 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to obtain the crude. The crude material was triturated with n-hexanes (2×5 mL) and dried under vacuum to afford VN-347 (40 mg, 0.17 mmol, 26%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 12.91 (br s, 1H), 7.78-7.71 (m, 2H), 7.46-7.38 (m, 2H), 7.31-7.25 (m, 2H), 7.22-7.14 (m, 3H), 2.36-2.28 (m, 1H), 2.27-2.20 (m, 1H), 1.49 (t, J=7.4 Hz, 2H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.75-7.67 (m, 2H), 7.43-7.38 (m, 2H), 7.29-7.23 (m, 2H), 7.18-7.11 (m, 3H), 2.28-2.21 (m, 1H), 2.20-2.13 (m, 1H), 1.46 (t, J=7.3 Hz, 2H). LC-MS: m/z 236.8 [M−H]−at 2.81 RT (98.07% purity). HPLC: 98.27%. Step-5: Synthesis of Methyl 3-((1R,2S)-2-phenylcyclopropyl)benzoate (5Z). To a stirred solution of compound 4Z (250 mg, 1.05 mmol) in diethylether (10 mL) were added Pd(OAc)2(93 mg, 0.42 mmol) followed by diazomethane (25 mL) drop wise at −50° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was filtered through a pad of celite and the celite bed was washed with EtOAc (20 mL). The filtrate was concentrated under reduced pressure to obtain the crude. The crude material was purified by silica gel column chromatography (eluent: 5% EtOAc/n-hexanes) followed by normal phase preparative HPLC (Method B) to afford compound 5Z (28 mg, 0.11 mmol, 11%) as colorless syrup. This material was not pure even after preparative HPLC and it is carried forward to the next step without further purification. LC-MS: m/z 253.1 [M+H]+at 4.52 RT (55.05% purity). Step-6: Synthesis of 3-((1R,2S)-2-phenylcyclopropyl)benzoic acid (VN-376). To a stirred solution of compound 5Z (25 mg, 0.1 mmol) in a mixture of THF/methanol (1:1, 2 mL) was added a solution of lithium hydroxide monohydride (12 mg, 0.3 mmol) in water (0.5 mL) at RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (10 mL) and extracted with ether (2×5 mL). The organic layer was separated and the aqueous layer was acidified with 2 N HCl solutions to pH ˜3-4 and extracted with EtOAc (2×10 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford VN-376 (15 mg, 0.06 mmol, 65%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 12.79 (br s, 1H), 7.61-7.56 (m, 2H), 7.21-7.13 (m, 2H), 7.10-7.05 (m, 2H), 7.02-6.96 (m, 3H), 2.60-2.53 (m, 2H), 1.56 (q, J=6.3 Hz, 1H), 1.48-1.40 (m, 1H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.58-7.48 (m, 2H), 7.21-7.13 (m, 2H), 7.07-7.01 (m, 2H), 6.99-6.91 (m, 3H), 2.53-2.51 (m, 2H), 1.52-1.38 (m, 2H). LC-MS: m/z 236.8 [M−H]−at 2.71 RT (99.62% purity). HPLC: 99.50%. Preparation of VN-348. The synthetic strategy for preparing VN-348 is detailed in the scheme below. Step-1: Synthesis of Methyl 3-(1H-indol-2-yl)benzoate (3). To a stirred solution of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole 1 (200 mg, 0.93 mmol) and methyl 3-bromobenzoate 2 (271 mg, 1.12 mmol) in 1,4-dioxane (3 mL) was added a solution of sodium carbonate (296 mg, 2.79 mmol) in water (1 mL) at RT and purged with argon for 5 min. Then Pd(dppf)Cl2·CH2Cl2(76 mg, 0.09 mmol) was added at RT. The reaction mixture was heated to 100° C. and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was cooled to RT, filtered through a pad of celite and the celite bed was washed with EtOAc (20 mL). The filtrate was concentrated under reduced pressure to obtain the crude. The crude material was purified by silica gel column chromatography (eluent: 10% EtOAc/n-hexanes) to afford compound 3 (185 mg, 0.74 mmol, 79%) as pale yellow liquid.1H NMR (400 MHz, CDCl3): δ 8.47 (br s, 1H), 8.33 (t, J=1.6 Hz, 1H), 7.98 (dt, J=7.7, 1.3 Hz, 1H), 7.89-7.86 (m, 1H), 7.66-7.62 (m, 1H), 7.52 (t, J=7.8 Hz, 1H), 7.44-7.40 (m, 1H), 7.24-7.20 (m, 1H), 7.16-7.11 (m, 1H), 6.91 (dd, J=2.1, 0.9 Hz, 1H), 3.97 (s, 3H). LC-MS: m/z 252.1 [M+H]+at 4.24 RT (73.82% purity). Step-2: Synthesis of Methyl 3-(1-methyl-1H-indol-2-yl)benzoate (4). To a stirred solution of compound 3 (100 mg, 0.4 mmol) in DMF (4 mL) was added cesium carbonate (195 mg, 0.6 mmol) at 0° C. under inert atmosphere and stirred at RT for 30 min. Then iodomethane (0.03 mL, 0.52 mmol) was added at 0° C.; warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with water (20 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 2% EtOAc/n-hexanes) to afford compound 4 (75 mg, 0.28 mmol, 71%) as pale brown liquid.1H NMR (500 MHz, CDCl3): δ 8.22-8.19 (m, 1H), 8.10-8.06 (m, 1H), 7.73-7.69 (m, 1H), 7.65 (d, J=8.1 Hz, 1H), 7.58-7.53 (m, 1H), 7.38 (d, J=8.1 Hz, 1H), 7.29-7.25 (m, 1H), 7.16 (t, J=7.5 Hz, 1H), 6.62 (s, 1H), 3.95 (s, 3H), 3.76 (s, 3H). Step-3: Synthesis of 3-(1-methyl-1H-indol-2-yl)benzoic acid (VN-348). To a stirred solution of compound 4 (75 mg, 0.28 mmol) in a mixture of THF/methanol (1:1, 4 mL) was added a solution of lithium hydroxide monohydride (36 mg, 0.85 mmol) in water (2 mL) at RT and stirred for 12 h. The progress of the reaction was monitored by TLC, after the completion, the volatiles were removed under reduced pressure. The aqueous layer was washed with EtOAc (10 mL) to remove water insoluble organic impurities. The organic layer was separated and the aqueous layer was acidified with 1 N HCl solutions to pH ˜3-2. The precipitated solid was extracted into EtOAc (2×20 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to obtain the crude. The crude material was passed through a pad of silica gel to remove colour impurities and dried under vacuum to afford VN-348 (45 mg, 0.18 mmol, 63%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 13.16 (br s, 1H), 8.11 (t, J=1.5 Hz, 1H), 8.01 (dt, J=7.7, 1.4 Hz, 1H), 7.88-7.83 (m, 1H), 7.68-7.63 (m, 1H), 7.61-7.57 (m, 1H), 7.51 (dd, J=8.3, 0.8 Hz, 1H), 7.24-7.18 (m, 1H), 7.12-7.06 (m, 1H), 6.64 (d, J=0.8 Hz, 1H), 3.76 (s, 3H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.05 (s, 1H), 7.99-7.95 (m, 1H), 7.82-7.78 (m, 1H), 7.67-7.61 (m, 1H), 7.56 (d, J=7.8 Hz, 1H), 7.45 (d, J=8.2 Hz, 1H), 7.22-7.16 (m, 1H), 7.09-7.03 (m, 1H), 6.60 (s, 1H), 3.69 (s, 3H). LC-MS: m/z 249.9 [M−H]−at 2.66 RT (98.80% purity). HPLC: 99.44%. Preparation of VN-349. The synthetic strategy for preparing VN-349 is detailed in the scheme below. Step-1: Synthesis of Methyl 3-(1H-indol-2-yl)benzoate (3). To a stirred solution of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole 1 (200 mg, 0.93 mmol) and methyl 3-bromobenzoate 2 (271 mg, 1.12 mmol) in 1,4-dioxane (3 mL) was added a solution of sodium carbonate (296 mg, 2.79 mmol) in water (1 mL) at RT and purged with argon for 5 min. Then Pd(dppf)Cl2·CH2Cl2(76 mg, 0.09 mmol) was added at RT. The reaction mixture was heated to 100° C. and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was cooled to RT, filtered through a pad of celite and the celite bed was washed with EtOAc (20 mL). The filtrate was concentrated under reduced pressure to obtain the crude. The crude material was purified by silica gel column chromatography (eluent: 10% EtOAc/n-hexanes) to afford compound 3 (185 mg, 0.74 mmol, 79%) as pale yellow liquid.1H NMR (400 MHz, CDCl3): δ 8.47 (br s, 1H), 8.33 (t, J=1.6 Hz, 1H), 7.98 (dt, J=7.7, 1.3 Hz, 1H), 7.89-7.86 (m, 1H), 7.66-7.62 (m, 1H), 7.52 (t, J=7.8 Hz, 1H), 7.44-7.40 (m, 1H), 7.24-7.20 (m, 1H), 7.16-7.11 (m, 1H), 6.91 (dd, J=2.1, 0.9 Hz, 1H), 3.97 (s, 3H). LC-MS: m/z 252.1 [M+H]+at 4.24 RT (73.82% purity). Step-2: Synthesis of 3-(1H-indol-2-yl)benzoic acid (VN-349). To a stirred solution of compound 3 (80 mg, 0.32 mmol) in a mixture of THF/methanol (1:1, 4 mL) was added a solution of lithium hydroxide monohydride (27 mg, 0.64 mmol) in water (2 mL) at RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the volatiles were removed under reduced pressure. The aqueous layer was washed with EtOAc (10 mL) to remove water insoluble organic impurities. The organic layer was separated and the aqueous layer was acidified with 1 N HCl solutions to pH ˜3-2. The precipitated solid was extracted into EtOAc (2×20 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 50% EtOAc/n-hexanes) to afford VN-349 (30 mg, 0.13 mmol, 40%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 11.70 (s, 1H), 8.43 (t, J=1.6 Hz, 1H), 8.13-8.08 (m, 1H), 7.87 (dt, J=7.8, 1.2 Hz, 1H), 7.61-7.53 (m, 2H), 7.41 (dd, J=8.0, 0.8 Hz, 1H), 7.14-7.08 (m, 1H), 7.03-6.96 (m, 2H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.35 (s, 1H), 8.07-8.00 (m, 1H), 7.85 (d, J=7.9 Hz, 1H), 7.61-7.51 (m, 2H), 7.40 (d, J=8.2 Hz, 1H), 7.14-7.06 (m, 1H), 7.03-6.96 (m, 1H), 6.92 (s, 1H). LC-MS: m/z 235.8 [M−H]−at 2.42 RT (98.72% purity). HPLC: 99.29%. Preparation of VN-351 & VN-380. The synthetic strategy for preparing VN-351 and VN-380 is detailed in the scheme below. Step-1: Synthesis of (3-(methoxycarbonyl)benzyl)triphenylphosphonium bromide (2). To a stirred solution of methyl 3-(bromomethyl)benzoate 1 (5 g, 21.83 mmol) in toluene (50 mL) was added triphenylphosphine (5.72 g, 21.83 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 6 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 2 (8.8 g, 17.91 mmol, 83%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.84 (m, 4H), 7.79-7.72 (m, 6H), 7.71-7.64 (m, 6H), 7.54-7.52 (m, 1H), 7.41 (t, J=7.8 Hz, 1H), 7.31-7.27 (m, 1H), 5.29-5.23 (m, 2H), 3.77 (s, 3H). Step-2: Synthesis of Methyl (E)-3-(2-(oxazol-4-yl)vinyl)benzoate (4). To a stirred solution of compound 2 (1.5 g, 3.06 mmol) in THF (25 mL) was added n-BuLi (2.5 M in hexanes, 3.06 mL, 7.65 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of oxazole-4-carbaldehyde 3 (356 mg, 3.67 mmol) in THF (5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 5 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with saturated NH4Cl solution (30 mL) and extracted with EtOAc (2×40 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by combi-flash column chromatography eluting with 10% EtOAc/n-hexanes to afford compound 4 (265 mg, 1.16 mmol, 38%) as a mixture of cis and trans-isomers as pale yellow semi solid. The mixture was taken to next step without further purification.1H NMR (400 MHz, DMSO-d6): δ 8.43-8.41 (m, 0.3H), 8.37-8.34 (m, 0.6H), 8.22 (d, J=0.8 Hz, 0.3H), 8.13-8.08 (m, 1H), 8.02 (s, 0.6H), 7.88-7.79 (m, 2H), 7.56-7.46 (m, 1H), 7.34-7.22 (m, 0.7H), 6.70 (d, J=12.7 Hz, 0.7H), 6.51 (d, J=12.5 Hz, 0.7H), 3.89-3.84 (m, 3H). LC-MS: m/z 230.0 [M+H]+at 3.34 RT (59.44% purity); m/z 230.0 [M+H]+at 3.40 RT (39.50% purity). Step-3: Synthesis of (E)-3-(2-(oxazol-4-yl)vinyl)benzoic acid (VN-351) & (Z)-3-(2-(oxazol-4-yl)vinyl)benzoic acid (VN-380). To a stirred solution of compound 4 (250 mg, mixture) in a mixture of THF/methanol (1:1, 4 mL) was added a solution of lithium hydroxide monohydride (137 mg, 3.27 mmol) in water (2 mL) at RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (15 mL) and extracted with ether (2×10 mL). The organic layer was separated; the aqueous layer was acidified with 1 N HCl solutions at 0° C. to pH ˜3-4. The obtained solid was filtered and dried under vacuum to afford the desired compound 5 (200 mg). The crude material was purified by preparative HPLC (Method U) to afford VN-351 (20 mg, 0.09 mmol, 8%) & VN-380 (30 mg, 0.14 mmol, 12%) as white solids respectively. Analytical data of VN-352:1H NMR (400 MHz, DMSO-d6): δ 13.01 (br s, 1H), 8.41 (s, 1H), 8.20 (s, 1H), 8.10 (s, 1H), 7.86-7.79 (m, 2H), 7.50 (t, J=7.7 Hz, 1H), 7.32-7.20 (m, 2H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.30 (s, 1H), 8.14 (s, 1H), 8.04 (s, 1H), 7.84-7.77 (m, 2H), 7.50 (t, J=7.7 Hz, 1H), 7.27-7.14 (m, 2H). LC-MS: m/z 216.1 [M+H]+at 1.97 RT (99.67% purity). HPLC: 98.79%. Analytical data of VN-380:1H NMR (400 MHz, DMSO-d6): δ 12.92 (br s, 1H), 8.35 (s, 1H), 8.04 (t, J=1.6 Hz, 1H), 7.99 (s, 1H), 7.83 (dt, J=7.8, 1.3 Hz, 1H), 7.79-7.75 (m, 1H), 7.46 (t, J=7.7 Hz, 1H), 6.69 (d, J=12.5 Hz, 1H), 6.48 (d, J=12.5 Hz, 1H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.23 (s, 1H), 8.00 (s, 1H), 7.89 (s, 1H), 7.83-7.79 (m, 1H), 7.72-7.68 (m, 1H), 7.45 (t, J=7.7 Hz, 1H), 6.67 (d, J=12.5 Hz, 1H), 6.47 (d, J=12.5 Hz, 1H). LC-MS: m/z 216.1 [M+H]+at 1.92 RT (99.85% purity). HPLC: 99.78%. Preparation of VN-353. The synthetic strategy for preparing VN-353 is detailed in the scheme below. Step-1: Synthesis of (3-(methoxycarbonyl)benzyl)triphenylphosphonium bromide (2). To a stirred solution of methyl 3-(bromomethyl)benzoate 1 (5 g, 21.83 mmol) in toluene (50 mL) was added triphenylphosphine (5.72 g, 21.83 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 6 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 2 (8.8 g, 17.91 mmol, 83%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.84 (m, 4H), 7.79-7.72 (m, 6H), 7.71-7.64 (m, 6H), 7.54-7.52 (m, 1H), 7.41 (t, J=7.8 Hz, 1H), 7.31-7.27 (m, 1H), 5.29-5.23 (m, 2H), 3.77 (s, 3H). Step-2: Synthesis of Methyl (E)-3-(2-(pyridin-2-yl)vinyl)benzoate (4E). To a stirred solution of compound 2 (1.5 g, 3.06 mmol) in THF (15 mL) was added n-BuLi (2.5 M in hexanes, 1.35 mL, 3.37 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of picolinaldehyde 3 (327 mg, 3.06 mmol) in THF (5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 6 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with saturated NH4Cl solution (30 mL) and extracted with EtOAc (2×40 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography eluting with 30% EtOAc/n-hexanes to afford compound 4 (600 mg). This mixture was purified by normal phase preparative HPLC (Method R) to afford compound 4E (80 mg, 0.33 mmol, 11%) and corresponding cis-isomer 4Z (60 mg, 0.25 mmol, 8%) as colorless syrups respectively. The compound 4E (trans-isomer) was taken to next step. Analytical data of compound 4E:1H NMR (500 MHz, DMSO-d6): δ 8.70 (d, J=4.6 Hz, 1H), 8.24 (s, 1H), 8.12 (br t, J=7.2 Hz, 1H), 7.99-7.85 (m, 4H), 7.61 (t, J=7.8 Hz, 1H), 7.56-7.51 (m, 1H), 7.47 (d, J=16.2 Hz, 1H), 3.90 (s, 3H). LC-MS: m/z 240.1 [M+H]+at 1.74 RT (99.55% purity). Analytical data of compound 4Z:1H NMR (400 MHz, DMSO-d6): δ 8.59 (d, J=4.3 Hz, 1H), 7.94 (s, 1H), 7.87-7.75 (m, 2H), 7.59-7.55 (m, 1H), 7.47-7.40 (m, 1H), 7.40-7.35 (m, 1H), 7.29 (d, J=7.9 Hz, 1H), 6.96 (d, J=12.7 Hz, 1H), 6.77 (d, J=12.5 Hz, 1H), 3.82 (s, 3H). LC-MS: m/z 240.1 [M+H]+at 3.61 RT (96.41% purity). Step-3: Synthesis of (E)-3-(2-(pyridin-3-yl)vinyl)benzoic acid (VN-353). To a stirred solution of compound 4E (60 mg, 0.25 mmol) in a mixture of THF/methanol (1:1, 2.4 mL) was added a solution of lithium hydroxide monohydride (32 mg, 0.75 mmol) in water (0.6 mL) at RT and stirred for 6 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (30 mL) and washed with Et2O (2×5 mL). The organic layer was separated; the aqueous layer was acidified with 1N HCl solutions to pH ˜4. The obtained solid was filtered, washed with water (2 mL), n-pentane (2×5 mL) and dried under vacuum to afford VN-353 (15 mg, 0.07 mmol, 25%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 13.06 (br s, 1H), 8.61-8.57 (m, 11H), 8.20 (t, J=1.6 Hz, 1H), 7.94-7.86 (m, 2H), 7.81 (td, J=7.7, 1.9 Hz, 1H), 7.74 (d, J=16.2 Hz, 1H), 7.62-7.58 (m, 1H), 7.54 (t, J=7.7 Hz, 1H), 7.40 (d, J=16.1 Hz, 1H), 7.30-7.25 (m, 11H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.56-8.53 (m, 1H), 8.16 (t, J=1.4 Hz, 1H), 7.92-7.85 (m, 2H), 7.79 (td, J=7.7, 1.8 Hz, 1H), 7.68 (d, J=16.2 Hz, 1H), 7.62-7.58 (m, 1H), 7.53 (t, J=7.7 Hz, 1H), 7.35 (d, J=16.2 Hz, 1H), 7.30-7.25 (m, 1H). LC-MS: m/z 223.7 [M−H]˜ at 1.79 RT (99.70% purity). HPLC: 99.81%. Preparation of VN-354 & VN-381. The synthetic strategy for preparing VN-354 and VN-381 is detailed in the scheme below. Step-1: Synthesis of (3-(methoxycarbonyl)benzyl)triphenylphosphonium bromide (2). To a stirred solution of methyl 3-(bromomethyl)benzoate 1 (2 g, 8.73 mmol) in toluene (20 mL) was added triphenylphosphine (2.29 g, 8.73 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 16 h. Then the solid was filtered, washed with toluene (2×10 mL), n-hexanes (2×10 mL) and dried under vacuum to afford compound 2 (3.5 g, 7.13 mmol, 83%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.84 (m, 4H), 7.79-7.72 (m, 6H), 7.71-7.64 (m, 6H), 7.54-7.52 (m, 1H), 7.41 (t, J=7.8 Hz, 1H), 7.31-7.27 (m, 1H), 5.29-5.23 (m, 2H), 3.77 (s, 3H). Step-2: Synthesis of Methyl (E)-3-(2-(pyridin-3-yl)vinyl)benzoate (4). To a stirred solution of compound 2 (1 g, 2.04 mmol) in THF (15 mL) was added n-BuLi (2.5 M in hexanes, 0.9 mL, 2.24 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of nicotinaldehyde 3 (218 mg, 2.04 mmol) in THF (5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with saturated NH4Cl solution (20 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography eluting with 30% EtOAc/n-hexanes to afford compound 4 (350 mg, 1.46 mmol, 73%) as a mixture of cis and trans-isomers as colorless syrup. The mixture was taken to next step without further purification. LC-MS: m/z 240.0 [M+H]+at 3.49 RT (38.99% purity). Step-3: Synthesis of (E)-3-(2-(pyridin-3-yl)vinyl)benzoic acid (VN-354) & (Z)-3-(2-(pyridin-3-yl)vinyl)benzoic acid (VN-381). To a stirred solution of compound 4 (340 mg, mixture) in a mixture of THF/methanol (1:1, 4 mL) was added a solution of lithium hydroxide monohydride (179 mg, 4.27 mmol) in water (1.5 mL) at RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (30 mL) and washed with Et2O (2×10 mL). The organic layer was separated; the aqueous layer was acidified with 1N HCl solutions to pH ˜3-4. The aqueous layer was lyophilized to afford the desired compound 5 (270 mg). This crude material was purified by normal phase preparative HPLC (Method Y) to afford VN-354 (80 mg, 0.35 mmol, 25%) & VN-381 (80 mg, 0.35 mmol, 25%) as off white solids respectively. Analytical data of VN-354:1H NMR (400 MHz, DMSO-d6): δ 13.06 (br s, 1H), 8.82 (d, J=1.8 Hz, 1H), 8.48 (dd, J=4.7, 1.4 Hz, 1H), 8.18 (s, 1H), 8.10 (dt, J=8.0, 1.8 Hz, 1H), 7.90-7.84 (m, 2H), 7.57-7.47 (m, 2H), 7.46-7.35 (m, 2H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.74 (s, 1H), 8.43 (d, J=4.6 Hz, 1H), 8.16-8.05 (m, 2H), 7.91-7.82 (m, 2H), 7.53 (t, J=7.8 Hz, 1H), 7.48-7.39 (m, 2H), 7.36-7.29 (m, 1H). LC-MS: m/z 226.1 [M+H]+at 1.50 RT (99.67% purity). HPLC: 98.03%. Analytical data of VN-381:1H NMR (400 MHz, DMSO-d6): δ 12.94 (br s, 1H), 8.44-8.35 (m, 2H), 7.83-7.76 (m, 2H), 7.58 (dt, J=7.9, 1.6 Hz, 1H), 7.45-7.37 (m, 2H), 7.30 (dd, J=7.8, 4.8 Hz, 1H), 6.87 (d, J=12.4 Hz, 1H), 6.73 (d, J=12.4 Hz, 1H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.39-8.29 (m, 2H), 7.79 (td, J=4.4, 1.6 Hz, 1H), 7.72 (s, 1H), 7.60-7.55 (m, 1H), 7.41 (d, J=5.1 Hz, 2H), 7.30 (dd, J=7.9, 4.9 Hz, 1H), 6.84 (d, J=12.4 Hz, 1H), 6.71 (d, J=12.2 Hz, 1H). LC-MS: m/z 226.1 [M+H]+at 1.48 RT (97.24% purity). HPLC: 99.80%. Preparation of VN-355 & VN-387. The synthetic strategy for preparing VN-355 and VN-387 is detailed in the scheme below. Step-1: Synthesis of (3-(methoxycarbonyl)benzyl)triphenylphosphonium bromide (2). To a stirred solution of methyl 3-(bromomethyl)benzoate 1 (5 g, 21.83 mmol) in toluene (50 mL) was added triphenylphosphine (5.72 g, 21.83 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 6 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 2 (8.8 g, 17.91 mmol, 83%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.84 (m, 4H), 7.79-7.72 (m, 6H), 7.71-7.64 (m, 6H), 7.54-7.52 (m, 1H), 7.41 (t, J=7.8 Hz, 1H), 7.31-7.27 (m, 1H), 5.29-5.23 (m, 2H), 3.77 (s, 3H). Step-2: Synthesis of Methyl (E)-3-(2-(pyridin-4-yl)vinyl)benzoate (4E) & methyl (Z)-3-(2-(pyridin-4-yl)vinyl)benzoate (4Z). To a stirred solution of compound 2 (1.5 g, 3.06 mmol) in THF (15 mL) was added n-BuLi (2.5 M in hexanes, 1.35 mL, 3.37 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of isonicotinaldehyde 3 (327 mg, 3.06 mmol) in THF (5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 6 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with saturated NH4Cl solution (30 mL) and extracted with EtOAc (2×40 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography eluting with 30% EtOAc/n-hexanes to afford compound 4 (900 mg). This mixture was purified by normal phase preparative HPLC (Method S) to afford compound 4E (200 mg, 0.84 mmol, 27%) and corresponding cis-isomer 4Z (260 mg, 1.09 mmol, 34%) as an off white solids respectively. Analytical data of compound 4E:1H NMR (500 MHz, DMSO-d6): δ 8.85-8.83 (m, 2H), 8.32 (s, 1H), 8.16 (br d, J=5.2 Hz, 2H), 8.08-7.97 (m, 3H), 7.68-7.58 (m, 2H), 3.90 (s, 3H). LC-MS: m/z 240.1 [M+H]+at 3.47 RT (99.90% purity). Analytical data of compound 4Z:1H NMR (500 MHz, DMSO-d6): δ 8.66 (d, J=6.4 Hz, 2H), 7.92-7.88 (m, 1H), 7.84 (s, 1H), 7.56 (d, J=6.4 Hz, 2H), 7.52-7.45 (m, 2H), 7.17 (d, J=12.2 Hz, 1H), 6.86 (d, J=12.8 Hz, 1H), 3.83 (s, 3H). LC-MS: m/z 240.1 [M+H]+at 3.42 RT (98.47% purity). Step-3: Synthesis of (E)-3-(2-(pyridin-4-yl)vinyl)benzoic acid (VN-355). To a stirred solution of compound 4E (200 mg, 0.84 mmol) in a mixture of THF/methanol (1:1, 6 mL) was added a solution of lithium hydroxide monohydride (105 mg, 2.51 mmol) in water (2 mL) at RT and stirred for 6 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (30 mL) and washed with Et2O (2×10 mL). The organic layer was separated; the aqueous layer was acidified with 1N HCl solutions to pH ˜4. The obtained solid was filtered, washed with water (5 mL), n-pentane (2×5 mL) and dried under vacuum to afford VN-355 (50 mg, 0.22 mmol, 28%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 13.09 (br s, 1H), 8.56 (br d, J=4.9 Hz, 2H), 8.22 (t, J=1.5 Hz, 1H), 7.94-7.86 (m, 2H), 7.68-7.51 (m, 4H), 7.35 (d, J=16.6 Hz, 1H). LC-MS: m/z 226.1 [M+H]+at 1.51 RT (97.36% purity). HPLC: 99.26%. Step-4: Synthesis of (Z)-3-(2-(pyridin-4-yl)vinyl)benzoic acid (VN-387). To a stirred solution of compound 4Z (250 mg, 1.05 mmol) in a mixture of THF/methanol (1:1, 3 mL) was added a solution of lithium hydroxide monohydride (132 mg, 3.14 mmol) in water (1 mL) at RT and stirred for 6 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (30 mL) and washed with Et2O (2×10 mL). The organic layer was separated; the aqueous layer was acidified with 1N HCl solutions to pH ˜4. The obtained solid was filtered, washed with water (5 mL), n-pentane (2×10 mL) and dried under vacuum to afford VN-387 (80 mg, 0.35 mmol, 34%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 12.95 (br s, 1H), 8.49-8.43 (m, 2H), 7.85-7.76 (m, 2H), 7.45-7.41 (m, 2H), 7.17-7.12 (m, 2H), 6.92 (d, J=12.3 Hz, 1H), 6.70 (d, J=12.3 Hz, 1H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.41 (d, J=5.5 Hz, 2H), 7.83-7.78 (m, 1H), 7.74 (s, 1H), 7.42 (d, J=4.9 Hz, 2H), 7.14 (d, J=5.8 Hz, 2H), 6.90 (d, J=12.3 Hz, 1H), 6.68 (d, J=12.3 Hz, 1H). LC-MS: m/z 226.2 [M+H]+at 1.43 RT (99.75% purity). HPLC: 99.47%. Preparation of VN-359. The synthetic strategy for preparing VN-359 is detailed in the scheme below. Step-1: Synthesis of Benzyltriphenylphosphonium bromide (2). To a stirred solution of (bromomethyl)benzene 1 (1.39 mL, 11.69 mmol) in toluene (20 mL) was added triphenylphosphine (3.06 g, 11.69 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 16 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×15 mL) and dried under vacuum to afford compound 2 (4.7 g, 10.85 mmol, 97%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.86 (m, 3H), 7.79-7.63 (m, 12H), 7.33-7.26 (m, 1H), 7.26-7.20 (m, 2H), 7.00-6.96 (m, 2H), 5.22-5.16 (m, 2H). Step-2: Synthesis of Methyl (E)-2-methoxy-5-styrylbenzoate (4E). To a stirred solution of compound 2 (1 g, 2.31 mmol) in THF (15 mL) was added n-BuLi (1.6 M in hexanes, 1.59 mL, 2.55 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of methyl 5-formyl-2-methoxybenzoate 3 (449 mg, 2.31 mmol) in THF (5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 6 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with saturated NH4Cl solution (20 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography eluting with 10% EtOAc/n-hexanes to afford compound 4 (630 mg). This mixture was purified by normal phase preparative HPLC (Method S) to afford compound 4E (200 mg, 0.75 mmol, 32%) and corresponding cis-isomer 4Z (230 mg, 0.86 mmol, 37%) as off white solids respectively. The compound 4E (trans-isomer) was taken to next step. Analytical data of compound 4E:1H NMR (400 MHz, CDCl3): δ 7.97 (d, J=2.5 Hz, 1H), 7.61 (dd, J=8.7, 2.4 Hz, 1H), 7.51-7.47 (m, 2H), 7.39-7.32 (m, 2H), 7.28-7.27 (m, 0.4H), 7.26-7.23 (m, 0.6H), 7.04 (d, J=2.3 Hz, 2H), 6.98 (d, J=8.7 Hz, 1H), 3.93 (s, 3H), 3.93 (s, 3H). LC-MS: m/z 269.1 [M+H]+at 4.12 RT (99.77% purity). Analytical data of compound 4Z:1H NMR (400 MHz, DMSO-d6): δ 7.52 (d, J=2.3 Hz, 1H), 7.34 (dd, J=8.7, 2.3 Hz, 1H), 7.31-7.26 (m, 2H), 7.25-7.20 (m, 3H), 7.03 (d, J=8.7 Hz, 1H), 6.64-6.55 (m, 2H), 3.79 (s, 3H), 3.72 (s, 3H)._LC-MS: m/z 269.2 [M+H]+at 4.36 RT (97.30% purity). Step-3: Synthesis of (E)-2-hydroxy-5-styrylbenzoic acid (VN-359). To a stirred solution of compound 4E (150 mg, 0.56 mmol) in CH2Cl2(7 mL) was added boron tribromide (1 M in CH2Cl2, 1.12 mL, 1.12 mmol) at −50° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 4 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with ice cold water (20 mL) and extracted with CH2Cl2(2×20 mL). The combined organic extracts were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to obtain the crude (˜120 mg). This lot was combined with another lot (35 mg, crude) and was purified by triturations with CH2Cl2/n-pentane (1:4, 10 mL) and dried under vacuum to afford VN-359 (21 mg, 0.09 mmol, 16%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 11.54 (br s, 1H), 7.97 (d, J=2.3 Hz, 1H), 7.80 (dd, J=8.7, 2.1 Hz, 1H), 7.58 (d, J=7.3 Hz, 2H), 7.36 (t, J=7.6 Hz, 2H), 7.27-7.21 (m, 2H), 7.15-7.09 (m, 1H), 6.97 (d, J=8.5 Hz, 1H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.94 (d, J=2.3 Hz, 1H), 7.78 (dd, J=8.7, 2.4 Hz, 1H), 7.56 (d, J=7.3 Hz, 2H), 7.34 (t, J=7.6 Hz, 2H), 7.27-7.16 (m, 2H), 7.11-7.04 (m, 1H), 6.95 (d, J=8.7 Hz, 1H). LC-MS: m/z 238.8 [M−H]−at 2.87 RT (98.04% purity). HPLC: 98.83%. Preparation of VN-362. The synthetic strategy for preparing VN-362 is detailed in the scheme below. Step-1: Synthesis of 4-(2-(3-iodophenoxy)ethyl)morpholine (3). To a stirred solution of 3-iodophenol 1 (1 g, 4.54 mmol) in DMF (10 mL) were added 4-(2-chloroethyl)morpholine hydrochloride 2 (1.01 g, 5.45 mmol) and potassium carbonate (1.25 g, 9.09 mmol) at RT under inert atmosphere. The reaction mixture was heated to 80° C. and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was cooled to RT; quenched with water (50 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with water (30 mL) and brine (20 mL). The organic layer was separated, dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 3 (1.1 g, 3.3 mmol, 73%) as colorless liquid.1H NMR (400 MHz, CDCl3): δ 7.31-7.27 (m, 2H), 7.02-6.96 (m, 1H), 6.89-6.85 (m, 1H), 4.08 (t, J=5.6 Hz, 2H), 3.75-3.71 (m, 4H), 2.78 (t, J=5.6 Hz, 2H), 2.59-2.54 (m, 4H). LC-MS: m/z 334.1 [M+H]+at 1.72 RT (66.36% purity). Step-2: Synthesis of Methyl 3-vinylbenzoate (4). To a stirred solution of methyl 3-bromobenzoate 6 (3 g, 13.95 mmol) in 1,2-dimethoxyethane (40 mL) were added 4,4,5,5-tetramethyl-2-vinyl-1,3,2-dioxaborolane 7 (2.15 g, 13.95 mmol), potassium carbonate (1.92 g, 13.95 mmol) and water (20 mL) at RT. The reaction mixture was purged with argon for 5 min. Then Pd(PPh3)4(1.61 g, 1.39 mmol) was added to the reaction mixture at RT; gradually heated to 80° C. and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was cooled to RT, filtered through a pad of celite and the celite bed was washed with EtOAc (20 mL). The filtrate was concentrated under reduced pressure. The residue was diluted with water (50 mL) and extracted with EtOAc (2×60 mL). The combined organic extracts were washed with brine (30 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography eluting with 5% EtOAc/n-hexanes to afford compound 4 (900 mg, 5.55 mmol, 40%) as colorless liquid.1H NMR (400 MHz, CDCl3): δ 8.08 (t, J=1.8 Hz, 1H), 7.92 (dt, J=7.7, 1.4 Hz, 1H), 7.59 (dt, J=7.7, 1.3 Hz, 1H), 7.40 (t, J=7.7 Hz, 1H), 6.75 (dd, J=17.6, 10.9 Hz, 1H), 5.83 (dd, J=17.6, 0.6 Hz, 1H), 5.33 (d, J=10.9 Hz, 1H), 3.93 (s, 3H). Step-3: Synthesis of Methyl (E)-3-(3-(2-morpholinoethoxy)styryl)benzoate (5). To a stirred solution of compound 3 (500 mg, 1.5 mmol) in acetonitrile (7 mL) were added compound 4 (292 mg, 1.8 mmol) and triethylamine (0.42 mL, 3.0 mmol) in a sealed tube at RT under inert atmosphere. The reaction mixture was purged with argon for 5 min. Then Pd(PPh3)4(260 mg, 0.22 mmol) was added to the reaction mixture at RT; the vessel was sealed, gradually heated to 80° C. and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was cooled to RT; diluted with EtOAc (30 mL) and filtered through a pad of celite and the celite bed was washed with EtOAc (20 mL). The filtrate was concentrated under reduced pressure. The crude material was purified by silica gel column chromatography eluting with 40% EtOAc/n-hexanes to afford compound 5 (320 mg, 0.87 mmol, 58%) as pale yellow oily liquid. The compound was not pure even after column purification. This material was taken to next step without further purification. LC-MS: m/z 368.3 [M+H]+at 2.05 RT (34.03% purity). Step-4: Synthesis of (E)-3-(3-(2-morpholinoethoxy)styryl)benzoic acid (VN-362). To a stirred solution of compound 5 (320 mg, impure) in a mixture of THF/methanol (1:1, 8 mL) was added a solution of lithium hydroxide monohydride (110 mg, 2.61 mmol) in water (4 mL) at RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (20 mL) and washed with EtOAc (2×10 mL) to remove insoluble organic impurities. The organic layer was separated; the aqueous layer was neutralized with saturated aqueous citric acid solution and extracted with EtOAC (2×30 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by triturating with Et2O (2×5 mL) and dried under vacuum to afford VN-362 (50 mg, 0.14 mmol, 16%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 12.69 (br s, 1H), 8.15 (s, 1H), 7.89-7.80 (m, 2H), 7.51 (t, J=7.7 Hz, 1H), 7.43-7.35 (m, 1H), 7.33-7.24 (m, 3H), 7.23-7.17 (m, 1H), 6.87 (dd, J=8.0, 1.6 Hz, 1H), 4.14 (t, J=5.8 Hz, 2H), 3.62-3.56 (m, 4H), 2.72 (t, J=5.7 Hz, 2H), 2.56-2.51 (m, 4H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.12 (s, 1H), 7.86-7.79 (m, 2H), 7.50 (t, J=7.7 Hz, 1H), 7.38-7.16 (m, 5H), 6.88-6.83 (m, 1H), 4.12 (t, J=5.7 Hz, 2H), 3.60-3.55 (m, 4H), 2.71 (t, J=5.6 Hz, 2H), 2.54-2.50 (m, 4H). LC-MS: m/z 354.3 [M+H]+at 1.87 RT (96.40% purity). HPLC: 96.72%. Preparation of VN-363. The synthetic strategy for preparing VN-363 is detailed in the scheme below. Step-1: Synthesis of 4-(2-(4-iodophenoxy)ethyl)morpholine (3). To a stirred solution of 4-iodophenol 1 (1 g, 4.54 mmol) in DMF (20 mL) were added 4-(2-chloroethyl)morpholine hydrochloride 2 (1.01 g, 5.45 mmol) and potassium carbonate (1.25 g, 9.09 mmol) at RT under inert atmosphere. The reaction mixture was heated to 80° C. and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was cooled to RT; quenched with water (50 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with water (30 mL) and brine (20 mL). The organic layer was separated, dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography eluting with 10% EtOAc/n-hexanes to afford compound 3 (1.1 g, 3.3 mmol, 73%) as pink liquid.1H NMR (500 MHz, CDCl3): δ 7.56 (d, J=8.7 Hz, 2H), 6.69 (d, J=9.3 Hz, 2H), 4.08 (t, J=5.8 Hz, 2H), 3.76-3.71 (m, 4H), 2.79 (t, J=5.5 Hz, 2H), 2.59-2.55 (m, 4H). LC-MS: m/z 334.0 [M+H]+at 3.59 RT (98.67% purity). Step-2: Synthesis of Methyl 3-vinylbenzoate (4). To a stirred solution of methyl 3-bromobenzoate 6 (3 g, 13.95 mmol) in 1,2-dimethoxyethane (40 mL) were added 4,4,5,5-tetramethyl-2-vinyl-1,3,2-dioxaborolane 7 (2.15 g, 13.95 mmol), potassium carbonate (1.92 g, 13.95 mmol) and water (20 mL) at RT. The reaction mixture was purged with argon for 5 min. Then Pd(PPh3)4(1.61 g, 1.39 mmol) was added to the reaction mixture at RT; gradually heated to 80° C. and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was cooled to RT, filtered through a pad of celite and the celite bed was washed with EtOAc (20 mL). The filtrate was concentrated under reduced pressure. The residue was diluted with water (50 mL) and extracted with EtOAc (2×60 mL). The combined organic extracts were washed with brine (30 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography eluting with 5% EtOAc/n-hexanes to afford compound 4 (900 mg, 5.55 mmol, 40%) as colorless liquid.1H NMR (400 MHz, CDCl3): δ 8.08 (t, J=1.8 Hz, 1H), 7.92 (dt, J=7.7, 1.4 Hz, 1H), 7.59 (dt, J=7.7, 1.3 Hz, 1H), 7.40 (t, J=7.7 Hz, 1H), 6.75 (dd, J=17.6, 10.9 Hz, 1H), 5.83 (dd, J=17.6, 0.6 Hz, 1H), 5.33 (d, J=10.9 Hz, 1H), 3.93 (s, 3H). Step-3: Synthesis of Methyl (E)-3-(4-(2-morpholinoethoxy)styryl)benzoate (5). To a stirred solution of compound 3 (500 mg, 1.5 mmol) in acetonitrile (7 mL) were added compound 4 (292 mg, 1.8 mmol) and triethylamine (0.42 mL, 3.0 mmol) in a sealed tube at RT under inert atmosphere. The reaction mixture was purged with argon for 5 min. Then Pd(PPh3)4(260 mg, 0.22 mmol) was added to the reaction mixture at RT; the vessel was sealed and gradually heated to 80° C. and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was cooled to RT; diluted with EtOAc (30 mL) and filtered through a pad of silica gel to remove the catalyst. The solvent was concentrated under reduced pressure to obtain the crude. The crude material was purified by silica gel column chromatography eluting with 30% EtOAc/n-hexanes to afford compound 5 (280 mg, 0.76 mmol, 51%) as pale yellow oily liquid. The compound was not pure even after column purification. This material was carried to next step without further purification. LC-MS: m/z 368.2 [M+H]+at 2.05 RT (38.01% purity). Step-4: Synthesis of (E)-3-(4-(2-morpholinoethoxy)styryl)benzoic acid (VN-363). To a stirred solution of compound 5 (280 mg, impure) in a mixture of THF/methanol (1:1, 6 mL) was added a solution of lithium hydroxide monohydride (96 mg, 2.29 mmol) in water (3 mL) at RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (20 mL) and washed with EtOAc (2×10 mL) to remove water insoluble organic impurities. The organic layer was separated; the aqueous layer was neutralized with saturated aqueous citric acid solution. The obtained solid was extracted into CH2Cl2(30 mL). The solvent was concentrated under reduced pressure to obtain the crude. The crude material was purified by triturating with Et2O (2×5 mL) followed by EtOH (2 mL) and dried under vacuum to afford VN-363 (50 mg, 0.14 mmol, 19%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 12.99 (br s, 1H), 8.11 (s, 1H), 7.81 (br t, J=6.3 Hz, 2H), 7.57 (d, J=8.7 Hz, 2H), 7.48 (t, J=7.7 Hz, 1H), 7.32-7.15 (m, 2H), 6.97 (d, J=8.8 Hz, 2H), 4.11 (t, J=5.7 Hz, 2H), 3.61-3.54 (m, 4H), 2.70 (t, J=5.7 Hz, 2H), 2.48-2.44 (m, 4H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.06 (s, 1H), 7.82-7.76 (m, 2H), 7.55 (d, J=8.8 Hz, 2H), 7.47 (t, J=7.7 Hz, 1H), 7.27-7.09 (m, 2H), 6.94 (d, J=8.7 Hz, 2H), 4.10 (t, J=5.6 Hz, 2H), 3.61-3.55 (m, 4H), 2.74 (t, J=5.5 Hz, 2H), 2.56-2.52 (m, 2H). LC-MS: m/z 354.3 [M+H]+at 1.82 RT (96.46% purity). HPLC: 97.08%. Preparation of VN-384. The synthetic strategy for preparing VN-384 is detailed in the scheme below. Step-1: Synthesis of 4-(2-(2-iodophenoxy)ethyl)morpholine (3). To a stirred solution of 2-iodophenol 1 (1 g, 4.54 mmol) in DMF (20 mL) were added 4-(2-chloroethyl)morpholine hydrochloride 2 (1.01 g, 5.45 mmol) and potassium carbonate (1.25 g, 9.09 mmol) at RT under inert atmosphere. The reaction mixture was heated to 80° C. and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was cooled to RT; quenched with water (50 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with water (30 mL) and brine (20 mL). The organic layer was separated, dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 3 (1.2 g, 5.11 mmol, 79%) as colorless liquid.1H NMR (400 MHz, CDCl3): δ 7.77 (dd, J=7.8, 1.5 Hz, 1H), 7.31-7.26 (m, 1H), 6.81 (dd, J=8.2, 1.3 Hz, 1H), 6.71 (td, J=7.6, 1.4 Hz, 1H), 4.16 (t, J=5.6 Hz, 2H), 3.75-3.72 (m, 4H), 2.88 (t, J=5.6 Hz, 2H), 2.68-2.64 (m, 4H). LC-MS: m/z 334.1 [M+H]+at 1.64 RT (99.48% purity). Step-2: Synthesis of Methyl 3-vinylbenzoate (4). To a stirred solution of methyl 3-bromobenzoate 6 (3 g, 13.95 mmol) in 1,2-dimethoxyethane (40 mL) were added 4,4,5,5-tetramethyl-2-vinyl-1,3,2-dioxaborolane 7 (2.15 g, 13.95 mmol), potassium carbonate (1.92 g, 13.95 mmol) and water (20 mL) at RT. The reaction mixture was purged with argon for 5 min. Then Pd(PPh3)4(1.61 g, 1.39 mmol) was added to the reaction mixture at RT; gradually heated to 80° C. and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was cooled to RT, filtered through a pad of celite and the celite bed was washed with EtOAc (20 mL). The filtrate was concentrated under reduced pressure. The residue was diluted with water (50 mL) and extracted with EtOAc (2×60 mL). The combined organic extracts were washed with brine (30 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography eluting with 5% EtOAc/n-hexanes to afford compound 4 (900 mg, 5.55 mmol, 40%) as colorless liquid.1H NMR (400 MHz, CDCl3): δ 8.08 (t, J=1.8 Hz, 1H), 7.92 (dt, J=7.7, 1.4 Hz, 1H), 7.59 (dt, J=7.7, 1.3 Hz, 1H), 7.40 (t, J=7.7 Hz, 1H), 6.75 (dd, J=17.6, 10.9 Hz, 1H), 5.83 (dd, J=17.6, 0.6 Hz, 1H), 5.33 (d, J=10.9 Hz, 1H), 3.93 (s, 3H). Step-3: Synthesis of Methyl (E)-3-(2-(2-morpholinoethoxy)styryl)benzoate (5). To a stirred solution of compound 3 (500 mg, 1.5 mmol) in acetonitrile (5 mL) were added compound 4 (292 mg, 1.8 mmol) and triethylamine (0.42 mL, 3.0 mmol) in a sealed tube at RT under inert atmosphere. The reaction mixture was purged with argon for 5 min. Then Pd(PPh3)4(173 mg, 0.15 mmol) was added to the reaction mixture at RT; the vessel was sealed, gradually heated to 80° C. and stirred for 16 h. The progress of the reaction was monitored by TLC; the starting material was not consumed completely, then the reaction mixture was cooled to RT, another lot of Pd(PPh3)4(87 mg, 0.07 mmol) was added; heated to 80° C. and stirred for 3 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was cooled to RT; diluted with EtOAc (30 mL), filtered through a pad of celite and the celite bed was washed with EtOAc (20 mL). The filtrate was concentrated under reduced pressure. The crude material was purified by silica gel column chromatography eluting with 5% MeOH/CH2Cl2to afford compound 5 (300 mg, 0.82 mmol, 54%) as brown syrupy liquid. The compound was not pure even after column purification. This material was taken to next step without further purification.1H NMR (400 MHz, CDCl3): δ 8.18 (t, J=1.8 Hz, 1H), 7.91 (dt, J=7.8, 1.4 Hz, 1H), 7.71-7.66 (m, 2H), 7.59 (dd, J=7.7, 1.6 Hz, 1H), 7.55-7.45 (m, 2H), 7.45-7.40 (m, 1H), 7.25-7.22 (m, 1H), 7.18 (d, J=16.6 Hz, 1H), 7.02-6.96 (m, 1H), 6.91 (dd, J=8.3, 0.8 Hz, 1H), 4.20 (t, J=5.7 Hz, 2H), 3.95 (s, 3H), 3.77-3.71 (m, 4H), 2.89 (t, J=5.7 Hz, 2H), 2.67-2.62 (m, 4H). LC-MS: m/z 368.2 [M+H]+at 2.04 RT (82.65% purity). Step-4: Synthesis of (E)-3-(2-(2-morpholinoethoxy)styryl)benzoic acid (VN-384). To a stirred solution of compound 5 (250 mg, impure) in a mixture of THF/methanol (1:1, 8 mL) was added a solution of lithium hydroxide monohydride (86 mg, 2.04 mmol) in water (4 mL) at RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (20 mL) and washed with EtOAc (2×10 mL) to remove water insoluble organic impurities. The organic layer was separated; the aqueous layer was neutralized with saturated aqueous citric acid solution and extracted into CH2Cl2(2×20 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by triturating with Et2O (2×3 mL) and dried under vacuum to afford VN-384 (80 mg, 0.23 mmol, 34%) as an off white solid.1H NMR (500 MHz, DMSO-d6): δ 13.03 (br s, 1H), 8.11 (s, 1H), 7.83 (d, J=7.5 Hz, 1H), 7.79 (br d, J=7.5 Hz, 1H), 7.71-7.66 (m, 1H), 7.54-7.47 (m, 2H), 7.42-7.36 (m, 1H), 7.30-7.24 (m, 1H), 7.07 (d, J=8.1 Hz, 1H), 6.99 (t, J=7.2 Hz, 1H), 4.18 (t, J=5.5 Hz, 2H), 3.62-3.56 (m, 4H), 2.79 (t, J=5.5 Hz, 2H), 2.57-2.53 (m, 4H);1H NMR (500 MHz, DMSO-d6, D2O Exc.): δ 8.08 (s, 1H), 7.82 (d, J=8.1 Hz, 1H), 7.77 (d, J=8.1 Hz, 1H), 7.66 (dd, J=7.5, 1.2 Hz, 1H), 7.53-7.46 (m, 2H), 7.37-7.31 (m, 1H), 7.29-7.22 (m, 1H), 7.04 (d, J=8.1 Hz, 1H), 6.98 (t, J=7.5 Hz, 1H), 4.16 (t, J=5.5 Hz, 2H), 3.60-3.54 (m, 4H), 2.79 (t, J=5.2 Hz, 2H), 2.56-2.54 (m, 4H). LC-MS: m/z 354.3 [M+H]+at 1.90 RT (99.24% purity). HPLC: 98.04%. Preparation of VN-365 & VN-385. The synthetic strategy for preparing VN-365 and VN-385 is detailed in the scheme below. Step-1: Synthesis of (3-(methoxycarbonyl)benzyl)triphenylphosphonium bromide (2). To a stirred solution of methyl 3-(bromomethyl)benzoate 1 (5 g, 21.83 mmol) in toluene (50 mL) was added triphenylphosphine (5.72 g, 21.83 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 6 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 2 (8.8 g, 17.91 mmol, 83%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.84 (m, 4H), 7.79-7.72 (m, 6H), 7.71-7.64 (m, 6H), 7.54-7.52 (m, 1H), 7.41 (t, J=7.8 Hz, 1H), 7.31-7.27 (m, 1H), 5.29-5.23 (m, 2H), 3.77 (s, 3H). Step-2: Synthesis of Methyl (E)-3-(2-(thiazol-2-yl)vinyl)benzoate (4). To a stirred solution of compound 2 (1 g, 2.04 mmol) in THF (10 mL) was added n-BuLi (2.0 M in hexanes, 1.12 mL, 2.24 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of thiazole-2-carbaldehyde 3 (231 mg, 2.04 mmol) in THF (5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with saturated NH4Cl solution (20 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography eluting with 20% EtOAc/n-hexanes to afford compound 4 (380 mg, 1.55 mmol, 76%) as a mixture of cis and trans-isomers as colorless syrup. The mixture was taken to next step without further purification. LC-MS: m/z 246.0 [M+H]+at 3.47 RT (68.38% purity) & m/z 246.3 [M+H]+at 3.59 RT (19.02% purity). Step-3: Synthesis of (E)-3-(2-(thiazol-2-yl)vinyl)benzoic acid (VN-365) & (Z)-3-(2-(thiazol-2-yl)vinyl)benzoic acid (VN-385). To a stirred solution of compound 4 (370 mg, mixture) in a mixture of THF/methanol (1:1, 4 mL) was added a solution of lithium hydroxide monohydride (190 mg, 4.53 mmol) in water (2 mL) at RT and stirred for 6 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (30 mL) and washed with Et2O (2×10 mL). The organic layer was separated; the aqueous layer was acidified with 1N HCl solutions to pH ˜3-4 and extracted with EtOAc (2×20 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to obtain the desired compound 5 (280 mg). The crude material was purified by normal phase preparative HPLC (Method V) to afford VN-366 (35 mg, 0.15 mmol, 10%) & VN-393 (60 mg, 0.26 mmol, 17%) as off white solids respectively. Analytical data of VN-365:1H NMR (400 MHz, DMSO-d6): δ 13.07 (br s, 1H), 8.20 (t, J=1.6 Hz, 1H), 7.98 (dt, J=7.8, 1.3 Hz, 1H), 7.92-7.87 (m, 2H), 7.73 (d, J=3.3 Hz, 1H), 7.59 (d, J=1.1 Hz, 2H), 7.54 (t, J=7.8 Hz, 1H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.16 (t, J=1.6 Hz, 1H), 7.96-7.87 (m, 2H), 7.85 (d, J=3.3 Hz, 1H), 7.67 (d, J=3.3 Hz, 1H), 7.57-7.51 (m, 3H). LC-MS: m/z 232.1 [M+H]+at 2.05 RT (98.56% purity). HPLC: 99.36%. Analytical data of VN-385:1H NMR (400 MHz, DMSO-d6): δ 12.99 (br s, 1H), 8.05 (t, J=1.6 Hz, 1H), 7.93 (dt, J=7.7, 1.2 Hz, 1H), 7.82 (d, J=3.3 Hz, 1H), 7.81-7.77 (m, 1H), 7.63 (d, J=3.3 Hz, 1H), 7.54 (t, J=7.7 Hz, 1H), 7.02 (d, J=12.3 Hz, 1H), 6.94 (d, J=12.7 Hz, 1H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.00 (s, 1H), 7.93-7.89 (m, 1H), 7.77 (d, J=3.3 Hz, 1H), 7.71-7.67 (m, 1H), 7.57-7.51 (m, 2H), 7.03 (d, J=12.2 Hz, 1H), 6.91 (d, J=12.2 Hz, 1H). LC-MS: m/z 232.1 [M+H]+at 1.98 RT (99.82% purity). HPLC: 99.74%. Preparation of VN-366 & VN-383. The synthetic strategy for preparing VN-367 and VN-394 is detailed in the scheme below. Step-1: Synthesis of (3-(methoxycarbonyl)benzyl)triphenylphosphonium bromide (2). To a stirred solution of methyl 3-(bromomethyl)benzoate 1 (1 g, 4.37 mmol) in toluene (10 mL) was added triphenylphosphine (1.14 g, 4.37 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 16 h. Then the solid was filtered, washed with toluene (2×10 mL), n-hexanes (2×10 mL) and dried under vacuum to afford compound 2 (1.7 g, 3.47 mmol, 81%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.84 (m, 4H), 7.79-7.72 (m, 6H), 7.71-7.64 (m, 6H), 7.54-7.52 (m, 1H), 7.41 (t, J=7.8 Hz, 1H), 7.31-7.27 (m, 1H), 5.29-5.23 (m, 2H), 3.77 (s, 3H). Step-2: Synthesis of Methyl (E)-3-(2-(thiazol-4-yl)vinyl)benzoate (4). To a stirred solution of compound 2 (1.3 g, 2.65 mmol) in THF (10 mL) was added n-BuLi (1.6 M in hexanes, 1.8 mL, 2.88 mmol) at −78° C. under inert atmosphere and stirred at the same temperature for 30 min. The reaction mixture was gradually warmed to RT and stirred for further 30 min. Then a solution of thiazole-4-carbaldehyde 3 (271 mg, 2.4 mmol) in THF (5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 4 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with saturated NH4Cl solution (20 mL) at −78° C. and gradually warmed to RT. Then the mixture was diluted with water (20 mL) and extracted with EtOAc (2×40 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by column purification eluting with 2% EtOAc/n-hexanes to afford compound 4 (438 mg, 1.79 mmol, 74%) as a mixture of cis and trans-isomers as pale yellow liquid. The mixture was taken to next step without further purification. LC-MS: m/z 246.0 [M+H]+at 3.56 RT (28.18% purity) & m/z 246.0 [M+H]+at 3.67 RT (27.18% purity). Step-3: Synthesis of (E)-3-(2-(thiazol-4-yl)vinyl)benzoic acid (VN-366) & (Z)-3-(2-(thiazol-4-yl)vinyl)benzoic acid (VN-383). To a stirred solution of compound 4 (50 mg, mixture) in a mixture of THF/methanol (1:1, 4 mL) was added a solution of lithium hydroxide monohydride (26 mg, 0.61 mmol) in water (2 mL) at RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (10 mL) and washed with EtOAC (2×5 mL) to remove water insoluble organic impurities. The organic layer was separated; the aqueous layer was neutralized with 1N HCl solutions. The obtained solid was extracted into EtOAc (20 mL). The solvent was removed under reduced pressure followed by triturations with n-pentane (2×5 mL) and dried under vacuum to afford the desired compound 5 (25 mg). This lot was combined with another lot (SMB-MA1706-014, 200 mg) and was purified by preparative HPLC (Method W) to afford VN-366 (34 mg, 0.15 mmol) & VN-383 (15.5 mg, 0.07 mmol) as off white solids respectively. Analytical data of VN-366:1H NMR (400 MHz, DMSO-d6): δ 13.03 (br s, 1H), 9.15 (d, J=1.6 Hz, 1H), 8.14 (t, J=1.5 Hz, 1H), 7.85 (dd, J=7.7, 1.7 Hz, 2H), 7.75 (d, J=1.9 Hz, 1H), 7.53-7.51 (m, 1H), 7.50-7.47 (m, 1H), 7.46-7.41 (m, 1H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 9.08 (d, J=1.5 Hz, 1H), 8.09 (t, J=1.6 Hz, 1H), 7.85-7.81 (m, 2H), 7.72 (d, J=1.9 Hz, 1H), 7.53-7.47 (m, 1H), 7.44-7.35 (m, 2H). LC-MS: m/z 232.1 [M+H]+at 2.07 RT (98.45% purity). HPLC: 96.51%. Analytical data of VN-383:1H NMR (400 MHz, DMSO-d6): δ 12.89 (br s, 1H), 9.04 (d, J=1.9 Hz, 1H), 7.97 (t, J=1.6 Hz, 1H), 7.82 (dt, J=7.8, 1.4 Hz, 1H), 7.67 (dt, J=7.7, 1.4 Hz, 1H), 7.51 (d, J=1.9 Hz, 1H), 7.43 (t, J=7.7 Hz, 1H), 6.73 (s, 2H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.96 (d, J=2.0 Hz, 1H), 7.93 (t, J=1.6 Hz, 1H), 7.80 (dt, J=7.7, 1.4 Hz, 1H), 7.61 (dt, J=7.9, 1.4 Hz, 1H), 7.45-7.40 (m, 2H), 6.71 (s, 2H). LC-MS: m/z 232.1 [M+H]+at 2.01 RT (99.71% purity). HPLC: 99.75%. Preparation of VN-367 & VN-386. The synthetic strategy for preparing VN-367 and VN-386 is detailed in the scheme below. Step-1: Synthesis of (3-(methoxycarbonyl)benzyl)triphenylphosphonium bromide (2). To a stirred solution of methyl 3-(bromomethyl)benzoate 1 (1 g, 4.37 mmol) in toluene (10 mL) was added triphenylphosphine (1.14 g, 4.37 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 16 h. Then the solid was filtered, washed with toluene (2×10 mL), n-hexanes (2×10 mL) and dried under vacuum to afford compound 2 (1.7 g, 3.47 mmol, 81%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.84 (m, 4H), 7.79-7.72 (m, 6H), 7.71-7.64 (m, 6H), 7.54-7.52 (m, 1H), 7.41 (t, J=7.8 Hz, 1H), 7.31-7.27 (m, 1H), 5.29-5.23 (m, 2H), 3.77 (s, 3H). Step-2: Synthesis of Methyl (E)-3-(2-(thiazol-5-yl)vinyl)benzoate (4). To a stirred solution of compound 2 (1.3 g, 2.65 mmol) in THF (10 mL) was added n-BuLi (1.6 M in hexanes, 1.8 mL, 2.89 mmol) at −78° C. under inert atmosphere and stirred at the same temperature for 30 min. The reaction mixture was gradually warmed to RT and stirred for further 30 min. Then a solution of thiazole-5-carbaldehyde 3 (0.2 mL, 2.41 mmol) in THF (5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with saturated NH4Cl solution (20 mL) at −78° C. and gradually warmed to RT. Then the mixture was diluted with water (20 mL) and extracted with EtOAc (2×40 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography eluting with 2% EtOAc/n-hexanes to afford compound 4 (400 mg, 1.63 mmol, 62%) as a mixture of cis and trans-isomers as pale yellow liquid. The mixture was taken to next step without further purification. LC-MS: m/z 246.1 [M+H]+at 2.37 RT (29.67% purity) & m/z 246.1 [M+H]+at 2.44 RT (40.16% purity). Step-3: Synthesis of (E)-3-(2-(thiazol-5-yl)vinyl)benzoic acid (VN-367) & (Z)-3-(2-(thiazol-5-yl)vinyl)benzoic acid (VN-386). To a stirred solution of compound 4 (50 mg, mixture) in a mixture of THF/methanol (1:1, 2 mL) was added a solution of lithium hydroxide monohydride (26 mg, 0.61 mmol) in water (1 mL) at RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (10 mL) and washed with EtOAC (2×5 mL) to remove water insoluble organic impurities. The organic layer was separated; the aqueous layer was neutralized with 1N HCl solutions. The obtained solid was extracted into EtOAc (20 mL). The solvent was removed under reduced pressure followed by triturations with Et2O (2×5 mL) and dried under vacuum to afford the desired compound 5 (35 mg). This lot was combined with another lot (SMB-MA1706-015, 300 mg) and was purified by preparative HPLC (Method X) to afford VN-367 (46 mg, 0.2 mmol) & VN-386 (98 mg, 0.42 mmol) as off white solids respectively. Analytical data of VN-367:1H NMR (400 MHz, DMSO-d6): δ 13.04 (br s, 1H), 9.02 (s, 1H), 8.15 (s, 1H), 8.03 (s, 1H), 7.87-7.82 (m, 2H), 7.64 (d, J=16.3 Hz, 1H), 7.51 (t, J=7.7 Hz, 1H), 7.11 (d, J=16.2 Hz, 1H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.95 (s, 1H), 8.09 (s, 1H), 8.00 (s, 1H), 7.85-7.80 (m, 2H), 7.58 (d, J=16.2 Hz, 1H), 7.50 (t, J=7.7 Hz, 1H), 7.08 (d, J=16.2 Hz, 1H). LC-MS: m/z 232.1 [M+H]+at 2.02 RT (98.68% purity). HPLC: 99.64%. Analytical data of VN-386:1H NMR (400 MHz, DMSO-d6): δ 13.02 (br s, 1H), 8.84 (s, 1H), 7.95-7.84 (m, 3H), 7.57-7.49 (m, 2H), 6.96 (d, J=11.9 Hz, 1H), 6.81 (d, J=11.9 Hz, 1H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.76 (s, 1H), 7.92-7.79 (m, 3H), 7.57-7.47 (m, 2H), 6.93 (d, J=12.0 Hz, 1H), 6.79 (d, J=11.8 Hz, 1H). LC-MS: m/z 232.1 [M+H]+at 2.00 RT (98.25% purity). HPLC: 98.87%. Preparation of VN-368 & VN-373. The synthetic strategy for preparing VN-369 and VN-374 is detailed in the scheme below. Step-1: Synthesis of (3-(methoxycarbonyl)benzyl)triphenylphosphonium bromide (2). To a stirred solution of methyl 3-(bromomethyl)benzoate 1 (5 g, 21.83 mmol) in toluene (50 mL) was added triphenylphosphine (5.72 g, 21.83 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 6 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 2 (8.8 g, 17.91 mmol, 83%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.84 (m, 4H), 7.79-7.72 (m, 6H), 7.71-7.64 (m, 6H), 7.54-7.52 (m, 1H), 7.41 (t, J=7.8 Hz, 1H), 7.31-7.27 (m, 1H), 5.29-5.23 (m, 2H), 3.77 (s, 3H). Step-2: Synthesis of Methyl (E)-3-(2-(thiophen-2-yl)vinyl)benzoate (4). To a stirred solution of compound 2 (400 mg, 0.82 mmol) in THE (10 mL) was added n-BuLi (2.5 M in hexanes, 0.36 mL, 0.9 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of thiophene-2-carbaldehyde 3 (91 mg, 0.82 mmol) in THF (2 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with saturated NH4Cl solution (15 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 10% EtOAc/n-hexanes) to afford compound 4 (90 mg, 0.37 mmol, 47%) as a mixture of cis and trans-isomers as colorless syrup. LC-MS: m/z 245.1 [M+H]+at 4.29 RT (44.77% purity) & m/z 245.4 [M+H]+at 4.39 RT (41.71% purity). Step-3: Synthesis of (E)-3-(2-(thiophen-2-yl)vinyl)benzoic acid (VN-368) & (Z)-3-(2-(thiophen-2-yl)vinyl)benzoic acid (VN-373). To a stirred solution of compound 4 (210 mg, mixture) in a mixture of THF (0.5 mL) and methanol (0.7 mL) was added a solution of lithium hydroxide monohydride (108 mg, 2.58 mmol) in water (0.5 mL) at RT and stirred for 6 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (15 mL) and extracted with ether (2×10 mL). The organic layer was separated and the aqueous layer was acidified with 2 N HCl solutions to pH ˜3-4 and extracted with EtOAc (2×20 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by normal phase preparative HPLC (Method C) to afford VN-368 (45 mg, 0.19 mmol, 23%) & VN-373 (35 mg, 0.15 mmol, 18%) as off white solids respectively. Analytical data of VN-368:1H NMR (400 MHz, DMSO-d6): δ 13.02 (br s, 1H), 8.11 (s, 1H), 7.82 (dd, J=7.8, 1.2 Hz, 2H), 7.58-7.45 (m, 3H), 7.29-7.26 (m, 1H), 7.08 (dd, J=5.0, 3.5 Hz, 1H), 7.03 (d, J=16.3 Hz, 1H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.05 (s, 1H), 7.79 (br d, J=7.8 Hz, 2H), 7.52-7.41 (m, 3H), 7.25 (d, J=3.3 Hz, 1H), 7.05 (dd, J=5.0, 3.6 Hz, 1H), 6.99 (d, J=16.3 Hz, 1H). LC-MS: m/z 228.7 [M−H]−at 2.63 RT (99.01% purity). HPLC: 97.03%. Analytical data of VN-373:1H NMR (400 MHz, DMSO-d6): δ 12.98 (br s, 1H), 7.93-7.86 (m, 2H), 7.60-7.48 (m, 2H), 7.35 (d, J=5.0 Hz, 1H), 7.09 (d, J=3.5 Hz, 1H), 6.96 (dd, J=5.1, 3.6 Hz, 1H), 6.86 (d, J=12.0 Hz, 1H), 6.63 (d, J=12.0 Hz, 1H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.91-7.83 (m, 2H), 7.55-7.47 (m, 2H), 7.26 (d, J=5.0 Hz, 1H), 7.05 (d, J=3.4 Hz, 1H), 6.93 (dd, J=5.1, 3.6 Hz, 1H), 6.83 (d, J=11.9 Hz, 1H), 6.60 (d, J=11.9 Hz, 1H). LC-MS: m/z 228.7 [M−H]−at 2.59 RT (97.55% purity). HPLC: 98.26%. Preparation of VN-369 & VN-374. The synthetic strategy for preparing VN-370 and VN-375 is detailed in the scheme below. Step-1: Synthesis of (3-(methoxycarbonyl)benzyl)triphenylphosphonium bromide (2). To a stirred solution of methyl 3-(bromomethyl)benzoate 1 (5 g, 21.83 mmol) in toluene (50 mL) was added triphenylphosphine (5.72 g, 21.83 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 6 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 2 (8.8 g, 17.91 mmol, 83%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.84 (m, 4H), 7.79-7.72 (m, 6H), 7.71-7.64 (m, 6H), 7.54-7.52 (m, 1H), 7.41 (t, J=7.8 Hz, 1H), 7.31-7.27 (m, 1H), 5.29-5.23 (m, 2H), 3.77 (s, 3H). Step-2: Synthesis of Methyl (E)-3-(2-(thiophen-3-yl)vinyl)benzoate (4). To a stirred solution of compound 2 (500 mg, 1.02 mmol) in THF (10 mL) was added n-BuLi (2.5 M in hexanes, 0.82 mL, 2.04 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 1 h. Then a solution of thiophene-3-carbaldehyde 3 (137 mg, 1.22 mmol) in THF (5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with saturated NH4Cl solution (20 mL) and extracted with EtOAc (2×25 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by combi-flash column chromatography (eluent: 5% EtOAc/n-hexanes) to afford compound 4 (100 mg, 0.41 mmol, 40%) as a mixture of cis and trans-isomers as colorless syrup. LC-MS: m/z 245.1 [M+H]+at 4.46 RT (62.36% purity). Step-3: Synthesis of (E)-3-(2-(thiophen-3-yl)vinyl)benzoic acid (VN-369) & (Z)-3-(2-(thiophen-3-yl)vinyl)benzoic acid (VN-374). To a stirred solution of compound 4 (100 mg, mixture) in a mixture of THF/methanol (1:1, 3 mL) was added a solution of lithium hydroxide monohydride (34 mg, 0.82 mmol) in water (1.5 mL) at 0° C. and stirred at RT for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (20 mL) and extracted with ether (2×5 mL). The organic layer was separated and the aqueous layer was acidified with 5 N HCl solutions to pH ˜3-2 and extracted with EtOAc (2×20 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by combi-flash column chromatography followed by preparative HPLC purification (Method Q) to afford VN-369 (30 mg, 0.13 mmol, 32%) & VN-374 (38 mg, 0.16 mmol, 40%) as off white solids respectively. Analytical data of VN-369:1H NMR (400 MHz, DMSO-d6): δ 13.03 (br s, 1H), 8.10 (s, 1H), 7.83-7.77 (m, 2H), 7.65-7.60 (m, 1H), 7.60-7.56 (m, 1H), 7.54-7.46 (m, 2H), 7.40-7.32 (m, 1H), 7.22-7.15 (m, 1H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.03 (s, 1H), 7.81-7.75 (m, 2H), 7.57-7.53 (m, 1H), 7.51-7.43 (m, 3H), 7.32-7.25 (m, 1H), 7.12-7.06 (m, 1H). LC-MS: m/z 228.7 [M−H]−at 2.53 RT (99.11% purity). HPLC: 98.96%. Analytical data of VN-374:1H NMR (500 MHz, DMSO-d6): δ 12.97 (br s, 1H), 7.88-7.80 (m, 2H), 7.52-7.37 (m, 4H), 6.77 (d, J=5.2 Hz, 1H), 6.70-6.59 (m, 2H);1H NMR (500 MHz, DMSO-d6, D2O Exc.): δ 7.85-7.79 (m, 2H), 7.50-7.41 (m, 2H), 7.39-7.34 (m, 2H), 6.74 (d, J=4.6 Hz, 1H), 6.67-6.58 (m, 2H). LC-MS: m/z 228.7 [M−H]−at 2.50 RT (98.50% purity). HPLC: 99.66%. Preparation of VN-390 & VN-372. The synthetic strategy for preparing VN-390 and VN-372 is detailed in the scheme below. Step-1: Synthesis of (3-(methoxycarbonyl)benzyl)triphenylphosphonium bromide (2). To a stirred solution of methyl 3-(bromomethyl)benzoate 1 (5 g, 21.83 mmol) in toluene (50 mL) was added triphenylphosphine (5.72 g, 21.83 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 6 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 2 (8.8 g, 17.91 mmol, 83%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.84 (m, 4H), 7.79-7.72 (m, 6H), 7.71-7.64 (m, 6H), 7.54-7.52 (m, 1H), 7.41 (t, J=7.8 Hz, 1H), 7.31-7.27 (m, 1H), 5.29-5.23 (m, 2H), 3.77 (s, 3H). Step-2: Synthesis of Methyl (E)-3-(4-fluorostyryl)benzoate (4). To a stirred solution of compound 2 (200 mg, 0.41 mmol) in THF (10 mL) was added n-BuLi (2.5 M in hexanes, 0.18 mL, 0.45 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 20 min. Then a solution of 4-fluorobenzaldehyde 3 (51 mg, 0.41 mmol) in THF (2 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with saturated NH4Cl solution (20 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to obtain the crude (˜200 mg). This lot was combined with another lot (SMB-MA1704-068, 300 mg crude) and was purified by silica gel column chromatography (eluent: 5% EtOAc/n-hexanes) to afford compound 4 (210 mg, 0.82 mmol, 80%) as a mixture of cis and trans-isomers as colorless liquid. LC-MS: m/z 257.2 [M+H]+at 4.48 RT (95.93% purity). Step-3: Synthesis of (E)-3-(4-fluorostyryl)benzoic acid (VN-390) & (Z)-3-(4-fluorostyryl)benzoic acid (VN-372). To a stirred solution of compound 4 (100 mg, mixture) in a mixture of THF/methanol (1:1, 1 mL) was added a solution of lithium hydroxide monohydride (25 mg, 0.58 mmol) in water (0.5 mL) at RT and stirred for 5 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (10 mL) and extracted with ether (2×10 mL). The organic layer was separated and the aqueous layer was acidified with 2 N HCl solutions to pH ˜3-4 and extracted with EtOAc (2×20 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to obtain the crude (˜100 mg). This batch was repeated with 100 mg to obtain the crude (˜100 mg). These crude materials (˜100 mg each) was combined and was purified by normal phase preparative HPLC (Method D) to afford VN-390 (40 mg, 0.16 mmol, 21%) & VN-372 (50 mg, 0.21 mmol, 26%) as off white solids respectively. Analytical data of VN-390:1H NMR (400 MHz, DMSO-d6): δ 13.02 (br s, 1H), 8.14 (s, 1H), 7.86-7.81 (m, 2H), 7.73-7.67 (m, 2H), 7.51 (t, J=7.7 Hz, 1H), 7.38-7.27 (m, 2H), 7.23 (t, J=8.9 Hz, 2H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.10 (s, 1H), 7.83 (t, J=7.2 Hz, 2H), 7.67 (dd, J=8.2, 5.8 Hz, 2H), 7.51 (t, J=7.7 Hz, 1H), 7.33-7.14 (m, 4H). LC-MS: m/z 240.7 [M−H]−at 2.80 RT (99.39% purity). HPLC: 99.22%. Analytical data of VN-372:1H NMR (400 MHz, DMSO-d6): δ 12.94 (br s, 1H), 7.81-7.77 (m, 2H), 7.44-7.36 (m, 2H), 7.26-7.20 (m, 2H), 7.14-7.07 (m, 2H), 6.70 (s, 2H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.78-7.70 (m, 2H), 7.43-7.35 (m, 2H), 7.20-7.14 (m, 2H), 7.07-6.99 (m, 2H), 6.66 (s, 2H). LC-MS: m/z 240.8 [M−H]−at 2.74 RT (99.18% purity). HPLC: 99.48%. Preparation of VN-371 & VN-379. The synthetic strategy for preparing VN-371 and VN-379 is detailed in the scheme below. Step-1: Synthesis of (3-(methoxycarbonyl)benzyl)triphenylphosphonium bromide (2). To a stirred solution of methyl 3-(bromomethyl)benzoate 1 (5 g, 21.83 mmol) in toluene (50 mL) was added triphenylphosphine (5.72 g, 21.83 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 6 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 2 (8.8 g, 17.91 mmol, 83%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.84 (m, 4H), 7.79-7.72 (m, 6H), 7.71-7.64 (m, 6H), 7.54-7.52 (m, 1H), 7.41 (t, J=7.8 Hz, 1H), 7.31-7.27 (m, 1H), 5.29-5.23 (m, 2H), 3.77 (s, 3H). Step-2: Synthesis of Methyl (E)-3-(4-chlorostyryl)benzoate (4E) & methyl (Z)-3-(4-chlorostyryl)benzoate (4Z). To a stirred solution of compound 2 (800 mg, 1.63 mmol) in THF (15 mL) was added n-BuLi (2.5 M in hexanes, 1.31 mL, 3.26 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 1 h. Then a solution of 4-chlorobenzaldehyde 3 (228 mg, 1.63 mmol) in THE (5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with saturated NH4Cl solution (20 mL) at 0° C. and extracted with EtOAc (2×25 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 10% EtOAc/n-hexanes) to afford a mixture of cis and trans-isomers as a pale yellow semi solid. This material was further purified by preparative HPLC (Method E) to afford compound 4E (80 mg, 0.29 mmol, 18%) & 4Z (90 mg, 0.33 mmol, 20%) as an off white solid and colorless liquid respectively. Analytical data of 4E:1H NMR (400 MHz, DMSO-d6): δ8.16 (s, 1H), 7.94-7.84 (m, 2H), 7.68 (d, J=8.5 Hz, 2H), 7.54 (t, J=7.7 Hz, 1H), 7.48-7.31 (m, 4H), 3.88 (s, 3H). LC-MS: [M+H]+not observed; no ionisation at 4.82 RT (98.97% purity). HPLC: 100.00%. Analytical data of 4Z:1H NMR (400 MHz, DMSO-de): δ 7.84-7.80 (m, 2H), 7.48-7.40 (m, 2H), 7.33 (d, J=8.5 Hz, 2H), 7.20 (d, J=8.4 Hz, 2H), 6.78-6.68 (m, 2H), 3.81 (s, 3H). LC-MS: m/z 273.2 [M+H]+at 4.79 RT (93.62% purity). HPLC: 100.00%. Step-3: Synthesis of (E)-3-(4-chlorostyryl)benzoic acid (VN-371). To a stirred solution of compound 4E (80 mg, 0.29 mmol) in a mixture of THE/methanol (1:1, 1 mL) was added a solution of lithium hydroxide monohydride (37 mg, 0.88 mmol) in water (0.5 mL) at 0° C. and stirred at RT for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (10 mL) and extracted with ether (2×5 mL). The organic layer was separated and the aqueous layer was acidified with 6 N HCl solutions to pH ˜3-2 and extracted with 10% MeOH/CH2Cl2(2×20 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford VN-371 (20 mg, 0.08 mmol, 26%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 8.15 (s, 1H), 7.87-7.80 (m, 2H), 7.67 (d, J=8.5 Hz, 2H), 7.52-7.42 (m, 3H), 7.41-7.29 (m, 2H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.11 (s, 1H), 7.83 (dt, J=7.7, 1.7 Hz, 2H), 7.65 (d, J=8.5 Hz, 2H), 7.49 (t, J=7.7 Hz, 1H), 7.42 (d, J=8.5 Hz, 2H), 7.37-7.25 (m, 2H). LC-MS: m/z 257.0 [M−H]−at 2.65 RT (98.69% purity). HPLC: 99.36%. Step-4: Synthesis of (Z)-3-(4-chlorostyryl)benzoic acid (VN-379). To a stirred solution of compound 4Z (80 mg, 0.29 mmol) in a mixture of THF/methanol (1:1, 1 mL) was added a solution of lithium hydroxide monohydride (37 mg, 0.88 mmol) in water (0.5 mL) at 0° C. and stirred at RT for 16 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (10 mL) and extracted with ether (2×5 mL). The organic layer was separated and the aqueous layer was acidified with 6 N HCl solutions to pH ˜3-2 and extracted with 10% MeOH/CH2Cl2(2×20 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford VN-379 (70 mg, 0.27 mmol, 92%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 7.82-7.77 (m, 2H), 7.42-7.37 (m, 2H), 7.35-7.30 (m, 2H), 7.21 (d, J=8.3 Hz, 2H), 6.77-6.72 (m, 1H), 6.71-6.65 (m, 1H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.80-7.71 (m, 2H), 7.41-7.36 (m, 2H), 7.31-7.25 (m, 2H), 7.20-7.14 (m, 2H), 6.75-6.68 (m, 1H), 6.68-6.62 (m, 1H). LC-MS: m/z 256.8 [M−H]−at 2.57 RT (98.16% purity). HPLC: 98.11%. Preparation of VN-375 & VN-378. The synthetic strategy for preparing VN-375 and VN-378 is detailed in the scheme below. Step-1: Synthesis of Benzyltriphenylphosphonium bromide (2). To a stirred solution of (bromomethyl)benzene 1 (5 g, 29.07 mmol) in toluene (50 mL) was added triphenylphosphine (7.62 g, 29.07 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 6 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 2 (11 g, 25.38 mmol, 88%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.86 (m, 3H), 7.79-7.63 (m, 12H), 7.33-7.26 (m, 1H), 7.26-7.20 (m, 2H), 7.00-6.96 (m, 2H), 5.22-5.16 (m, 2H). Step-2: Synthesis of Methyl (E)-2-styrylbenzoate (4). To a stirred solution of compound 2 (700 mg, 1.62 mmol) in THF (10 mL) was added n-BuLi (2.0 M in hexanes, 0.89 mL, 1.78 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 30 min. Then a solution of methyl 2-formylbenzoate 3 (266 mg, 1.62 mmol) in THF (5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 6 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was quenched with saturated NH4Cl solution (20 mL) and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine (15 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography (eluent: 5% EtOAc/n-hexanes) to afford compound 4 (210 mg, 0.88 mmol, 52%) as a mixture of cis and trans-isomers as colorless syrup. LC-MS: m/z 239.2 [M+H]+at 4.40 RT (28.23% purity) & m/z 239.0 [M+H]+at 4.51 RT (69.37% purity). Step-3: Synthesis of (E)-2-styrylbenzoic acid (VN-375) & (Z)-2-styrylbenzoic acid (VN-378). To a stirred solution of compound 4 (100 mg, mixture) in a mixture of THF/methanol (1:1, 3 mL) was added a solution of lithium hydroxide monohydride (53 mg, 1.26 mmol) in water (1.5 mL) at RT and stirred for 6 h. The progress of the reaction was monitored by TLC, after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (10 mL) and extracted with ether (2×7 mL). The organic layer was separated and the aqueous layer was acidified with 2 N HCl solutions to pH ˜3-4 and extracted with EtOAc (2×20 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to obtain the crude (˜100 mg). This crude material was combined with another lot (˜100 mg crude) and was purified by normal phase preparative HPLC (Method F) to afford VN-375 (80 mg, 0.36 mmol, 42%) & VN-378 (30 mg, 0.13 mmol, 16%) as off white solids respectively. Analytical data of VN-375:1H NMR (400 MHz, DMSO-d6): δ 13.03 (br s, 1H), 7.92 (d, J=16.3 Hz, 1H), 7.87-7.82 (m, 2H), 7.60-7.53 (m, 3H), 7.44-7.36 (m, 3H), 7.33-7.27 (m, 1H), 7.17 (d, J=16.3 Hz, 1H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.85-7.76 (m, 3H), 7.57-7.48 (m, 3H), 7.40-7.34 (m, 3H), 7.30-7.24 (m, 1H), 7.11 (d, J=16.3 Hz, 1H). LC-MS: m/z 222.8 [M−H]−at 2.35 RT (99.16% purity). HPLC: 99.60%. Analytical data of VN-378:1H NMR (400 MHz, DMSO-d6): δ 12.95 (br s, 1H), 7.96-7.90 (m, 1H), 7.40-7.34 (m, 2H), 7.20-7.09 (m, 4H), 7.05-6.99 (m, 3H), 6.61 (d, J=12.3 Hz, 1H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.92-7.87 (m, 1H), 7.39-7.32 (m, 2H), 7.18-7.06 (m, 4H), 7.02-6.94 (m, 3H), 6.59 (d, J=12.3 Hz, 1H). LC-MS: m/z 222.8 [M−H]−at 2.39 RT (96.78% purity). HPLC: 99.33%. Preparation of VN-384. The synthetic strategy for preparing VN-384 is detailed in the scheme below. Step-1: Synthesis of 2-(2-morpholinoethoxy)benzaldehyde (3). To a stirred solution of 2-hydroxybenzaldehyde 1 (1 g, 8.2 mmol) in DMF (20 mL) were added 4-(2-chloroethyl)morpholine hydrochloride 2 (1.83 g, 9.84 mmol) and potassium carbonate (2.26 g, 16.39 mmol) at RT under inert atmosphere. The reaction mixture was heated to 80° C. and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was cooled to RT; quenched with water (50 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with water (30 mL) and brine (20 mL). The organic layer was separated and dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 3 (1 g, 4.25 mmol, 52%) as brown liquid.1H NMR (400 MHz, CDCl3): δ 10.50 (d, J=0.9 Hz, 1H), 7.84 (dd, J=7.7, 1.8 Hz, 1H), 7.57-7.52 (m, 1H), 7.07-6.97 (m, 2H), 4.24 (t, J=5.6 Hz, 2H), 3.75-3.70 (m, 4H), 2.87 (t, J=5.6 Hz, 2H), 2.61-2.57 (m, 4H). LC-MS: m/z 236.0 [M+H]+at 2.61 RT (93.48% purity). Step-2: Synthesis of (3-(methoxycarbonyl)benzyl)triphenylphosphonium bromide (4). To a stirred solution of methyl 3-(bromomethyl)benzoate 6 (5 g, 21.83 mmol) in toluene (50 mL) was added triphenylphosphine (5.72 g, 21.83 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 6 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 4 (8.8 g, 17.91 mmol, 83%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.84 (m, 4H), 7.79-7.72 (m, 6H), 7.71-7.64 (m, 6H), 7.54-7.52 (m, 1H), 7.41 (t, J=7.8 Hz, 1H), 7.31-7.27 (m, 1H), 5.29-5.23 (m, 2H), 3.77 (s, 3H). Step-3: Synthesis of Methyl (E)-3-(2-(2-morpholinoethoxy)styryl)benzoate (5). To a stirred solution of compound 4 (800 mg, 1.63 mmol) in THF (20 mL) was added n-BuLi (2.5 M in hexanes, 1.63 mL, 4.08 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 1 h. Then a solution of compound 3 (384 mg, 1.63 mmol) in THF (5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with saturated NH4Cl solution (30 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by combi flash column chromatography to afford compound 5 (590 mg, 1.61 mmol, 98%) as a mixture of cis and trans-isomers as pale yellow semi solid. The mixture was taken to next step without further purification. LC-MS: m/z 368.2 [M+H]+at 4.04 RT (27.29% purity) & m/z 368.2 [M+H]+at 4.24 RT (26.32% purity). Step-4: Synthesis of (E)-3-(2-(2-morpholinoethoxy)styryl)benzoic acid hydrochloride (VN-384). To a stirred solution of compound 5 (350 mg, mixture) in methanol (3 mL) was added a solution of sodium hydroxide (114 mg, 2.86 mmol) in water (1 mL) at RT. The reaction mixture was heated to reflux temperature and stirred for 3 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was concentrated under reduced pressure. The residue was acidified with saturated citric acid solutions to pH ˜3-4 and extracted with 10% MeOH/CHCl3(2×20 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The obtained solid was diluted with water (5 mL), acidified with 6N HCl solution to pH˜2 and extracted with 10% MeOH/CHCl3(2×20 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The solid was recrystallized with CH3CN (2×5 mL), filtered and dried under vacuum to afford VN-384 (40 mg, 0.1 mmol, 11%) as an off white solid as HCl salt.1H NMR (400 MHz, DMSO-d6): δ 13.04 (br s, 1H), 10.88 (br s, 1H), 8.12 (s, 1H), 7.91-7.82 (m, 2H), 7.76 (br d, J=7.5 Hz, 1H), 7.57-7.49 (m, 2H), 7.37-7.27 (m, 2H), 7.12 (d, J=8.0 Hz, 1H), 7.05 (t, J=7.5 Hz, 1H), 4.50-4.48 (m, 2H), 4.01-3.96 (m, 2H), 3.81 (br t, J=11.7 Hz, 2H), 3.69-3.67 (m, 2H), 3.59-3.55 (m, 2H), 3.29-3.21 (m, 2H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 8.11 (s, 1H), 7.85-7.80 (m, 2H), 7.73 (dd, J=7.7, 1.3 Hz, 1H), 7.55-7.49 (m, 2H), 7.33-7.24 (m, 2H), 7.10-7.02 (m, 2H), 4.38 (t, J=4.9 Hz, 2H), 3.95-3.88 (m, 2H), 3.81-3.74 (m, 2H), 3.62-3.55 (m, 2H), 3.35-3.33 (m, 4H). LC-MS: m/z 354.3 [M+H]+at 1.85 RT (98.50% purity). HPLC: 97.70%. Preparation of VN-388. The synthetic strategy for preparing VN-388 is detailed in the scheme below. Step-1: Synthesis of 3-(2-morpholinoethoxy)benzaldehyde (3). To a stirred solution of 3-hydroxybenzaldehyde 1 (1 g, 8.2 mmol) in DMF (20 mL) were added 4-(2-chloroethyl)morpholine hydrochloride 2 (1.83 g, 9.84 mmol) and potassium carbonate (2.26 g, 16.39 mmol) at RT under inert atmosphere. The reaction mixture was heated to 80° C. and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was cooled to RT; quenched with water (50 mL) and extracted with EtOAc (2×30 mL). The combined organic extracts were washed with water (2×30 mL) and brine (20 mL). The organic layer was separated and dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford compound 3 (1.4 g, 5.95 mmol, 73%) as colorless liquid.1H NMR (400 MHz, CDCl3): δ 9.97 (s, 1H), 7.48-7.39 (m, 3H), 7.21-7.18 (m, 1H), 4.17 (t, J=5.6 Hz, 2H), 3.76-3.72 (m, 4H), 2.83 (t, J=5.6 Hz, 2H), 2.61-2.57 (m, 4H). LC-MS: m/z 236.0 [M+H]+at 2.64 RT (96.90% purity). Step-2: Synthesis of (3-(methoxycarbonyl)benzyl)triphenylphosphonium bromide (4). To a stirred solution of methyl 3-(bromomethyl)benzoate 7 (5 g, 21.83 mmol) in toluene (50 mL) was added triphenylphosphine (5.72 g, 21.83 mmol) at RT under inert atmosphere. The reaction mixture was heated to reflux temperature and stirred for 6 h. Then the solid was filtered, washed with toluene (2×20 mL), n-hexanes (2×20 mL) and dried under vacuum to afford compound 4 (8.8 g, 17.91 mmol, 83%) as white solid.1H NMR (400 MHz, DMSO-d6): δ 7.95-7.84 (m, 4H), 7.79-7.72 (m, 6H), 7.71-7.64 (m, 6H), 7.54-7.52 (m, 1H), 7.41 (t, J=7.8 Hz, 1H), 7.31-7.27 (m, 1H), 5.29-5.23 (m, 2H), 3.77 (s, 3H). Step-3: Synthesis of Methyl (E)-3-(3-(2-morpholinoethoxy)styryl)benzoate (5). To a stirred solution of compound 4 (1.5 g, 3.06 mmol) in THF (25 mL) was added n-BuLi (2.5 M in hexanes, 3.06 mL, 7.65 mmol) at −78° C. under inert atmosphere. The reaction mixture was gradually warmed to RT and stirred for 1 h. Then a solution of compound 3 (863 mg, 3.67 mmol) in THF (5 mL) was added at −78° C. The reaction mixture was gradually warmed to RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was quenched with saturated NH4Cl solution (30 mL) at 0° C. and extracted with EtOAc (2×40 mL). The combined organic extracts were washed with brine (20 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude material was purified by combi-flash column chromatography eluting with 50% EtOAc/n-hexanes to afford compound 5 (900 mg, 2.45 mmol, 80%) as a mixture of cis and trans-isomers as colorless semi solid. The mixture was taken to next step without further purification. LC-MS: m/z 368.2 [M+H]+at 4.03 RT (24.78% purity) & m/z 368.2 [M+H]+at 4.08 RT (20.04% purity). Step-4: Synthesis of (Z)-3-(3-(2-morpholinoethoxy)styryl)benzoic acid (VN-388). To a stirred solution of compound 5 (700 mg, mixture) in a mixture of THF/methanol (1:1, 6 mL) was added a solution of sodium hydroxide (229 mg, 5.72 mmol) in water (3 mL) at RT and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was concentrated under reduced pressure. The residue was diluted with water (15 mL) and extracted with ether (2×10 mL). The organic layer was separated; the aqueous layer was acidified with 1 N HCl solutions to pH ˜2 and extracted with 10% MeOH/CH2Cl2(2×30 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to afford the desired compound 6 (500 mg). The crude material was purified by normal phase preparative HPLC (Method T) to afford VN-388 (90 mg, 0.25 mmol, 13%) as an off white solid.1H NMR (400 MHz, DMSO-d6): δ 9.93 (br s, 1H), 7.86-7.77 (m, 2H), 7.48-7.37 (m, 2H), 7.22 (t, J=7.8 Hz, 1H), 6.91-6.81 (m, 3H), 6.76-6.66 (m, 2H), 4.22-4.20 (m, 2H), 4.00-3.62 (m, 4H), 3.56-3.43 (m, 2H), 3.22-3.08 (m, 2H);1H NMR (400 MHz, DMSO-d6, D2O Exc.): δ 7.80-7.75 (m, 2H), 7.46-7.36 (m, 2H), 7.19 (t, J=8.0 Hz, 11H), 6.89-6.78 (m, 3H), 6.72-6.64 (m, 2H), 4.16 (t, J=4.8 Hz, 2H), 3.81-3.72 (m, 4H), 3.43 (br t, J=4.7 Hz, 2H), 3.24-3.20 (m, 4H). LC-MS: m/z 354.2 [M+H]+at 2.63 RT (99.50% purity). HPLC: 99.74%. Preparative HPLC Methods: Final compounds were purified by prep-HPLC, using different methods given below. Prep HPLCS. No:TargetMethod1VN-317N & J2VN-318J3VN-321G4VN-378H5VN-378I6VN-323P7VN-328K8VN-329 & VN-338N9VN-330 & VN-339F & M10VN-331D11VN-322J & N12VN-333 & VN-342F13VN-383 tetrazoleO14VN-335L15VN-336J16VN-341G17VN-343J18VN-344M19VN-347 & VN-377A20VN-348 & VN-377B21VN-351 & VN-380U22VN-353R23VN-354 & VN-380Y24VN-355 & VN-387S25VN-359S26VN-365 & VN-385V27VN-366 & VN-383W28VN-367 & VN-386X29VN-368 & VN-373C30VN-369 & VN-371Q31VN-371 & VN-372D32VN-371 & VN-396E33VN-375 & VN-378F34VN-376B35VN-388T Method-AColumn: Chiral pak IC (250×20 mm), 5uMobile phase A: 0.1% DEA in n-HEXANE; Mobile phase B: EtOH:MeOH (50:50)Flow Rate: 20 ml/min; Programme: (95:05) Method-BColumn: Chiral pak IC (250×20 mm), 5uMobile phase A: n-HEXANE, Mobile phase B: IPAFlow Rate: 20 ml/min; Programme: (99:01) Method-CColumn: Inertsil Diol (250×20 mm), 5uMobile phase A: 0.1% TFA in n-HEXANE, Mobile phase B: DCM:EtOH (90:10)Flow Rate: 20 ml/min; Programme: (88:12) Method-DColumn: YMC Diol (250×20 mm), 5uMobile phase A: n-HEXANE, Mobile phase B: DCM:MeOH (80:20)Flow Rate: 20 ml/min; Programme: (75:25) Method-EColumn: Inertsil Diol (250×20 mm), 5uMobile phase A: 0.1% TFA in n-HEXANE, Mobile phase B: DCMFlow Rate: 20 ml/min; Programme: (99:01) Method-FColumn: Inertsil Diol (250×20 mm), 5uMobile phase A: n-HEXANE, Mobile phase B: DCM:MeOH (50:50)Flow Rate: 20 ml/min; Programme: A:B (95:05) Method-GColumn: Chiral pak IC (250×20 mm), 5uMobile phase A: 0.1% TFA in n-HEXANE, Mobile phase B: THF, Mobile phase C: DCM:MeOH (80:20)Flow Rate: 20 ml/min Programme: (90:05:05) Method-HColumn: Chiral pak IC (250×20 mm), 5uMobile phase A: n-HEXANE, Mobile phase B: EtOH:MeOH (50:50)Flow Rate: 20 ml/min Programme: (98:02) Method-IColumn: X-Select CSH C-18 (250×20 mm), 5uMobile phase A: ACN, Mobile phase B: 5 Mm Ammonium bicarbonate.Flow Rate: 15 ml/min Programme: B %-0.01-95%, 2-95%, 4-70%, 12-55%, 30-0%, 35-0% Method-JColumn: X-Select CSH C-18 (250×20 mm), 5uMobile phase A: ACN, Mobile phase B: 0.05% TFA in waterFlow Rate: 15 ml/min Programme: B %-0.01-95%, 2-95%, 10-70%20-30%, 25-10%, 35-10% Method-KColumn: X-Select CSH C-18 (250×19 mm), 5uMobile phase A: ACN, Mobile phase B: 0.05% Aq. TFAFlow Rate: 15 ml/min Programme: B %-0.01-80%, 2-80%, 5-70%, 15-30%, 22-10%, 22.1-0%, 30-0% Method-LColumn: X-Select CSH C-18 (250×19 mm), 5uMobile phase A: ACN, Mobile phase B: 0.05% Aq. TFAFlow Rate: 15 ml/min Programme: B %-0.01-80%, 2-80%, 8-50%, 16-30%, 20-30%, 25-0%, 30-0% Method-MColumn: X-Select CSH C-18 (250×20 mm), 5uMobile phase A: ACN, Mobile phase B: 5 Mm Ammonium acetate.Flow Rate: 15 ml/min Programme: B %-0.01-95%, 3-95%, 10-70%, 20-10%, 25-10% Method-NColumn: Inertsil Diol (250×20 mm), 5uMobile phase A: n-HEXANE, Mobile phase B: DCM:MeOH (50:50)Flow Rate: 20 ml/min; Programme: A:B (99:01) Method-OColumn: X-Select CSH C-18 (250×20 mm), 5uMobile phase A: ACN, Mobile phase B: 0.05% TFA in waterFlow Rate: 15 ml/min Programme: B %-0.01-80%, 2-80%, 8-60%, 20-30%, 28-10%, 35-10% Method-PColumn: X-Select CSH C-18 (250×20 mm), 5uMobile phase A: ACN, Mobile phase B: 0.05% TFA in water.Flow Rate: 15 ml/min Programme: B %-0.01/90, 2/90, 8/65/20/30, 27/10, 35/10 Method-QColumn: Inertsil Diol (250×20 mm), 5uMobile phase A: n-HEXANE, Mobile phase B: EtOH:MeOH (50:50)Flow Rate: 20 ml/min; Programme: A:B (95:05) Method-RColumn: Inertsil Diol (250×20 mm), 5 umMobile phase A: 0.1% TFA in n-Hexane, Mobile phase B: EtOH:MeOH (50:50)Flow Rate: 20 ml/min; Programme: A:B::(80:20) Method-SColumn: Chiral pak IA (250×20 mm), 5 umMobile phase A: 0.1% TFA in n-Hexane, Mobile phase B: EtOH:MeOH (50:50)Flow Rate: 20 ml/min Programme: A:B::(80:20) Method-TColumn: Chiral pak IA (250×20 mm), 5 umMobile phase A: 0.1% TFA in n-Hexane, Mobile phase B: DCM:MeOH (50:50)Flow Rate: 20 ml/min Programme: A:B::(75:25) Method-UColumn: Chiral pak IC (250×20 mm), 5 umMobile phase A: 0.1% TFA in n-HEXANE, Mobile phase B: DCM:MeOH (50:50)Flow Rate: 20 ml/min Programme: A:B::(75:25) Method-VColumn: Chiral pak IA (250×20 mm), 5 umMobile phase A: 0.1% TFA in n-Hexane, Mobile phase B: DCM:MeOH (50:50)Flow Rate: 20 ml/min Programme: A:B::(80:20) Method-WColumn: Chiral pak IC (250×20 mm), 5 umMobile phase A: 0.1% DEA in n-HEXANE; Mobile phase B: DCM:MeOH (50:50)Flow Rate: 20 ml/min; Programme: (75:25) Method-XColumn: Chiral pak IA (250×20 mm), 5 umMobile phase A: 0.1% DEA in n-Hexane, Mobile phase B: DCM:MeOH (50:50)Flow Rate: 20 ml/min Programme: A:B::(80:20) Method-YColumn: Chiral pak IA (250×20 mm), 5 umMobile phase A: n-Hexane, Mobile phase B: EtOH:MeOH (50:50)Flow Rate: 20 ml/min Programme: A:B::(80:20) Evaluation of the Activity of ADMA-Lowering Agents The structure and activity of example ADMA-lowering agents are shown in Tables 1 and 2 below. TABLE 1Structure and Activity of Stilbene-Based ADMA-Modulating AgentsCmpdEC50nMR1R2R3R4R5R6R7StereoVN-33053HHHHHHHTransVN-339AmbiguousHHHHHHHCisVN-3298.7HHHHCH3HHTransVN-3590.16HOHHHHHHTransVN-32818.6HHHHHHOHTransVN-338AmbiguousHHHHHHOHCisVN-200—OHHHHHHHTransVN-201—HHOHHHHHTransVN-202—HHHOHHHHTransVN-3903.4HHHHHHFTransVN-37210.4HHHHHHFCisVN-3177HHHHCH3HOHTransVN-3711.4HHHHHHClTransVN-3793.9HHHHHHClCisVN-3331.8HHHHCH3HOCH3TransVN-34281.5HHHHCH3HOCH3CisVN-3630.97HHHHHHYTransVN-3621.3HHHHHYHTransVN-3841.6HHHHYHHtransVN-36411.31HHHHYHHtransVN-388AmbiguousHHHHHYHcisY = 2-(morpholin-4-yl)ethoxy- TABLE 2Structure and Activity of ADMA-LoweringAgents Including Heterocycles.NameREC50 nMStereoVN-3800.17CisVN-3810.73CisVN-3871.7CisVN-3730.76CisVN-374—CisVN-3862.8CisVN-385—CisVN-35187Transnot synth—Transnot synth—TransVN-35358TransVN-355651TransVN-354672TransVN-3680.79TransVN-3691.23TransVN-365180TransVN-3671056TransVN-3661366Trans TABLE 3Structure and Activity of Other ADMA-Lowering Agents.EC50CmpdStructurenMVN-3473.3VN-32290VN-376527.1 In Vivo Activity of the ADMA-Lowering Compounds A rat model of monocrotalin induced PAH was used for in vivo studies. Male Sprague Dawley rats about 250 g were purchased from Charles river. PAH was induced by a single s.c. injection of 60 mg/kg monocrotalin. VN-317 (1 mg/kg) or vehicle was administered subcutaneously on day one and once a day thereafter. After 6 weeks, the disease development was determined by pulmonary artery (PA) pressure measurements, echocardiography, and histology. PA pressure was determined by right heart catheterization using a 1.4-F micromanometer-tipped Millar catheter with fluoroscopy guidance. Transthoracic echocardiography was performed using a GE vivid i with 5.0-13.0 MHz i12L-RS linear array transducer. Pulmonary artery acceleration time (PAAT) was measured using pulse-wave Doppler echocardiography with the sample volume centrally positioned in the PA distal to the pulmonary valve. M-mode was applied to measure the right ventricular cavity thickness during end diastole using the parasternal long-axis view obtained from the right side of the rat. Tissue and blood samples were collected at termination. Tissues were fixed in 10% formalin, embedded in paraffin, and then processed for histomorphometry. Macrophage in lung tissues were determined by immunostaining using CD68 antibodies. DDAH Modulating Activity of Compounds Expression of DDAH was determined in human pulmonary artery smooth muscle cells (FIG.1A) and human retinal microvascular endothelial cells (FIG.1B). Cells were treated with different concentrations of VN-317. After 24 hours, cells were extracted in lysis buffer as described under methods. Extracts were subjected to SDS gel electrophoresis. Proteins from SDS gel were transferred to PVDF membrane and for western blotting using DDAH-1 antibodies. As shown inFIG.1A, VN-317 enhanced DDAH-1 protein in pulmonary artery smooth muscle cells whereas reduced DDAH-1 protein in human retinal microvascular cells. Therese data illustrate differential modulation of DDAH by VN-317 in different cell types. FIG.2shows effect of the compounds on collagen synthesis in myofibroblast like smooth muscle cells. Cells were treated with VN-317 in the presence or absence of TGF-beta. After 48 hours, cells were extracted in 50 ul lysis buffer and cell extract was subjected to SDS gel electrophoresis. Proteins from the 12% polyacrylamide gels were transferred to PVDF membranes for westerns and blotted collagen 1a antibodies from Abcam. The results show that VN-317 reduced collagen production in response to TGF-beta, supporting the potential antifibrotic activity of the compounds. As shown inFIG.3, VN-317 reduced pulmonary artery medial thickening, reduced vascular disease in the lung, and reduced inflammation in the lung in a model of PAH. As shown inFIG.4, VN-317 reduced pulmonary artery pressure in a model of PAH. As shown inFIGS.5A-5B, VN-317 also reduced right ventricle cavity thickness (FIG.5A), increased pulmonary artery blood and acceleration time (PAAT,FIG.5B), in a model of PAH. As shown inFIG.6, VN-317 reduced mortality in a model of PAH. As shown inFIG.6, VN-317 treatment prevented the body weight loss and mortality in a model of PAH.FIG.6Ashows MCT treated group over time (number indicate animal ID) andFIG.6Bshows MCT plus VN-317 treated animals. The compounds, compositions, and methods of the appended claims are not limited in scope by the specific compounds, compositions, and methods described herein, which are intended as illustrations of a few aspects of the claims. Any compounds, compositions, and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compounds, compositions, and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative compounds, compositions, and method steps disclosed herein are specifically described, other combinations of the compounds, compositions, and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein or less, however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated. The term “comprising” and variations thereof as used herein is used synonymously with the term “including” and variations thereof and are open, non-limiting terms. Although the terms “comprising” and “including” have been used herein to describe various embodiments, the terms “consisting essentially of” and “consisting of” can be used in place of “comprising” and “including” to provide for more specific embodiments of the invention and are also disclosed. Other than where noted, all numbers expressing geometries, dimensions, and so forth used in the specification and claims are to be understood at the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, to be construed in light of the number of significant digits and ordinary rounding approaches. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of skill in the art to which the disclosed invention belongs. Publications cited herein and the materials for which they are cited are specifically incorporated by reference. | 303,652 |
11858890 | DETAILED DESCRIPTION OF THE INVENTION In the context of the invention described here, the average particle size distribution is to be understood as meaning the volume-average particle size distribution. This may be determined for example via various sieving steps. In accordance with the invention, a Beckmann Coulter LS particle size measurement was however performed. The basis of the measurement and the measurement principle are elucidated in the standard “DIN ISO22412:2019-09Particle size analysis—Dynamic light scattering(DLS)”. Employed in principle is a diluted suspension which contains in addition to the component to be measured just under 0.1% by weight of sodium pyrophosphate as a stabilizer. The component to be measured is needed in such that an absorbance/scattering of the light source of 10-20% is achieved. The evaluation is based on the principle that all measured objects approximate to spheres. The respective sphere volumes are then plotted as a function of sphere diameter to obtain the particle distribution function. This accordingly results in a volume distribution which may inter alia be converted into a weight distribution using the material density. Volume distribution should always be assumed unless otherwise stated. The oxidative conversion of (meth)acrolein preferably employs a pulverulent fresh catalyst which comprises gold or palladium as the central active oxidation metal in a concentration of between 0.1% by weight and 10% by weight based on the total weight including further support material. These preferably employed particles of the catalyst have a size of 0.1 to 300 μm, wherein more than 95% by volume of the catalyst particles present have a size of less than 200 μm. It is also preferable when more than 50% by volume of the catalyst particles have a size between 10 and 90 μm and the fines fraction of the catalyst particles in the reactor having a size of 0.1 μm to 10 μm is less than 10% by volume. It is particularly preferable when less than 0.5% by weight per hour of the catalyst powder present in the reactor are discharged from the reactor in a classifying manner together with the product solution during the reaction. After 1000 operating hours the catalyst fraction remaining in the reactor comprises catalyst particles which to an extent of at least 98% by volume have a particle size above 10 μm. The catalyst discharge is in turn collected in at least one further filter which allows retention of particles of 1 to 30 μm and the particles retained in the filters downstream of the inclined settler are to an extent of more than 50% by volume particles smaller than 30 μm. The employed pulverulent catalyst preferably has an average particle size distribution of 30 to 100 μm based on its volume fractions, wherein these sizes may be reduced through mechanical stress in the case of prolonged, continuous operation. The fines fraction discharged with the reactor medium in turn preferably has an average particle size distribution of 1 to 15 μm which is likewise based on the volume fractions. It has proven particularly advantageous when a particle collective consisting to an extent of at least 50% by volume of particles smaller than 30 μm is continuously discharged from the reactor. It is moreover advantageous to supply these particles to the filters in suspended form in a reaction medium containing MMA, methacrylic acid, water and methanol. In preferred embodiments of the present invention, the reaction medium exiting the reactor has an MMA content of more than 20% by weight and less than 50% by weight. In these embodiments the water content is then between 1% and 15% by weight. Less than 20% by weight of unconverted methacrolein is then also present. It has proven particularly advantageous in the process according to the invention to use a combination of at least one classifying sedimentation apparatus and at least 2 filters. These are continuously traversed by the reaction medium containing fines fractions of the catalyst particles. It is preferable when in addition the first filter after the at least one classifying sedimentation apparatus has a lower retention capacity than the subsequent second filter. It is particularly preferable when the classifying sedimentation apparatus is installed in the reactor shell in such a way that at least one of the downstream filters is arranged outside the reactor shell. Additionally or independently of the other embodiments of the present invention it is advantageous when a final filter upstream of the next process engineering operation, preferably upstream of a distillation, a degassing, a phase separation or an extraction, has a retention capacity for particles smaller than 10 μm. This results in less than 1 ppm of catalyst particles having a diameter greater than 10 μm passing into the next the process engineering operation. It is advantageous when this filter is suitable for the separation of particles having a size of at least 1 μm. The reaction may for example and preferably be performed in a reactor in which the ratio of diameter to height of the gasified liquid level is between 1:1 and 1:50. The reactor comprises here at least three zones A, B and C, wherein present at the transition from zone A to each zone B are internals which homogenize the flow of the reaction mixture upon entry of the reaction mixture into zone B. Each zone B is connected to at least one zone C which comprises a sedimentation apparatus. It is particularly preferable when the ratio of the volume of zone A to the total volume of all zones B in such a reactor is greater than 1 and less than 500. Zone A comprises the reactor. The reactor preferably comprises one or more feed conduits through which the mixtures of alkyl alcohol and (meth)acrolein may be supplied. The reactor additionally comprises at least one classifying sedimentation apparatus. It is further preferable when the classifying sedimentation apparatus consists of a plurality of channel-like profiles, tubes or lamellae having an angle of inclination to the horizontal, which each have the same pressure at the inlet and where the liquid flowing therethrough has the same flow velocity at each inlet. The sedimentation apparatus in zone C is particularly preferably an inclined settler or a hydrocyclone. Also particularly preferred is an embodiment of the invention in which the relatively large catalyst particles are retained in the sedimentation apparatus and recycled into zone B. It is preferable when the relatively large catalyst particles return to zone A via zone B. In such an embodiment the relatively small catalyst particles which pass through zone C are collected using at least one filter apparatus and simultaneously zone A in the lower portion of the reactor is actively supplied with the oxygen-containing gas via nozzles or gasification apparatuses. Simultaneously, one or more zones B, particularly preferably all zones B, comprise no apparatuses for active gasification of the reaction mixture, thus minimizing gas entry into zone C. The reaction mixture in zone A may optionally be vertically conveyed with a stirring means or a pump in such a way that the gas bubbles are as small as possible and the gas residence time in zone A is high. Optionally, in zone A the stirring means is arranged such that zone A and at least one zone B are separated from one another by internals, preferably by dividing walls, wherein the internals at the transition from zone A to each zone B largely prevent entry of gas bubbles into zone B. The process according to the invention may be performed particularly efficiently when the average catalyst particle size is between 50 and 120 μm. EXPERIMENTAL SECTION Methacrolein was produced according to U.S. Pat. No. 4,496,770. However, alternative procedures may also be used, for example that in U.S. Pat. No. 9,580,374. Example 1 Production of a Pulverulent, Abrasion-Resistant SiO2—Al2O3—MgO Support Material An enamel-lined receiver was initially charged with 21.36 kg of Mg(NO3)2*6H2O and 31.21 kg of Al(NO3)3*9H2O and the mixture was dissolved in 41.85 kg of demineralized water while stirring with an impeller stirrer. 1.57 kg of 60% HNO3was then added while stirring. 166.67 kg of silica sol (Köstrosol 1530AS from Bad Köstritz, 30% by weight SiO2, average particle size: 15 nm) was initially charged in an enamel-lined 500 L reactor and cooled to 15° C. while stirring with an impeller stirrer. 2.57 kg of 60% HNO3was slowly added to the solution while stirring. At 15° C. the nitrate solution from the receiver was added to the sol over 45 min while stirring. After the addition, the mixture was heated to 50° C. over 30 min and held at this temperature for a further 4 h, the mixture undergoing gelation. At the end of this time, the gelled mixture was continuously pumped into a spray dryer as a suspension and spray dried at an outlet temperature of 130° C. The dried green product (the mixture initially obtained after spray drying) was calcined in a rotary kiln, wherein the residence time in the hot zone (600° C.) was about 45 minutes. The residence time and throughput time for the calcination in the rotary kiln was controlled via the inclination of the rotary kiln (about 1° to 2° inclination). The nitrous gases occurring during the calcination operation were removed in gaseous form and appropriately treated by absorption and chemisorption. The passage through the rotary kiln was repeated at identical residence times and identical temperature settings in the hot zone. The nitrate content in the finished support particles was less than 1000 ppm. After calcination, 55 kg of a white, flowable pulverulent support material were obtained. The mass yield was about 95%. The support was analysed by SEM and laser diffraction which revealed a spherical support having an average particle size distribution of about 60 μm. The support was subsequently subjected to classification by sieving with several passes and various sieve sizes, wherein the fractions above 120 μm and below 15 μm were very largely removed. Because of technical limitations, a fines fraction of about 3.6% by volume remained, i.e. particles which despite sieving had a particle size of between 1 and 15 microns. The yield of the classification step (sifting/sieving) was about 70% and the obtained average particle size distribution of the finished support material was about 68 μm. Example 2 Production of a Nanoparticulate Gold-Containing Catalyst for Continuous Performance of a Direct Oxidative Esterification of Methacrolein to MMA In an enamel-lined reactor, 15 kg of the support was suspended in 50 kg of demineralized water while stirring with an impeller stirrer. The resulting mixture was heated to 90° C. and aged for 15 minutes after reaching 90° C. A solution of 852.9 g of Co(NO3)2*6H2O in 7.5 kg of demineralized was metered in over 10 minutes and the mixture was aged for 30 minutes. 3.7 L of 1 molar NaOH solution was then added over 10 minutes. Immediately thereafter, a solution of 376.8 g of auric acid (41% gold) in 7.5 kg of demineralized water was added and the mixture was aged for 30 minutes. The resulting suspension was cooled to 40° C. and filtered using a centrifuge. The filter cake was washed in the centrifuge with demineralized water until the filtrate became clear and had a conductivity below 100 μS/cm. The wet catalyst was dried at 105° C. in a vacuum drying oven until the residual moisture was below 5%. The dried catalyst was calcined in a rotary kiln, wherein the residence time in the hot zone (450° C.) was about 45 minutes. The yield was about 99%. The calcined catalyst was analysed by SEM-(EDX) and laser diffraction, which revealed a spherical eggshell catalyst having an average particle size distribution of about 68 μm. The fines fraction was about 5.2% by volume. ICP revealed a gold content of 0.85% by weight. The catalyst was employed in this form in the continuous oxidative esterification of methacrolein to MMA in example 3. Example 3 Continuous Performance of a Direct Oxidative Esterification of Methacrolein to MMA I. Reactor, Reaction System and Configuration of the Catalyst Retention System A stirred-tank reactor fitted with a stirrer was used for the reaction. The employed materials are made of conventional stainless steel to withstand the slightly corrosive media. The reactor has a double jacket which is connected to a thermostat which can in turn effect cooling and heating via its medium. The reactor lid is connected to a condenser via a vapor tube (100 mm nominal width). The stirred tank had an inner diameter of 400 mm and the reactor height up to the lid was 1500 mm. The stirrer is connected to the reactor from below via the base and is fitted with special stirring means which allow both optimal gas dispersion for the oxygen-containing gas (in this case compressed air) and optimal suspension of the particulate catalyst in the medium. A commercial stirrer system consisting of a primary disperser for large gas volumes (Ekato Phasejet) for gas-liquid mixtures having a radial conveying direction and a Kombijet stirring means, i.e. two stirring means secured to the stirrer shaft, is employed. The distance of the stirring means from the base of the reactor was 100 mm and 400 mm for the second stirring means. The gas conduit for supplying the oxygen-containing gas terminates directly below the dispersion means and ensures uniform distribution of the gas over the reactor cross section and fine dispersion of the oxidation gas. Above the reactor, lid feed conduits for reactants, recycle streams and auxiliaries are instated in the reactor in such a way that the feed conduits terminate wet below the media fill level. The top of the reactor is connected via a conduit with a receiver vessel containing a methanolic stabilizer solution (1000 ppm Tempol). II. Catalyst Retention System In the upper portion of the reactor is a take-off tube which passes the reaction suspension into the externally instated inclined settler. The slurry is initially degassed in the degassing vessel (internal diameter 200 mm with conical lower outflow) so that only dissolved gas constituents remain in the slurry suspension. The lower portion of the degassing vessel is connected to a pipeline having a 30 mm internal diameter and constitutes the upper portion of the downcomer. The now degassed, only biphasic suspension thus flows vertically downward to a Y-shaped branching. The right-hand arm of the branching passes the suspension to the inclined settler element where the biphasic system undergoes efficient sedimentation. The catalyst thus returns to the reactor. At the outlet of the inclined settler is a pressure-resistant sightglass to allow visual examination of the quality of the separation as well as a pressure maintenance means and a valve to control the amount removed. Installed downstream of the pressure valve are two parallel filters made of polypropylene which allow a maximum separation performance of 1 micron (according to manufacturer specifications). The filters are continuously traversed and also integrated via a three way valve such that it is possible for only one filter to be traversed while the other may be changed during ongoing operation. The lamella elements of the inclined settler are cuboidal four-edged profiles made of stainless steel having internal dimensions of: L=700 mm, H=20 mm, W=50 mm. The usable internal volume is thus 700 mL. A total of 8 lamella elements are installed. III. Commencement of Reaction and Continuous Reaction: The reactor was charged with a mixture of methanol, water and MMA as well as dissolved Na methacrylate. Initial charging of this reaction mixture results in faster attainment of steady-state concentrations. The reactor was charged with 130 kg of this starting medium having a composition of 3% by weight of methacrylic acid, wherein 50% thereof was in the form of the sodium salt, 33% by weight of MMA, 5% by weight of water and 59% by weight of methanol. The fill level was about 80% of the fill height of the reactor. The reactor is additionally charged with 13 kg of the catalyst according to example 2. The slurry density is thus 10% by weight based on the employed catalyst amount and operating volume of the reaction solution. The reaction mixture is heated to 80° C. and the stirrer set to 260 rpm. The reactor is brought to an operating pressure of 5 bar absolute (using nitrogen as the starting medium). After reaching the reaction temperature, air is introduced in steps of 1 kg/h, thus causing immediate onset of the reaction, as apparent from the fall in the methacrolein level in the reactor and the increase in the MMA concentration in the reaction mixture. The amount of air is increased in the abovementioned steps until the offgas has an oxygen concentration of 5% by volume. This is advisable, since the explosive limit of the offgas from the reaction is an oxygen content of barely 8% by volume. The temperature of the offgas after condensation of the condensable organic constituents, in particular methanol, methacrolein, MMA, water and low-boilers, is −20° C. NIR is used to measure and quantify the concentration of the various offgas constituents, in particular CO2, CO, oxygen, water, propene, nitrogen, methanol, acetone, methyl formate and optionally other low boilers discharged with the offgas. The offgas having a total content of volatile organic constituents of less than 1.5% by volume is subjected to thermal treatment and incinerated. Methacrolein is continuously supplied to the reactor via a metering pump. 140 mol of methacrolein is metered into the reactor per hour to establish a steady-state conversion of between 70% and 72%. Over the total running time in continuous operation, a conversion of 98 to 102 mol of methacrolein is determined. According to this operating mode, the reactor is operated with essentially two methacrolein feed streams, namely the fresh methacrolein feed (at a metered addition rate of about 100 mol/h) and the methacrolein recycle feed, this being the top fraction from the MAL-MeOH recycle column. This stream contains about a further 40 mol/h of methacrolein. The discharge of the steady-state reaction mixture via the catalyst retention system (inclined settler and filtration units) is controlled via a pressure valve and is on average 32.5 kg/h. This corresponds to an average reaction time of about 4 h. The ratio of the discharged volume to the volume of the inclined settler element may be calculated as a defined parameter especially for the quality of the solid separation. In the present example this ratio is about 4.06 kg of liquid per lamella element (700 mL) per hour. One parameter which describes the separation efficiency of the inclined settler is the volume flow of the medium based on the cross-sectional area of the inclined settler; if the resulting formal velocity is less than the descent velocity of the particles/the particle collective, separation of the particles will result. In the present example this parameter is about 0.17 m/h or 0.17 m3/m2×h (density of 800 kg/m3, lamella area 700 mm×50 mm, projected area scaled with the sine function of the angle of inclination of 60°). The reaction mixture is decompressed and passed into a column via an intermediate vessel having a volume of 10 L. In this so-called methacrolein-methanol recovery column (operating pressure 1 bar absolute), the methacrolein that is not converted in the reaction and excess methanol condense at the top of the column and are recycled into the reactor. In addition, certain concentrations of other low boilers are condensed in the overhead product of the column. These include inter alia MMA, water, acetone, methyl propionate, methyl formate and methyl acrylate and also further traces of other low-boiling components, some of which form azeotropes with one another and with the main components. The column is operated at a reflux ratio of 1:1. The bottoms temperature of the column is 72° C. to 73° C. The control parameter of the column is inter alia the residual methacrolein content of the bottom product (bottom discharge), which is typically well below 1% by weight. In continuous operation of the unit, methacrolein contents in the bottoms between 0.05% to 0.2% by weight are achieved. The bottom product contains crude MMA as well as the higher boiling byproducts of the reaction, in particular methyl methoxyisobutyrate (“MMIB”) and methacrylic acid (“MAA”) which is in turn partly in the form of the sodium salt. A sequence of extraction and multistage distillation affords MMA of commercial quality and purity. The selectivity of the reaction is determined by gas chromatography (GC) and is on average 94.4% for MMA, 3.0% for methacrylic acid and 1.2% for MMIB, the respective reference value being the amount of the methacrolein used. Including the losses of the reactants (methacrolein) and MMA, the C4 reconciliation in the offgas comes to virtually 100%. The course of the conversion and selectivity over a running time of the unit of nearly 1000 operating hours is shown inFIG.1. According to the invention the classification in the inclined settler leads to a decrease in catalyst present in the reactor over the first almost 100 hours of operating time, with the result that the conversion of methacrolein falls. The selectivities for MMA and MMIB are unaffected by this, unlike the selectivities for MAA and methyl isobutyrate. The reason for this is firstly the discharging of a—more active—fines fraction which generates more methyl isobutyrate and secondly, for MAA, a deferred change in the water content in the reaction matrix which results in a change in the selectivity for MAA as shown inFIG.2. A fall in the selectivity for methyl formate surprisingly also results, as shown inFIG.3. This has several advantages, such as decreased hydrolysis to formic acid, thus causing the NaOH demand of the reaction to fall, and smaller amounts of methyl formate in the offgas stream. Methyl formate can react with water from the offgas at the condensation site to form formic acid and methanol, thus increasing the corrosivity of the offgas condensate. FIG.4shows the determination of the catalyst discharge of the invention and catalyst retention as a function of running time. Time0represents fresh catalyst. The reactor discharge from the above-described continuous reaction was sampled at regular intervals and the amount of catalyst exiting the inclined settler and present therein was determined. To this end, the sample of reaction medium was filtered through a 1 μm depth filter and the residue determined gravimetrically after drying. Immediately after commencement the suspension still has a concentration of about 1200 ppm of catalyst. This is apparent inter alia from the slight purple coloration of the suspension. The catalyst concentration then rapidly decreases and after barely 20 reactor volumes of discharge, corresponding to a reaction time of 80 to 100 hours, reaches an asymptotic minimum of about 1 ppm. Sampling was then stopped. The catalyst of the final sample was homogenized and its particle size distribution analysed by the Coulter method. The result is shown inFIG.5A.FIG.5Bshows a magnified section. According to the invention the classifying effect which ensures that only very small residual particles are discharged via the inclined settler is observed. This is consistent with the stable conversion function after almost 100 hours. It was therefore demonstrated thata.) over a short operating time of just a few days the disruptive fines fraction of the fresh catalyst is discharged from the reactor effectively and in a classifying manner by the present inventive catalyst retention system, thatb.) this discharge can be very largely recovered and subsequently recycled with a fine filter, and thatc.) after this startup and conditioning phase, the conversion and the steady-state reaction concentration remain stable, thus allowing problem-free operation of the workup portion without substantial adaptation of the operating parameters. FIG.6shows the time-course of the catalyst concentration in the reactor discharge as a function of discharge volume. Example 4 Continuous Performance of a Direct Oxidative Esterification of Methacrolein to MMA The reaction is performed with the same reactor setup as described in example 3. The catalyst from example 2 is employed. The slurry density is in turn 10% by weight based on the steady-state reaction medium. However, the means for primary retention of the catalyst is now installed internally in the reactor. Arranged in the upper portion of the reactor is an overflow, about 150 mm below the steady-state operation fill level. The slurry thus overflows freely in the upper portion. The slurry is initially degassed in the degassing vessel (internal diameter 200 mm with conical lower outflow) so that only dissolved gas constituents remain in the slurry suspension. The lower portion of the degassing vessel is connected to a pipeline having a 30 mm internal diameter and constitutes the upper portion of the downcomer. The now degassed, only biphasic suspension thus flows vertically downward to a Y-shaped branching. The right-hand arm of the branching passes the suspension to the inclined settler element where the biphasic suspension undergoes efficient sedimentation. At the outlet of the inclined settler is a pressure-resistant sight glass to allow visual examination of the quality of the separation as well as a pressure maintenance means and a valve to control the amount removed. Installed downstream of the pressure valve are two parallel filters made of polypropylene which allow a maximum separation performance of 1 micron (according to manufacturer specifications). The filters are continuously traversed and also integrated via a three way valve such that it is possible for only one filter to be traversed while the other may be changed during ongoing operation. The lamella elements of the inclined settler are cuboidal four-edged profiles made of stainless steel having internal dimensions of: L=700 mm, H=20 mm, W=50 mm. The usable internal volume is thus 700 mL. A total of 8 lamella elements are installed. The reactor is brought online as described in example 3 and initially operated without feed streams for one hour until a steady-state circulation is ensured in the reactor and in the downcomer. Removal of 65 kg/h is then established and the feed streams are supplied. Half of the discharge is recycled to the reactor after cooling to 40° C. and supply of the stream is thus effected in the lower third of the reactor. Similarly to example 3, the following parameters are established: 8.1 kg of liquid per lamella element per hour; the loading of the settler is thus 0.34 m/h or 0.34 m3/h m2. This relatively high rate means that a relatively high discharge of catalyst is to be expected. 100 mol of fresh methacrolein is metered in per hour, as well as a further 40 mol of methacrolein from the recycle stream from the column. The air consumption over the entire operating time is about 8500 L. A residual oxygen concentration of 4% to 4.5% by volume is established in the offgas. Under these conditions the space-time yield of the catalyst is about 7.5 to 8 mol of MMA/h/kg of catalyst. The unit is operated continuously for 7 days. During this time one filter is continuously traversed and the starting back pressure of the 1 micron PP filter is about 100 mbar. There is a continuous buildup of pressure during this first operating time through loading of the filter; after an operating time of 7 days this pressure is about 900 mbar. After this first operation time of 168 h, a switchover from the first filter to the second filter is effected. The unit is continuously operated for a further 10 days and the crude product is continuously discharged via the second filter. In this second operating phase, the pressure increase due to the new filter is markedly lower. For the reconciliation, the two filters are washed with water, first carefully in a recirculating air stream in an oven at 70° C. and then at 120° C. for a further 12 h. The weight and particle size of the filtered catalyst fines fraction is then determined. These results are reported in table 1 which follows. After the total operating time of 308 hours, the reaction is stopped by terminating the metered addition of methacrolein. The reactor is gasified at operating temperature for a further 16 hours, resulting in a residual methacrolein content of less than 0.2% by weight. The reactor contents are then discharged through a filter, the catalyst is washed and dried and the dried powder is subjected to treatment at 400° C. in air in a muffle furnace. Finally, the residual mass is determined. 12.75 kg of catalyst are found. This corresponds to about 93% of the catalyst amount initially employed. TABLE 1Example 4,Example 4,first phasesecond phaseExperiment duration [h]168240Experiment phase [h]0 to 168168 to 308Crude product discharged [kg]54607800Catalyst discharge in filter [g]15852MMA produced [kg]19112730Specific fines discharge [mg/kg MMA]8219 Conclusion: Converting from the specific discharge rate, 19 g of catalyst per ton of MMA is discharged from the reactor. Assuming that the catalyst has a noble metal content of 1% by weight, this would correspond to 190 mg of gold, which in turn would correspond to a value of about 8 US$/ton of MMA of gold in the fine filter (assuming a hypothetical price of an ounce of gold of 1400 US$/ounce). The loss is correspondingly low, while the reaction makes marked gains in selectivity and the fines fraction of the catalyst causes no problems during product workup. In addition, a major part of the discharged fines fraction may even be subsequently recycled. Example 4b) Continuous Performance of a Direct Oxidative Esterification of Methacrolein to MMA In the same setup as in example 4, a narrowing was welded to the ends of the respective lamellae. The narrowing had only 1.6% of the opening compared to example 4. The narrowing of the lamellae had the result that the discharge in both phases was reduced by a factor of about 2-4 depending on whether phase 1 or 2 is considered. Example 4,Example 4,first phasesecond phaseExperiment duration [h]168240Experiment phase [h]0 to 168168 to 308Crude product discharged [kg]54567792Catalyst discharge in filter [g]4824MMA produced [kg]19092728Specific fines discharge [mg/kg MMA]259 | 30,654 |
11858891 | DETAILED DESCRIPTION OF DISCLOSED EMBODIMENTS Hereinafter, embodiments of the disclosure will be described in detail. However, these embodiments are illustrative, and the disclosure is not limited thereto. In the present specification, a range represented by “a numerical value to another numerical value” is a schematic representation for avoiding listing all of the numerical values in the range in the specification. Therefore, the recitation of a specific numerical range covers any numerical value in the numerical range and a smaller numerical range defined by any numerical value in the numerical range, as is the case with any numerical value and a smaller numerical range thereof in the specification. The disclosure provides a decolorization and purification method of BHET material, which sequentially includes the following four procedural steps. The first procedural step is that a first dose of activated carbon is added to preliminarily treat the BHET material. The second procedural step is that after the preliminary treatment, a first cooling crystallization process and filtration are performed to obtain BHET crystals. The third procedural step is that an oxidant is used to chemically react with the BHET crystals to destroy a dye or impurities, and then a second dose of activated carbon is added to adsorb a chemically reacted oxide. The fourth procedural step is that a second cooling crystallization process, filtration, and drying are performed to obtain a finished product of BHET. In the first procedural step, solvent extraction is used to identify an impurity content in the BHET material, and based on this, an additive amount of the activated carbon for the preliminary treatment (the first dose of activated carbon) is determined. In this embodiment, the BHET material is, for example, dark BHET material, and a CIELAB color is, for example, defined as having an L value of 30 to 45, an a value of −1 to −3, and a b value of −2 to −4. The solvent extraction is, for example, to extract a PET fabric with an alcohol ether solvent. A weight ratio of the alcohol ether solvent to the PET fabric is, for example, 20:1, and a reaction condition is, for example, at a temperature of 140° C. for 2 hours. Based on a total weight of the PET fabric, the minimum extracted impurity content is, for example, 0.2 wt % to 1 wt %. In this embodiment, based on a total weight of the BHET material, the first dose of activated carbon is, for example, 0.5 wt % to 8 wt %, and a treatment temperature and time of the preliminary treatment are, for example, at 80° C. to 90° C. for 3 hours. For example, the preliminary treatment of the activated carbon is performed after adding water. Afterwards, the filtration is performed to remove the activated carbon. In the second procedural step, a process temperature of the first cooling crystallization process is, for example, 20° C., and the first cooling crystallization process and the filtration are performed for 6 hours to obtain the BHET crystals while trace impurities are removed to an aqueous phase. In the third procedural step, the oxidant may include hydrogen peroxide, calcium hypochlorite, or sodium hydrosulfite. Based on the total weight of the BHET material, an additive amount of the oxidant is, for example, 0.1 wt % to 1 wt %, and a reaction temperature and time for the chemical reaction of the BHET crystals using the oxidant is, for example, at 80° C. to 90° C. for 1 hour. For example, the oxidant is used to chemically react after adding the water to destroy the dye or the impurities that are difficult to remove. In this embodiment, based on the total weight of the BHET material, the second dose of activated carbon is, for example, 0.1 wt % to 3 wt %, and a treatment temperature and time of adding the second dose of activated carbon are, for example, at 80° C. to 90° C. for 3 hours to adsorb the chemically reacted oxide, and then completely remove the impurities. Afterwards, the filtration is performed to remove the activated carbon. In the fourth procedural step, a process temperature of the second cooling crystallization process is, for example, 20° C., and the second cooling crystallization process, filtration, and drying are performed for 6 hours, while the trace impurities are removed to the aqueous phase, so as to obtain the BHET crystals. For the obtained finished product of BHET, the CIELAB color is, for example, defined as having the L value of 95 or more, the a value of −1.0 to 1.0, and the b value of 4.0 or less. Therefore, according to the decolorization and purification method of the BHET material in the disclosure, the dark BHET material may be decolorized and purified to obtain clean white BHET. Based on the above, the decolorization and purification method of the BHET material in the disclosure is optimized in the specific sequence of steps. A total of four procedural steps are included in sequence, which may decolorize and purify BHET formed by the depolymerization of various waste PET fabrics to obtain clean white BHET. Especially for the dark BHET material with the impurities such as textile auxiliaries and the dye, the dye and the impurities that are difficult to remove may be completely destroyed and removed, so as to effectively improve the hue of the finished product of BHET. The CIELAB color of the finished product of BHET is defined as having the L value of 95 or more, the a value of -−1.0 to 1.0, and the b value of 4.0 or less. | 5,486 |
11858892 | DESCRIPTION The present invention meets that need by providing an adsorbent comprising a type 3A zeolite which can be used to remove methanol and CO2from hydrocarbon streams. The adsorbent has higher methanol removal capacity and low olefin co-adsorption capacity, as well as low reactivity in an olefin stream. This allows reduced adsorbent loading while maintaining downstream catalyst performance and product quality. The adsorbent comprises a type 3A zeolite comprising less than 5% of a binder. An optional additive can be included. In that case, the total amount of the binder and the additive is less than 5%. The adsorption process can obtain an outlet methanol content of 10 ppmw or less, or 7 ppmw or less, or 5 ppmw or less, or 3 ppmw or less, or 1 ppmw or less. The adsorption process can obtain an outlet CO2content of 10 ppmv or less, or 8 ppmv or less, or 6 ppmv or less, or 4 ppmv or less, or 2 ppmv or less. The 3A type zeolite is a potassium exchanged Linde Type A (LTA) zeolite which has a chemical formula of: mNa2O·nK2O·2.0SiO2·Al2O3 where m+n=1. The pore opening is approximately 3 Å. Used as an adsorbent, zeolite-binder agglomerates as spheres or pellets which have high mechanical attrition resistance and strength are needed. The binder content is at least 10%, and in most cases it is above 15%. Considering the small pore opening size of 3A zeolite and molecular sieving properties of the zeolite, it was mainly used as a dehydration adsorbent. Here, a binderless 3A zeolite adsorbent was used in which the binder was converted to zeolite. The 3A type zeolite can have K ion exchange ratio (K mol/(Kmol+Na mol)) of 30% to 70%. For example, at a 30% ion exchange ratio: m=0.7 and n=0.3, and at a 60% ion exchange ratio: m=0.4 and n=0.6. When potassium is at cationic exchangeable sites within the 3A zeolite adsorbent at 30% to 60%, the potassium ranges from about 8 wt. % to about 16 wt. % of the 3A zeolite adsorbent on a volatile-free basis. In some embodiments, the type 3A zeolite may have one or more of the following characteristics: a porosity of 20% to 40% (ASTM 4284-17); and an ion exchange ratio of 30% to 60% (UOP 961-12 (available through ASTM International)). The porosity can be in the range of 15% to 50%, or 20% to 40%, or 20% to 35%. The ion exchange ratio can be in the range of 30% to 70%, or 30% to 60%, or 30% to 50%, or 35% to 70%, or 40% to 70%, or 40% to 60%. In one embodiment, the adsorbent comprises a type 3A zeolite with less than 5% binder and a K ion exchange rate of 0.40-0.44 (K/K+Na). The elemental composition of the molecular sieve samples was analyzed using −X-ray fluorescence, inductively coupled plasma optical emission spectrometry (ICP-OES), or both. The adsorbent can be used to remove methanol from hydrocarbons, such as propene, and isobutylene. The adsorption selectivity of methanol/C3H6at 1 mmHg and 298K is greater than 5000 mol/mol. The equilibrium adsorption capacities of methanol and C3H6can be tested by physical adsorption isotherm using an accelerated surface area and porosimetry system at 298K, such as Micromeritics' 3Flex Surface Characterization Analyzer or BELSORP-max surface area and pore size distribution analyzer. The adsorption selectivity was defined as the adsorption capacity ratio of methanol/C3H6. The adsorbent can also be used to remove CO2from hydrocarbons, such as ethylene. The adsorbent has high CO2/C2H4selectivity. The adsorption selectivity of CO2/C2H4at 250 mm HG is about 23 mol/mol. The equilibrium adsorption capacities of CO2, and C2H4can be tested by physical adsorption isotherm using an accelerated surface area and porosimetry system at 298K, such as Micromeritics' 3Flex Surface Characterization Analyzer or BELSORP-max surface area and pore size distribution analyzer. The adsorption selectivity was defined as the adsorption capacity ratio of CO2/C2H4. This is much higher than the typical selectivity of a carbon molecular sieve and other types of zeolite adsorbents. In addition, CO2has a smaller molecular size (kinetic diameter 3.3 Å) and higher affinity toward zeolite type adsorbents, both of which benefit CO2/C2H4separation. The CO2capacity at 25° C. and 250 mm Hg is about 4-7%. The C2H4capacity at 25° C. and 250 mm Hg is about 0.11%. The adsorbent has a high water capacity. For example, the static water capacity may be in the range of 23-25%, while the dynamic water capacity may be greater than 18-20% at 25° C. and 17.5 mm Hg. A typical 3A type zeolite has a static water capacity greater than about 15-19%, while the dynamic water capacity is greater than about 13-14%. The adsorbent can be made in the following manner. A binderless base 4A bead or pellet can be formed from a normal clay conversion process. A KCl solution can be used for ion exchange such that the K ion exchange ratio of the finished product is between 30% to 70%. The ion exchanged 3A type zeolite can be dried to remove moisture to the range of 8-25%. The dried adsorbent is then calcined at a temperature of 400-750° C. to obtain the finished adsorbent. The adsorbent can be used in a purification unit which includes adsorption, desorption, and cooling. The adsorption is performed at a temperature typically in the range of 15-50° C. The regeneration of the adsorbent typically takes places at a temperature greater than 150° C. under a gas including, but not limited to, nitrogen, air, or methane. Example A 3A type zeolite was made from a binderless 4A type zeolite. The binderless 4A type zeolite was made by mixing adsorbent agglomerates comprised of 850 g Zeolite A and 150 g inert Kaolin binder. 30 g carboxymethyl cellulose (CMC) was added during the agglomerate-forming step which was formed into 8×12 mesh bead in an accretion bead forming equipment. The formed agglomerate was dried at 150° C. for 2 hr. The dried agglomerate was calcined by increasing the temperature at 5° C./min ramp to 675° C. and holding for 3 hr to convert the kaolin clay binder into meta-kaolin clay binder. The material was cooled down to 100° C. for packaging. The adsorbent was caustic digested at a temperature of about 88° C. using 1.8N sodium hydroxide solution for 20 hr to convert the meta-kaolin binder to binder-converted zeolite. The liquid was decanted, and deionized water at ambient temperature was used to wash the solid until the pH of the wash water was less than 11. The binderless 4A zeolite adsorbent was exposed to 1N KCl solution at 45° C. and held for 8 hr for ion-exchange to produce the 3A type binderless zeolitic adsorbent. The methanol adsorption capacity of the 3A type zeolite adsorbent was measured using physical adsorption isotherm and compared with several commercial adsorbents. Table 1 shows the results of methanol adsorption capacity comparison. TABLE 1Methanol Adsorption Capacity0.1 KPa1 KPaStandard 3A Type Adsorbent0.81%2.3%OG4911-3%n/aAZ3003-5%n/aDisclosed 3A adsorbent14.37%15.8% The 3A type zeolite adsorbent of the present invention has significantly higher methanol adsorption then the commercially available adsorbents. FIG.1shows the methanol vapor adsorption isotherm comparison between the 3A type zeolite adsorbent of the present invention and a commercial 3A type zeolite adsorbent. FIG.2show the adsorption isotherm of 3A type zeolite adsorbent of the present invention to methanol and ethylene. It has high methanol adsorption capacity even at low partial pressure, e.g., 0.2 mm Hg, which can achieve 12 wt %. For ethylene, the adsorption capacity is only 0.15 wt % at 750 mm Hg. Specific Embodiments While the following is described in conjunction with specific embodiments, it will be understood that this description is intended to illustrate and not limit the scope of the preceding description and the appended claims. A first embodiment of the invention is a process of removing methanol, CO2or both from a hydrocarbon stream, comprising contacting a hydrocarbon stream comprising hydrocarbon and the methanol, the CO2, or both with an adsorbent comprising a 3A type zeolite to remove at least a portion of the methanol, the CO2, or both to produce a purified hydrocarbon stream comprising 10.0 ppmw or less of methanol, or 10.0 ppmv or less of CO2, or both, wherein the 3A type zeolite comprises less than 5% of a binder and has an ion exchange ratio of 30% to 70%. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the hydrocarbon comprises an olefin. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the olefin comprises ethylene or propene. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the 3A type zeolite has an ion exchange ratio of 30% to 50%. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the purified hydrocarbon stream comprises 1.0 ppmw or less of methanol. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the adsorbent has a porosity of 15% to 50%. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the adsorbent further comprises an additive. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein a total amount of the binder and the additive is less than 5% wt. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the contacting takes place at a temperature in a range of 15° C. to 50° C. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the purified hydrocarbon stream comprising 2.0 ppmv or less of CO2. A second embodiment of the invention is a process of removing methanol, CO2, or both from an ethylene or propene stream, comprising contacting the ethylene stream comprising ethylene or the propene stream comprising propene and the methanol, the CO2, or both with an adsorbent comprising a 3A type zeolite to remove a portion of the methanol, the CO2, or both to produce a purified ethylene or propene stream comprising 1.0 ppmw or less of methanol, or 10.0 ppmv or less of CO2, or both, wherein the 3A type zeolite comprises less than 5% of a binder and has an ion exchange ratio of 30% to 70%. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the 3A type zeolite has an ion exchange ratio of 30% to 50%. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the purified ethylene or propene stream comprises 2.0 ppmv or less of CO2. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the adsorbent has a porosity of 15% to 50%. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the adsorbent further comprises an additive. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein a total amount of the binder and the additive is less than 5 wt. %. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the contacting takes place at a temperature in a range of 15° C. to 50° C. A third embodiment of the invention is a composition comprising a 3A type zeolite comprising less than 5% of a binder, an ion exchange ratio of 30% to 60%, and a porosity of 15% to 50%. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph wherein the ion exchange ratio is 30% to 50%. Without further elaboration, it is believed that using the preceding description that one skilled in the art can utilize the present invention to its fullest extent and easily ascertain the essential characteristics of this invention, without departing from the spirit and scope thereof, to make various changes and modifications of the invention and to adapt it to various usages and conditions. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limiting the remainder of the disclosure in any way whatsoever, and that it is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims. In the foregoing, all temperatures are set forth in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated. | 13,256 |
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