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fig1 illustrates schematically three stacked hub units , designated ‘ unit 1 ’, ‘ unit 2 ’, and ‘ unit 3 ’, connected together to form a ring for the circulation of packets that may be put on the ring by any one of the units . it will be understood that only one unit at any time may in normal operation place packets on the ring . each of the units is similar and for convenience only the middle unit will be described in detail . this unit is a hub unit 10 which has two duplex ports , a first port 11 , conveniently called ‘ down ’ port and a second port 12 , conveniently called ‘ up ’ port . the unit 10 has two signal paths . a first path , which for various reasons is preferably termed the arbitration path , proceeds from the ‘ down ’ port 11 of the unit to the ‘ up ’ port 12 . it is convenient to sub - divide the functions of the ports into receive and transmit ( rx and tx respectively ). thus the arbitration path proceeds from the down rx terminal to the up tx terminal . a second or return path 14 extends from the port 12 to the port 11 , and in particular from the ‘ up rx ’ part of the second port 12 to the ‘ down tx ’ part of port 11 . the forward or arbitration path 13 includes a processing section 15 which in the normal operation of the hub unit cooperates with arbitration packets that are sent around the ring and which , as briefly described later , and more fully described in the aforementioned applications , enable the units to determine which will be the master unit ( placing packets on the ring ) at any time in a manner which grants the units a fair access to the ring . in fig1 the processing function 15 is shown as connected to a transmit ( tx ) section 17 and a receive ( rx ) section 18 . these are intended to represent the transmitting and receiving functions respectively of the hub unit , which in respect of its connection to ports ( not shown ) is intended to be of known form . a single hub can broadcast a packet received at any port to all its other ports and the purpose of stacking units is to provide a hub unit with many more ports than can conveniently be provided on a single commercially acceptable unit . fig2 illustrates a simple way of connecting a cascade of units so that they form a mutual ring as indicated in fig1 . in the simple connection shown in fig2 the ‘ up ’ port of the lower of each adjacent pair of units is connected by a known form of cable to the ‘ down ’ port of the next unit up . fig2 illustrates four stacked units arranged in this manner . before leaving fig2 and by way of introduction to fig3 it may be remarked that each unit is adapted to sense whether a given port is connected to another operative unit . this may be performed in known manner , by the process set out in ieee standard 802 . 3 - 1998 , clause 37 , but briefly , the effect is that if a port is not connected to another operative unit , the unit causes that port to be internally bypassed by packets which would otherwise proceed towards that port . thus as shown for unit 1 , for which the ‘ down ’ port is not connected to another unit , packets that would proceed along the return or repeat path towards the down port internally bypassed that port and proceed to the first or arbitration path . likewise , as shown for unit 3 , of which the ‘ up ’ port is not connected to another unit , packets that proceed towards the ‘ up ’ port along the arbitration path internally bypassed that port to the return path . in this manner , as also explained in the aforementioned patent applications , the units define a cascade within which is provided a ring for the circulation of packets , enabling both arbitration for access to the ring and also enabling packets to pass from one unit to the others . in the example shown in fig1 unit 1 is at the ‘ bottom ’ of the stack as will be further explained hereinafter , owing to the possibility of the use of ‘ resilient ’ cable or incorrect combinations of cables , it cannot be presumed that unit 1 will be at the bottom of the stack and it is desirable to provide a configuration process by means of which the unit that effectively is at the bottom of the stack is determined . fig3 illustrates the general layout of a unit . this is generally in the form described in the earlier applications and accordingly need only be described in a summary form signals received at the down rx terminal 101 are de - serialised block 102 , aligned in block 103 , decoded in an 8b10b decoder 104 , stored temporarily in elastic buffer 105 , and coupled to one input of multiplexer 106 . the output of multiplexer 106 is coupled to an arbitration unit 107 ( generally described in the aforementioned applications ) and the arbitrator path includes a multiplexer 108 , an 8b 10b encoder 109 , and serialiser 110 coupled to the up transmit terminal 111 . the down path commences with the up receive terminal 112 and proceeds through a deserialiser 113 , an alignment block 114 , an 8b10b decoder 115 , an elastic buffer 116 , a multiplexer 117 , an 8b10b encoder 118 , and a serialiser 119 to the down transmit terminal 120 . a conventional auto - negotiation circuit 123 is coupled to the decoder 104 and the encoder 118 and a corresponding auto - negotiation circuit 124 is connected to the decoder 115 and the encoder 109 . among other things , the purpose of the multiplexers 106 and 117 is to provide a bypass of the down port ( 101 / 120 ) and one purpose of the multiplexer 108 and the multiplexer 117 is to provide bypass of the up port ( 111 / 112 ). multiplexer 108 also serves , under the control of the arbitration unit 107 , to provide packets onto the ring if the unit is acting as a master , as described in the aforementioned applications . packets from ports ( not shown ) arrive by way of a bus 125 . packets can leave the ring at arbitration unit 107 , if the respective unit is the ‘ master ’, and travel by way of bus 126 to those ports . at all other units in the ring , the arbitration unit copies the packet to the encoder 109 via the multiplexer 108 and , if the relevant destination box id is set , also copies the packet to the bus 126 . a link detection function 128 coupled to decoder 104 is generally configured as a rx sync function in accordance with the ieee standard 802 . 3 - 1998 clause 37 , but may include an error rate threshold counter with a threshold which , if exceeded , is used as a criteria for a link fail . thus if the down port ( 101 / 120 ) is not receiving signals , either the unit is at the bottom of the stack or a stack failure has occurred . there is also a link detect function 127 which is coupled to decoder 115 the link detect functions 127 and 128 can determine by way of the cascade configuration function 129 , operate multiplexers 106 , 108 and 117 , depending on circumstances , so that if there is no unit connected to the down port , packets or headers arriving at multiplexer 117 will be routed by way of multiplexer 106 back to the up path . likewise , if there is no unit connected to the up port , packets or headers passing through arbitration unit 107 and arriving at multiplexer 108 will be routed by way of multiplexer 117 , thereby bypassing the up port . thus when a cascade port is connected to another port it will first use ( in this example ) the rx sync function to establish if a valid connection exists . if so , it will auto - negotiate to establish the capabilities of the connected device and , if the device is capable of being connected in the cascade , this will be indicated to the link detect block and the multiplexers will be set such that the port is connected into the cascade ring . fig8 illustrates a standard form of connector , an eight pin shielded ansi fibre channel style - 2 connector which may have a mechanical mating interface as defined by iec 61076 - 3 - 103 . in essence pins 1 and 3 of this connector constitute the transmit path and pins 6 and 8 constitute the receive path , pins 1 and 8 being positive and pins 3 and 6 being negative . connection of pins 4 and 5 denotes a ‘ resilient ’ cable . the connection may be sensed internally by means of a pull - up resistor connected to pin 4 and a ground connection to pin 5 , so that pin 4 will go ‘ low ’ for a resilient cable . in the simply connected system shown in fig2 it is easy to identify which unit is at the ‘ bottom ’ of the stack . however , it is not necessary to make such a simple connection wherein each unit has its ‘ up ’ port connected to the ‘ down ’ port of the unit which is physically next to it in the ascending direction . furthermore , it is customary and desirable to employ a loop back cable such as is shown in fig4 wherein unit 4 in that figure has its ‘ up ’ port connected to the ‘ down ’ port of unit 1 . the advantage of using a resilient cable is that it enables a maximum of units to continue functioning in the event that one of the units is subject to failure . the configuration phase has several sub phases . first , it needs to detect valid code words and auto - negotiation to determine that a connection with valid coding exists on its cascade up or cascade down ports and that the connected unit is either operating as a cascade unit or is capable of so doing . second , having verified that a valid connection exists , the unit must connect to that unit by setting the data path multiplexers appropriately so that the up or down port ( or both of them as the case may be ) is no longer bypassed . third , it needs to send configuration frames ( which may be generated in the arbitration unit 107 ) in order to resolve the bottom of the stack condition and unit numbering . once the ‘ bottom of stack ’ has been resolved , a unit needs to enter the idle master arbitration state if the unit is at the bottom of the stack or the idle state if it is not . configuration may need to be performed when power is turned on or reset . further , link status changes can occur when units power up or down or cables are removed . the insertion or removal of a cable may cause several status changes because in practice a resilient cable detection circuit is separate from the data circuit . further , a system may enter the configuration state if a unit fails to detect an arbitration header within a set length of time , typically set to be twice the maximum length of the packets plus some arbitrary margin . furthermore , whenever a packet passes the ‘ bottom of stack ’ unit , that unit sets a bit ( illustrated as the ‘ boss ’ bit ) to indicate its presence . this provides two detectable error conditions . first , if the master is stripping its own packet off , the bit is not set then a ring master error has occurred . second , if the bottom of stack unit receives a packet with the boss bit set and no parity error , there is a boss error either because there are no masters on the ring or there is a second unit that is acting as if it were the bottom of the stack . the general principle is that if any of the above circumstances are detected , then a unit may send out a configuration packet . these packets are sent out without arbitrating for access to the ring . such a packet is shown in fig5 . fig5 illustrates a configuration packet as put on the ring . it has an arb / gnt field set to ‘ 0 ’ to indicate that it is not an arbitration packet and a ‘ config ’ field set to ‘ 1 ’ to indicate that it is a configuration packet . the ‘ boss ’ field is ‘ 0 ’ because the bottom of the stack has not yet been restored . the packet will have its ‘ loop ’, ‘ none ’ and ‘ normal ’ bits set as indicated below and its boxid field set as explained below . fig6 illustrates a configuration packet which is provided by a unit in a repeat mode . the symbol r means that the values possessed by a packet as received are merely repeated . the only change is the incrementing of the boxid field by unity . a packet such as shown in fig5 indicate the down port status of its source unit and will be compared with the down port status of a unit that receives it , according to the table shown in fig7 . in the configuration packets and fig7 ‘ nothing present ’ means that there is no other unit connected to the relevant down port that is to say nothing being received is indicated by the link configuration for that port . this would normally indicate that the unit is at the bottom of the stack but it could occur ( as indicated above ) if a unit in the middle of the stack failed , leaving the unit above it seeing ‘ nothing present ’. ‘ resilient cable ’ means that the down port has a resilient cable present , as indicated by a status signal specific to this type of cable on one of its connector pins . this parameter is asserted regardless of whether anything is being received on the down port . ‘ normal cable ’ means that there is a unit connected to the down port of the unit , and valid activity is being received from it , as indicated by the link configuration . these three parameters in the source unit are indicated by the ‘ none ’, ‘ loop ’ and ‘ normal ’ fields and are used to determine if a unit is at the bottom of the stack by the following reasoning : ( a ) if there is no resilient cable being used within a stack and all the units are working correctly , only the ‘ bottom ’ unit will see ‘ nothing present ’. all the other units will see ‘ normal ’ cable at their down ports . clearly therefore the bottom unit is at the bottom of the stack . if a resilient cable is being used in the stack it must be connected between the bottom of the stack unit and the top of the stack unit ( units 1 and 4 in fig4 ). since there is now no unit present in the stack with nothing present , the only way of distinguishing the bottom of the stack unit is by way of the presence of the resilient cable on the down port . if while a resilient cable is being used one of the units in the stack fails , then the unit above it will see nothing present . in this case the unit with the resilient cable connected to its down port is still the ‘ bottom of stack ’. however , there are other circumstances which can be accommodated by the resolution scheme shown in the table . if a customer chooses to use several resilient cables within a stack or if he chooses to try and use a normal cable as a resilient cable , it is desirable to ensure that the stack still works even though the stack numbering may not be conventional and to resolve a single unit to perform the bottom of stack functions . the table summarises the decision each receiving unit must make based on the cable status of its own cascade down port versus that indicated by the configuration packet . if the result is ‘ win ’ the unit enters the configuration master mode and must continue as a source for configuration packets until it sees its own packet returned , as indicated by unique mac address for each unit . if the result is ‘ lose ’, the unit must enter a configuration repeat mode wherein it repeats the incoming configuration packets , but modifies them so as to increment the unit number in the status box location as shown by the packet in fig6 . the configuration master mode will provide such a packet with this value set to zero . the resulting number is stored and will become the stack unit of that number , that is to say the physical location of the stack , once the ‘ bottom of stack ’ is resolved . if the result is ‘ lowest address wins ’, there is a mis - configuration in the stack and the unique mac address value is used to resolve the decision . the option shown in fig7 is either ‘ lose ’ or ‘ lowest mac address wins ’. the former will prevent a loop being made with normal cables because the configuration process would continue indefinitely but the latter will allow a loop to be made with normal cables instead of a resilient cable . the result of this process is that one and only one unit will remain as the configuration master , sourcing configuration packets onto the ring while all the other units merely repeat the packet and store the result of the incremented status box value as there are source unit numbers . the single remaining configuration master will thus be ‘ bottom of the stack ’ and all the other units will be numbered in ascending order above it . in the case of a mis - configuration the units will still be numbered in ascending order from the configuration master which will assume the ‘ bottom of stack ’ function , but its location may be anywhere within the stack . | 7 |
the construction of an optical disk drive of the invention will be described first with reference to fig1 and 2 . referring to fig1 , there are shown a disk 1 for recording / reproducing data , an objective lens 2 for use in gathering beam flux on the disk 1 , a focusing actuator 3 to drive the objective lens 2 in the rotation - axis direction of the disk 1 , a tracking actuator 4 to drive the objective lens 2 in the radius direction of the disk 2 , an aberration correcting lens 5 for correcting the aberrations and an aberration correcting actuator 6 to drive the aberration correcting lens 5 in the optical - axis direction . in addition , there are shown an optical detector 7 for optically detecting the disk 1 , a position detector 8 for detecting the position of the aberration correcting lens , a position signal generator 9 for setting the operating point and sensitivity relative to the output from the position detector 8 , and an aberration correction control signal generator 10 to control the aberration correcting actuator 6 so that the aberration correcting lens 5 can be set in a predetermined position . moreover , there are shown an aberration - correcting actuator drive unit 11 for driving the aberration correcting actuator , a focusing error signal generator 12 for generating a signal of the focusing - direction error of the objective lens relative to the disk , a focusing - control signal generator 13 to control the focusing actuator so that the beam spot can be located just on the recording surface or reproducing surface of the disk , a focusing - actuator drive unit 14 for driving the focusing actuator , and a tracking - error signal generator 15 for generating a signal of the tracking error of the objective lens relative to the track of the disk . also , there are shown a tracking - control signal generator 16 to control the tracking actuator so that the beam spot can be located just on a predetermined track of the disk , a tracking - actuator drive unit 17 for driving the tracking actuator , a spindle motor 18 for rotating the disk , a frequency generator 19 for generating a signal proportional to the rotation speed of the spindle motor , a motor control unit 20 to control the spindle motor to rotate with a predetermined speed , and a temperature sensor 21 . in addition , fig2 is a block diagram of the aberration correction control signal generator 10 . in fig2 , there are shown a target position setting unit 101 for setting the target position of the aberration correcting lens , a low - pass compensation filter 102 , a phase compensation filter 103 , a target range judging unit 104 for judging whether the error between the aberration correcting lens position and the target position is within a predetermined range , and a dither signal generator 105 . the outline of the operation of each block and the relation between the blocks will be described next . referring to fig1 , the focusing actuator 3 moves the objective lens 2 in the rotation axis direction of the disk , and the tracking actuator 4 moves the objective lens 2 in the radius direction of the disk . the optical detector 7 converts the reflected light into an electric signal , and supplies the electric signal to the focusing - error signal generator 12 and tracking - error signal generator 15 . the focusing - error signal generator 12 generates a focusing error signal based on the fed signal , and supplies it to the focusing - control signal generator 13 and aberration - correction control signal generator 10 . the focusing - control signal generator 13 generates a focusing control signal based on the fed signal , and supplies it to the focusing - actuator drive unit 14 . the focusing - actuator drive unit 14 drives the focusing actuator 3 in accordance with the fed signal . the tracking - error signal generator 15 generates a tracking error signal based on the fed signal , and supplies it to the tracking - control signal generator 16 and aberration - correction control signal generator 10 . the tracking - control signal generator 16 generates a tracking control signal based on the fed signal , and supplies it to the tracking - actuator drive unit 17 . the tracking - actuator drive unit 17 drives the tracking actuator 4 in response to the fed signal . in addition , the aberration correcting actuator 6 moves the aberration - correcting lens 5 in the optical - axis direction . the aberration - correcting lens position detector 8 converts the aberration correcting lens position into an electric signal , and supplies it to the position signal generator 9 . the position signal generator 9 corrects its operating point and sensitivity relative to the fed signal , and supplies the corrected signal to the aberration - correction control signal generator 10 . in the aberration correction control signal generator 10 , the target - position setting unit 101 compares the fed signal with a target value , and supplies the resulting signal to the low - pass compensation filter 102 , phase compensation filter 103 and target range judging unit 104 . the temperature sensor 21 converts the drive - inside temperature into an electric signal , and supplies it to the dither signal generator 105 . the target - range judging unit 104 uses the fed signal from the target - position setting unit 101 to judge whether the aberration - correcting lens is out of a predetermined range with respect to the target position , and supplies the judgment signal to the dither signal generator 105 . the dither signal generator 105 determines the frequency and amplitude of a dither signal based on the signal fed from the temperature sensor 21 , and turns the generation of this dither signal on or off in accordance with the signal fed from the target range judging unit 104 . the aberration correction control signal generator 10 produces a sum signal of the output signals produced from the low - pass compensation filter 102 , phase compensation filter 103 and dither signal generator 105 , and supplies it to the aberration - correcting actuator drive unit 11 . the aberration - correcting actuator drive unit 11 drives the aberration correcting actuator 6 in response to the fed signal . the spindle motor 18 drives the disk 1 to rotate . the frequency generator 19 converts the rotation speed information of the spindle motor 18 into an electric signal , and supplies it to the motor control unit 20 . the motor control unit 20 controls the spindle motor 18 for rotating the disk 1 to rotate with a predetermine speed based on the fed signal . the adjustment of the operating point and sensitivity of the position signal generator 9 to the input signal will be first described with reference to fig4 . here , the adjustment of the operating point and sensitivity means that the offset and gain of the signal to the aberration correction control signal generator 10 that makes digital processing are adjusted before the supply of this signal to the generator 10 so that the maximum resolution can be surely obtained within the practical movement range of the aberration correcting lens . in other words , the operating point is adjusted by the offset control , and the sensitivity is adjusted by the gain control . thus , this adjustment enables the aberration to be corrected with high precision . the aberration - correcting lens is required to move within a wide range and to control with high precision , and thus it needs a high resolution . in order for both wide dynamic range and high resolution to be achieved when the control system partially makes digital processing , it is considered to employ a method for increasing the bit number or bit - precision of the ad converter . however , since the specification of dsp ( digital signal processor ) is necessary to change , it is not easy to achieve . therefore , first the operating point and sensitivity are adjusted according to the method shown in fig4 . as illustrated in fig4 , the movable range of the aberration correcting lens has a practical range and an unused range . the practical range is the region lying between the target positions of the aberration - correcting lens relative to the layers of the two - layer recording / reproducing disk . the unused range is the region corresponding to the distance by which the aberration - correcting lens can be additionally moved considering the optical pickup assembly tolerance , but it is not used in the actual operation . although the location of the practical range in its movable range depends upon each optical disk drive , it suffices to detect the position signal within the practical range if it can be detected after the target position of the aberration - correcting lens is determined relative to the 0 - layer or 1 - layer of the disk on each drive . ( fig4 shows the case in which the practical range lies substantially at the center of the movable range .) accordingly , the operating point of the position signal generator 9 can be adjusted to lie at the center of the signal level by applying an offset to the input signal as indicated by ( 1 ). in addition , the practical range can be adjusted to enter in the whole dynamic range of dsp by controlling the gain as indicated by ( 2 ), thus assuring the resolution . when the target position of the aberration correcting lens is determined relative to the 0 - layer or 1 - layer , adjustment is performed so that the position signal within the movable range can be detected as shown in fig5 . in other words , the position signal generator 9 determines the target position under the conditions that an offset is applied to the input signal as indicated by ( 3 ) and that the gain is set as indicated by ( 4 ). description will be made of the operation of the target position setting unit 101 at the focusing jump time when the beam spot moves between the layers of the two - layer disk . when the beam spot moves between the layers , it is necessary to also change the target position of the aberration - correcting lens . when the aberration - correcting lens moves slower than the focusing control in which the objective lens is moved in the focusing direction , the target position of the aberration - correcting lens is required to previously change to the destination layer . however , when the aberration - correcting lens is moved from the original - layer target position , the amplitudes of the focusing and tracking error signals are reduced , thus making the focusing and tracking control unstable . when the target position is abruptly changed in a single step as shown in fig6 a , the operation of the aberration - correcting lens gives rise to an overshoot , incurring further instability . thus , the target - position setting unit 101 changes from the original position to the destination target position in steps as shown in fig6 b to reduce the overshoot . alternatively , the low - pass compensation filter 102 and phase compensation filter 103 may be changed in their characteristics to achieve the same effect . in addition , the tracking control in which the error signal amplitude could be remarkably reduced may be disabled before the aberration - correcting lens switches the target positions . the operation of the target - range judging unit 104 will be described in detail with reference to fig7 . the aberration - correcting lens position target range of the target - range judging unit 104 is set according to the suppression specification of the deviation and variation necessary for each layer as shown in fig7 . fig7 is graphs schematically showing the lens position for the movement of the beam spot between the layers , the on / off of the dither signal ( high - frequency signal ), and the aberration - correction control signal . before the change of the target position , the target - range judging unit 104 turns on the output of the dither signal generator 105 . then , the target - position setting unit 101 sets the target on the destination layer . the purpose of the application of the dither signal to the drive signal for driving the spherical aberration correcting element is to enable it to be smoothly driven . in other words , the linear actuator for use in driving the beam expander for correcting the spherical aberration enables the optical pickup to be small - sized as compared to the current stepping motor , and it has a merit of lower cost than the piezoactuator . however , the friction to the drive shaft increases for the necessity of looseness reduction and high retainability . therefore , if the object to be driven is tried to control without application of dither signal , it suddenly moves , thus accurate control being difficult . in this case , if the dither signal is applied to the drive signal for the spherical aberration correcting element , or for the linear actuator , the actuator is continuously controlled to perate finely as indicated at the bottom graph in fig7 , thus less affected by the static friction so that it can be smoothly driven . the target range judging unit 104 maintains the dither signal generator 105 to operate until the output of the target position setting unit 101 enters in the target range . after the output of the target position setting unit 101 moves into the target range , the judging unit 104 controls the dither signal generator 105 to be made in the off - state . when the position of the actuator is being changed through the stepwise ranges toward the target range as described above , the dither signal generator 105 is kept in operation to output fine signals or to be ceased even if the output of the target position setting unit 101 comes into each of the stepwise ranges . in other words , the dither signal is applied only when the linear actuator is being driven . the dither signal is not impressed when it is not driven , or during the recording or reproduction . if the dither signal were always applied , the spherical aberration correcting element would continue to finely vibrate even after the arrival at the target position , thus adversely affecting the focusing control . the phrase “ linear actuator is being driven ” given above means that , when the target position is controlled to change , the high - frequency signal is continuously applied to the element to adjust its position until the element arrives in the target range . in addition , the driving of the linear actuator as described above is performed before the reproduction processing of the read - out signal from the optical disk , or before the demodulation of the read - out signal from the optical disk and production of video signal or audio signal . moreover , the dither signal generator 105 generates such a signal as to start changing with a zero - amplitude phase and to stop at another zero - amplitude phase as shown in fig8 . alternatively , it generates such a signal as to gradually increase the amplitude when starting to produce the signal and to gradually decrease the amplitude when stopping from producing the signal . the reason why the dither signal is started to apply at the zero - amplitude phase or stopped from applying at the zero - amplitude phase is that the sudden application or stop of the dither signal might adversely affect the control even if the dither signal is a very small oscillation as compared with the drive signal . in this connection , the start or stop of application of the dither signal at the zero - amplitude phase will result in smooth control , thus better results being acquired . the gradual increase or decrease of the amplitude of the dither signal at the start or stop of application will also result in smooth control . description will be made of a method for determining the frequency and amplitude of the signal produced from the dither signal generator 105 . the signal from the dither signal generator 105 needs a predetermined frequency or below and a predetermined amplitude or above in order that the movable portion of the aberration correcting mechanism including the aberration correcting lens can be operated without influence of the static friction to the stationary part . in addition , in order to suppress the effect of the movement of the aberration correcting lens on the focusing control and tracking control , the frequency and amplitude of the signal must be increased above and decreased below predetermined values , respectively . the influence on the focusing control and tracking control is determined according to the amplitude variation of the focusing error signal and tracking error signal before the application of the dither signal . alternatively , it is determined on the basis of the performance fluctuation of the reproduction of the data recorded on the disk . thus , the dither signal generator 105 determines the amplitude and frequency for each temperature that meet these conditions , and generates the most appropriate dither signal based on the output from the temperature sensor 21 . in other words , the amplitude of the signal must be set so high as to reduce the effect of the static friction and so low as not to adversely affect the focusing control and tracking control . similarly , the frequency needs to be determined so high as not to adversely affect the focusing control and tracking control and so low as to reduce the effect of the static friction . here , the frequency will be specifically mentioned . the frequency f of the dither signal takes the following range . in other words , if the main resonance of the aberration correction driving actuator is represented by f0_s , the control bandwidth of the aberration correction driving actuator by fc_s , the control band of the focusing actuator by fc_f , and the control band of the tracking actuator by fc_t , then the following expressions can be obtained . in the present circumstances , the condition of fc_s = 0 . 5 khz & lt ; fc_f , fc_t = 5 ˜ 10 khz is estimated . the construction of the optical disk drive of the invention will be described with reference to fig1 and 3 . in the embodiment 2 , the blocks 1 through 21 shown in fig1 are the same as in embodiment 1 , and thus will not be described . fig3 is a block diagram of the aberration correction control signal generator 10 of the embodiment 2 . the blocks 101 through 104 shown in fig3 are the same as in embodiment 1 , and thus will not be described . in fig3 , there are shown a timer 106 , a gain control unit 107 for the aberration correction control , and a gain amplifier 108 of the aberration correction control loop . the outline of the operation of each block and the relation between the blocks will be described . the focusing control , tracking control and spindle control are the same as in embodiment 1 , and thus will not be described . the aberration correcting actuator 6 moves the aberration correcting lens 5 in the optical - axis direction . the aberration - correcting lens position detector 8 converts the position of the aberration correcting lens into an electric signal , and supplies it to the position signal generator 9 . the position signal generator 9 corrects the operating point and sensitivity given for the fed signal , and supplies the corrected signal to the aberration correction control signal generator 10 . in the aberration correction control signal generator 10 , the target position setting unit 101 compares the fed signal and the target value , and supplies the compared result to the low - pass compensation filter 102 , phase compensation filter 103 and target range judging unit 104 . the temperature sensor 21 converts the drive - inside temperature into an electric signal , and supplies it to the gain control unit 107 . the timer 106 supplies time information to the gain control unit 107 . the target range judging unit 104 judges whether the aberration correcting lens is located out of a predetermined range of the target position on the basis of the fed signal , and supplies the judgment result signal to the gain control unit 107 . the gain control unit 107 determines a set value of gain on the basis of the signals from the temperature sensor 21 and target range judging unit 104 , and sets the gain of the gain amplifier 108 according to the set value . the aberration correction control signal generator 10 supplies the sum signal of the low - pass compensation filter 102 and phase compensation filter 103 to the aberration correcting actuator drive unit 11 through the gain amplifier 108 . the aberration correcting actuator drive unit 11 drives the aberration correcting actuator 6 according to the fed signal . the operation of the main blocks will be described in detail . the adjustment of the operating point and sensitivity of the position signal generator 9 is the same as in embodiment 1 . the operation of the target position setting unit 101 at the time of focusing jump is the same as in embodiment 1 . the operation of the target range judging unit 104 and gain control unit 107 will be described in detail with reference to fig9 and 10 . the target range of the target range judging unit 104 about the position of the aberration correcting lens is set according to the deviation and variation suppression specification necessary for each layer as shown in fig9 . the target range judging unit 104 judges whether the signal fed from the target position setting unit 101 is within the target range , and supplies the judgment result signal to the gain control unit 107 . the gain control unit 107 judges the signal fed from the temperature sensor 21 by using thresholds t 1 and t 2 ( t 1 & lt ; t 2 ), and sets g 01 , g 02 , g 03 , g 11 , g 12 and g 13 in the gain amplifier 108 according to the judgment result signal fed from the target range judging unit 104 . the gains have the relations of g 01 & lt ; g 11 , g 02 & lt ; g 12 , g 03 & lt ; g 13 . in addition , when the static friction between the movable portion and fixed portion of the aberration correcting mechanism decreases with the increase of temperature , the relations of gains are g 01 & lt ; g 02 & lt ; g 03 , and g 11 & lt ; g 12 & lt ; g 13 . when the static friction increases with the increase of temperature , the relations of gains are g 01 & gt ; g 02 & gt ; g 03 , g 11 & gt ; g 12 & gt ; g 13 . here , the target range judging unit 104 may have one or more target ranges except the target range based on the suppression specification as shown in fig1 . in this case , the gains g 21 , g 22 , g 23 , g 31 , g 32 and g 33 are added on the table of fig1 as established gains . the gain control unit 107 has the table shown in fig1 . in this case , the gains respectively take the lowest values in the target range 0 that means that the lens has arrived at the target position , and take higher values in the other ranges as the lens approaches to the target range , that is , g 01 & lt ; g 31 & lt ; g 21 & lt ; g 11 , g 02 & lt ; g 32 & lt ; g 22 & lt ; g 12 , g 03 & lt ; g 33 & lt ; g 23 & lt ; g 13 . in addition , the gain control unit 107 increases the gains to be set in the gain amplifier 108 to exceed the values shown in the above table according to the time information fed from the timer 106 when the signal fed from the target position setting unit 101 does not come into each target range in a predetermined time . the flowchart of a specific control in embodiment 1 will be described with reference to fig1 and 14 . first , referring to fig1 , when the aberration correcting element needs to be driven with the focusing control on and with the tracking control off , condition setting is first performed in order to suppress the effect of the superposition of high - frequency signal and the drive signal for the aberration correcting element on the focusing control . at this time , the condition setting is made so that the focusing error signal can be observed when the focusing control and tracking control are both turned off . in addition , the high - frequency signal is not applied . then , the focusing error signal amplitude is acquired under the condition that the high - frequency signal is not applied ( s 11 ). this value is represented by fe 0 . next , the dither signal ( high - frequency signal ) is added to the drive signal for the aberration correcting element ( s 12 ). at this time , the initial amplitude ( scd 0 ) of the high - frequency signal is assumed to be small enough such as zero . then , the output amplitude of the position sensor is measured , and the amplitude of the high - frequency signal is increased δscd by δscd ( s 15 ) until the measured amplitude ( se 1 ) becomes larger than a predetermined value ( seth ) ( s 14 ). the amplitude of the high - frequency signal satisfying the condition of se 1 & gt ; seth is represented by scd 1 . then , the amplitude of the focusing error signal is measured ( s 16 ), and the amplitude of the high - frequency signal is increased δscd by δscd ( s 18 ) until the absolute value of the difference between the measured amplitude ( fe 1 ) and the previously given amplitude fe 0 becomes larger than a predetermined value ( feth ) ( s 17 ). the amplitude of the high - frequency signal satisfying the condition of | fe 1 − fe 0 |& gt ; feth is represented by scd 2 . the actually used high - frequency signal amplitude scd is set to satisfy the condition of scd 1 & lt ; scd & lt ; scd 2 by using the obtained values scd 1 and scd 2 . for example , the amplitude scd may take an intermediate value between scd 1 and scd 2 , or as scd =( scd 1 + scd 2 )/ 2 . referring to fig1 , when the aberration correcting element needs to be driven with the focusing control on and the tracking control on , it is necessary to suppress the effect of the superposition of the high - frequency signal and the drive signal for the aberration correcting element on the focusing control and tracking control . in this case , the processing shown in fig1 is necessary in addition to that shown in fig1 . the condition setting in the flowchart of fig1 is performed so that the tracking error signal can be observed with the focusing control on and tracking control off . in addition , the high - frequency signal is not applied . then , the tracking error signal amplitude is acquired with the high - frequency signal not applied ( s 101 ). this value is represented by te 0 . next , the high - frequency signal is added to the drive signal for the aberration correcting element ( s 102 ). at this time , the initial amplitude ( scd 1 ) of the high - frequency signal is assumed to be the value detected in the flowchart shown in fig1 . then , the tracking error signal amplitude is measured ( s 103 ), and the amplitude of the high - frequency signal is increased δscd by δscd ( s 105 ) until the absolute value of the difference between the measured amplitude ( te 1 ) and the above given te 0 becomes larger than a predetermined value ( teth ) ( s 104 ). the amplitude of the high - frequency signal satisfying the condition of | te 1 − te 0 |& gt ; teth is represented by scd 3 . the actual used high - frequency signal amplitude scd is set to satisfy the condition of scd 1 & lt ; scd & lt ; scd 2 or scd 3 ( any smaller one ) by using the above scd 1 , scd 2 and scd 3 . for example , the amplitude may take an intermediate value between scd 1 and scd 2 or scd 3 , or as scd =( scd 1 + scd 2 or scd 3 )/ 2 in order to assure the margin to the environmental change such as temperature change . as described above , according to the above embodiments , when the aberration correcting lens is moved , the dither signal is superimposed on the control signal or the gain of the control loop is increased , thereby enabling the aberration correcting lens to be controlled with high precision . therefore , the linear actuator can be used with less lens tilt and less looseness in the aberration correcting mechanism , and thus a small - sized and inexpensive optical disk drive can be provided . it should be further understood by those skilled in the art that although the foregoing description has been made on embodiments of the invention , the invention is not limited thereto and various changes and modifications may be made without departing from the spirit of the invention and the scope of the appended claims . | 6 |
with reference to fig1 a crystallization tray 100 constructed in accordance with an embodiment of the invention will now be described . the tray 100 is especially useful in crystallizing biological macromolecules such as proteins and nucleic acids ; however , the tray 100 may be used to crystallize any crystallizable substance . some general material properties of the tray 100 will first be described , followed by a description of the elements of the tray 100 and the tray 100 in use . the tray 100 preferably has a single - piece , integrated construction and is manufactured using an injection molding process . the tray 100 is preferably made from an optically clear , plastic material such as , but not by way of limitation , a clear polystyrene material or polypropylene polymer . an optically clear , inert , plastic material allows crystal growth to be viewed under a microscope . crystal growth may also be viewed using an imaging system , such as , for example , a video camera operably linked to a computer having a computer monitor that can display the image . the plastic material of the tray 100 preferably is a low - wettability material having a relatively high contact angle with respect to water so that the solution of the sample to be crystallized will tend to form discrete drops when placed in contact with the crystallization tray 100 . the plastic material selected should be moldable so that the inner surfaces of the tray 100 that come into contact with the macromolecule solution have a smooth texture . the material used should be resistant to chemicals such as methyl pentane diol , organic acids and alcohols , and should be stable for long term storage in ph 3 - 10 solutions . the tray 100 includes a rectangular base 110 with an array of crystallographic cells 120 and a rectangular skirt 130 joined with the base 110 through a step 140 . the rectangular dimensions of the base 110 are slightly smaller than the rectangular dimensions of the skirt 130 , and the undersurface of the rectangular skirt 130 is open and hollow , allowing for stacking of multiple trays 100 . the base 110 includes a first side wall 150 , a second side wall 160 , a first end wall 170 , a second end wall 180 , and a top wall 190 . where the first side wall 150 and first end wall 170 would normally intersect , the base 110 includes a single beveled or cut corner 200 for orienting the tray 100 ( e . g ., always knowing which way is up ) and to denote a first cell 210 in the array . in a preferred embodiment , the tray 100 includes ninety - six cells 120 organized in twelve columns denoted respectively by the numbers 1 - 12 and eight rows denoted respectively by the letters a - h . the beveled corner 200 preferably indicates the position of the a - 1 cell ( i . e ., the first cell , the cell in the first row and first column , or the cell located in column a , row 1 ). the top wall 190 preferably includes three knobs 220 that are used for orienting the tray 100 in the imaging system . with reference to fig2 - 5 and especially fig3 - 5 , the crystallization cells 120 will now be described in more detail . each cell 120 generally includes a reservoir 230 , a shelf 240 , and a sample receptacle 250 . the cell 120 is generally defined by opposite side walls 260 , a first end wall 270 , a second end wall 280 comprised of a lower wall portion 290 and an upper wall portion 300 joined by the shelf 240 , and a bottom wall 310 . the side walls 260 and end walls 270 , 280 terminate at the top of the cells 120 in ridges 320 . the ridges 320 include top walls 330 that define a second plane that is parallel with and extends above a first plane defined by the top wall 190 of the base . when a cover is applied to the top of the tray 100 , the cover is supported by the ridges 320 . the cover seals each cell 120 along the cell &# 39 ; s surrounding ridge 320 and isolates the cell 120 from adjacent cells 120 . the space between adjacent ridges 320 is preferably just wider than a blade of a cutting instrument for selectively cutting the cover around one or more select cells 120 in the tray 100 to access the crystallized substance in the cell ( s ) 120 without disturbing the cover for adjacent cells 120 . widening the ridges 320 , causing the space between adjacent ridges 320 to be narrower , creates a better top wall sealing surface around the cells 120 for the cover and creates a better , more defined cutting path for the blade of the cutting instrument . the reservoir 230 is preferably a generally rectangular block - shaped void . in a preferred embodiment , the reservoir 230 is sized to accommodate approximately 100 μl of equilibrating solution . in alternative embodiments , the reservoir 230 may have a different configuration and / or may be sized to accommodate other volumes of equilibrating solution . with reference to fig4 the sample receptacle 250 is preferably cup - shaped with a flat bottom surface 340 . the flat bottom surface 340 allows for optical clarity for viewing the drop , and the size of the sample receptacle 250 helps to keep the sample solution held together in a tight drop and prevents spreading of the drop . this makes the sample receptacle 250 appropriate for both macromolecule crystallography and for more general crystallography . this also keeps the drop centered , in a consistent position for visualization with a microscope . the sample receptacle 250 is preferably sized to accommodate a 2 μl sample drop . sizing the sample receptacle this small is advantageous because it limits where the sample is in the receptacle , making it easier to locate for visualization , removal , etc . the flat bottom surface 340 of the sample receptacle 250 is curved at the edge where it meets the side wall of the sample receptacle 250 , allowing for a crystallization sample retrieving device ( e . g . nylon fiber microloop connected to shaft ) to be used to smoothly scoop the crystal out of the well without jarring the crystal against the side wall . preferably , the ratio of the reservoir volume to the sample receptacle volume is at least large enough to create an appropriate gradient to drive the concentration of the protein drop high enough to cause the protein to crystallize . those of ordinary skill in the art are aware that the larger the reservoir volume , as compared to the sample receptacle volume , the steeper the gradient will be . this allows for more reproducibility , and the easiest way to determine the likeliness that the crystallization step has been driven to completion . the ratio , however , is preferably within a practical range that allows for high - throughput crystallization . thus , the ratio of the reservoir volume to sample size may be , for example , at least about 500 : 1 , preferably at least about 100 : 1 , preferably at least 75 : 1 , more preferably at least about 50 : 1 , preferably at least about 40 : 1 , and preferably at least about 25 : 1 . in one preferred example , the reservoir is sized to accommodate an equilibrating solution volume of about 100 μl and the sample receptacle is sized to accommodate a sample volume of about 2 μl . with reference back specifically to fig2 the shelf 240 carries the sample receptacle 250 adjacent one of the side walls 260 and includes a flat upper surface 350 . a majority portion 360 of the flat upper surface 350 is located between the sample receptacle 250 and opposite side wall 260 . as used herein , “ majority ” means greater than 50 %. when the tray 100 is oriented in the standard position shown in fig2 so that the a - 1 cell 210 is the upper - left corner of the tray 100 ( i . e ., beveled corner 200 is upper - left corner of tray 100 ), the majority portion 360 of the flat upper surface 350 is located away from the user with respect to the sample receptacle 250 it has been determined by the inventor of the present invention that locating the flat surface of the shelf 240 in this position is ideal for right - handed users ( right - handed users are statistically more common than left - handed users ) because it allows the crystallized sample to be easily moved forward onto the flat surface of the shelf 240 with a crystallization sample retrieving device ( e . g . nylon fiber microloop connected to shaft ). it has been determined that this is more convenient for the user than drawing or dragging the crystallized sample rearward , towards the user . further , when the tray 100 is oriented in the position shown , the shelf 240 is located on the left side of the cell 120 . because the crystallization sample retrieving device is typically operated by the right hand of a right - handed user , locating the shelf 240 on the left side of the cell 120 allows for easier access to the sample receptacle 250 and shelf 240 with the crystallization sample retrieving device . the majority portion 360 of the flat upper surface 350 of the shelf 240 may serve as a cryoprotection holding area for the crystallized sample between crystallization and x - ray diffraction . it is important to cryoprotect the crystallized sample after crystallization and before x - ray diffraction . instead of having to remove the crystallized sample from the cell and cryoprotect outside of the cell , this can be done in the holding area , within the cell 120 . providing a cryoprotection holding area is important because once the crystallized sample is removed from the cell 120 , it may quickly deteriorate in the air because a macromolecule crystal is about 50 % solvent and prone to dehydration . the majority portion 360 of the flat upper surface 350 may also hold a sample drop in addition to , or instead of , the receptacle 250 . this may be desirable for performing , in each cell , two different experiments with the same type of sample or different types of samples , or a single experiment with the sample only placed on the shelf 240 . because the shelf 240 is flatter than the receptacle 250 , the drop spreads out more when placed on the shelf 240 , increasing the surface - to - volume ratio of the drop , changing the kinetics of the equilibrium experiment . in use , the tray 100 is oriented in the standard position shown in fig2 so that the a - 1 cell 210 is the upper - left corner of the tray 100 ( i . e ., angled corner 200 is upper - left corner of tray 100 ). each reservoir 230 is carefully filled with a selected equilibrating solution . different equilibrating solutions can be added to each of the reservoirs 230 if this is desired . typically , aqueous mixtures of buffer , salts , and precipitants such as polyethylene glycol or ammonium sulfate are used as precipitating agents in the equilibrating solution . this solution may contain other components such as organic molecules or other additives . preferably , approximately 100 μl of equilibrating solution is added to each of the reservoirs 230 . in alternative embodiments , the amount of equilibrating solution added to each of the reservoirs 230 may be greater than 100 μl , less than 100 μl , different amounts of equilibrating solution may be added to the reservoirs 230 , and / or different types of equilibrating solution may be added to the reservoirs 230 . following the addition of the equilibrating solution to the reservoirs 230 , a selected macromolecule ( e . g ., protein ) solution drop is deposited within each sample receptacle 250 . the drop is preferably approximately 2 μl and includes a protein in a buffered salt solution containing a lower concentration of the same precipitating agent used in the equilibrating solution . usually , a concentrated protein solution is mixed with the equilibrating solution to obtain the final total volume of , for example , 2 μl . the ratio of protein to equilibrating solution may be varied , and may be , for example , 1 : 1 . it is to be understood that the equilibrating solution as well as the macromolecule solution drops may be added to the cells 120 either by hand or by a sophisticated automated pipetting apparatus which is readily commercially available . because of the novel construction of the tray 100 and the systematic placement of the reservoirs and receptacles , the tray 100 is readily adaptable to most commercially available pipetting systems . once the equilibrating solution and protein drops have been added to the apparatus in the manner described , the cover is carefully placed over the tray 100 so that the top walls 330 of the ridges 320 are positively sealed relative to atmosphere . the tray is designed to provide effective sealing between the top walls 330 and the under surface of the cover , using adhesive tape or a plate sealer . alternatively , a layer of grease , such as silicon grease , or petroleum jelly , may be applied manually or automatically to the top walls 330 of the ridges 320 , and some other clear , impermeable layer plated over the tray . instead of a sitting - drop technique , in an alternative embodiment , a hanging - drop technique may be used for applying the protein drops to the cells 120 . the protein drops may be applied to an undersurface of the cover ( with the undersurface face up ), and the cover may be inverted and the undersurface sealed against the top walls 330 of the ridges 320 so that the protein drops are hanging into the cells 120 . with either technique , each protein drop is positively sealed within each reservoir cell 120 and can equilibrate against the particular equilibrating solution that was earlier deposited into the particular reservoir 230 . since the starting concentration of precipitating agent is always higher in the reservoir 230 than in the protein drop , once the cell 120 is sealed , water will diffuse from the protein drop to the reservoir 230 until the concentration of precipitating agent at equilibrium is the same in the drop as in the reservoir 230 . in general , this diffusion results in a controlled steady increase in the concentration of both the protein and precipitating agent within the drop which forces the protein to come out of solution , hopefully as a crystal . or , in the instance where there is a dilution effect , where the buffer that is in the protein sample is more concentrated than in the reservoir , the protein is said to “ salt into solution ” and the crystallization drop tends to grow . because the tray 100 is made of an optically clear material , the crystallization of each sample may be viewed using a microscope or other visualization apparatus . following crystallization of the protein drops , the cover of the tray 100 is removed . as described above , a blade may be used between the ridges 320 to cut the cover into one or more cover segments that may be individually removed from the top wall 330 of the ridge 320 . after removal of the cover segment ( s ), the crystals are preferably moved onto the majority portion 360 of the flat surface 350 of the shelf 240 with the crystallization sample retrieving device . the flat surface 360 may serve as a cryoprotection holding area for the crystal . a cryoprotectant may be added to the shelf 240 before or after , preferably before , the crystallized sample is moved to the majority portion 360 of the shelf 240 . the crystallized sample may then be swept through the cryoprotectant . as indicated above , moving the crystallized sample to the cryoprotection holding area before removing the sample from the cell 120 helps preserve the crystallized protein . from the flat surface 360 , each crystal may be removed from the cell 120 with the crystallization sample retrieving device and analyzed through x - ray diffraction . in alternative embodiments , the crystals may be analyzed within the tray 100 , the crystals may be removed directly from the receptacles 250 or removed in another manner , and / or the crystals may be analyzed by a technique other than x - ray diffraction . because the crystallization tray 100 includes a rectangular array of ninety - six crystallization cells 120 , the user may simultaneously screen up to ninety - six different combinations of factors that affect crystallization . additionally , the number of factors that can be simultaneously tested can be increased by placing an additional sample drop on the flat majority portion 360 of the shelf 240 . thus , the crystallization tray 100 offers many advantages over crystallization trays in the past , some of which are summarized below . the shelf 240 provides a cryoprotection holding area and additional flat sample holding surface for performing an additional and / or different type of crystallization experiment in the cell 120 . the shape of the sample receptacle 250 maintains the sample drop held together , in a tight drop , and prevents spreading of the drop . the small size of the sample receptacle 250 makes it easy to locate the crystallized sample in the receptacle 250 . the configuration of the shelf 240 makes it ideal for right - handed users to access , move , and / or remove the crystallized sample . the three knobs 220 on the top wall 190 of the tray 100 help for orientation and calibration of the tray 100 . the cut corner 200 also helps for orienting the tray 100 and quickly identifying the first cell in the array . the raised , rectangular ridges 320 provide a sealing support surface for the cover ( s ), allow the cover ( s ) around individual cells 120 to be selectively removed without disturbing the cover ( s ) on adjacent cells 120 , and allow access between ridges for cutting away the cover ( s ) around one or more selected cells . the flat bottom 340 of the sample receptacle 250 allows for ease of imaging . the curvature of the angle between the walls and the bottom of the sample receptacle 250 is suitable for sweeping out the crystallized sample with a mounting loop . it will be readily apparent to those skilled in the art that still further changes and modifications in the actual concepts described herein can readily be made without departing from the spirit and scope of the invention as defined by the following claims . | 2 |
fig1 shows the inventive rectifier assembly 11 including case , casing or housing 13 formed as a can - like container preferably of a relatively high density plastic . casing 13 is closed at one end 15 and open at its other end 17 . a mounting flange 19 has suitable mounting holes 20 to enable the assembly 11 to be mounted in position on a suitable bracket or board . the closed end of the casing 13 includes an extending lug 18 to provide additional shielding and strain relief for the lead 21 connecting to the rectifier assembly 11 . referring now also to fig2 and 4 , a rectifier diode 23 is positioned within the casing 13 and an electrical connection made from lead 21 to one electrode of the rectifier 23 and the other elctrode of the rectifier 23 is connected in series to a second rectifier 24 . rectifier 24 connects to a suitable cylindrical terminal 25 . in operation , a . c . input cap 29 is snapped over terminal 25 substantially to shoulder 23 on terminal 25 to make a good electrical connection . lead 21 connects to the anode of the associated picture tube , not shown . in assembly , one or more rectifier diodes 23 and 24 ( indicated schematically in fig4 ) are mounted concentrically along the axis of the casing 13 . note that as shown in fig5 the rectifier diodes 23 and 24 may be poled in either direction . also , the rectifier diodes of either fig4 or 5 can be mounted or formed in a single block as indicated in fig5 . the encapsulating or potting compound 37 , of any known suitable dielectric , is then poured through the open end 17 of the casing 13 and allowed to solidify . the encapsulating compound 37 thus securely mounts the rectifier diodes 23 and 24 in concentric axial relation within the casing 13 . note that casing could likewise be square or rectangular in cross section , and the rectifier diodes would be mounted in the cross section center . fig2 also shows a square mounting flange 22 for the casing 13 and includes mounting holes 20a positioned on one side of the mounting flange 22 to permit mounting casing 13 such as along the side of a chassis . fig5 shows another embodiment of the inventive assembly 11a wherein the assembly 11a is formed with the casing and the encapsulating compound being of the same material . also , in fig5 in addition to the rectifier diodes 23 and 24 , a resistor 41 may be mounted in series with the diodes ; and , a capacitor 43 may be mounted to have one plate connected to the junction of resistor 41 and diode 35 , and the other plate of capacitor 43 may connect externally of assembly 11a through a suitable lead 44 . in fig5 diodes 23 and 24 are connected in series with the anode of the diode 23 connected to lead 19 , and the cathode of the diode 24 connected to the cap or terminal 25 to thereby provide a relatively negative voltage through lead 31 and contacts 33 to the anode . in the structure of fig5 the various components may be initially assembled and positioned , and the entire assembly molded by insert or transfer molding techniques as one compositely housed assembly . also as shown in fig5 the metal cap 25 can be directly mounted in an associated electrical mounting receptacle indicated generally as 40 . fig6 shows another embodiment of the invention showing a mounting flange 45 comprising a pair of semi - circular members formed around the periphery of the casing 13 and extending normally to the surface of case 11 . a basic advantage of the structure of fig6 is that the case 11 can be snapped or plugged into position . for this purpose , snap - in flexible lugs 47 and 49 are formed in spaced circumferential position to extend outwardly and at an angle with respect to the surface of the case 11 and to cooperate with an outwardly extending flange 45 . the lugs 47 and 49 extend outwardly to approximately the same diametrical dimension as the edge of the flange 45 . as seen in fig7 the upper edges of the lugs 47 and 49 are cut along a horizontal line to thereby accommodate and fit snuggly against the bottom surface of the associated mounting panel 50 ; and , with the bottom surface of the flange 45 fitting against the top of the panel 50 . flange 45 is notched along its lower peripheral surface as at 52 to accommodate or fit within the opening 51 in the panel 50 , to thereby secure the casing from sideward movement . additionally , a lower support 55 can accommodate the lower end of casing 13 . while the invention has been particularly described with reference to a preferred embodiment , 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 disclosed as the best mode contemplated for carrying out this invention , but that the invention will include all embodiments falling within the scope of the appended claims . | 7 |
the compositions of the invention can be single - component silicone compositions or two - component silicone compositions . in the latter case , the two components of the compositions of the invention can comprise all of the constituents in any desired combination , generally with the proviso that a component does not simultaneously comprise siloxanes having an aliphatic multiple bond , siloxanes having si - bonded hydrogen , and catalyst , i . e . in essence does not simultaneously comprise the constituents ( a ), ( b ), and ( d ) or , respectively , ( c ) and ( d ). however , it is preferable that the compositions of the invention are single - component compositions . the single - component silicone elastomer compositions of the invention are produced via mixing of the constituents , via mixing of components ( a ), ( b ), ( d ), and ( e ), or ( c ), ( d ), and ( e ) as in the prior art . the compounds ( a ) and ( b ) or , respectively , ( c ) used in the addition - crosslinking compositions of the invention are selected in a known manner so as to permit crosslinking : by way of example , compound ( a ) has at least two aliphatically unsaturated moieties and ( b ) has at least three si - bonded hydrogen atoms , or compound ( a ) has at least three aliphatically unsaturated moieties and siloxane ( b ) has at least two si - bonded hydrogen atoms , or else siloxane ( c ) is used instead of compound ( a ) and ( b ) and has aliphatically unsaturated moieties and si - bonded hydrogen atoms in the abovementioned ratios . another possibility is mixtures of ( a ) and ( b ) and ( c ) using the abovementioned ratios of aliphatically unsaturated moieties and si - bonded hydrogen atoms . it is preferable that the silicone compositions of the invention comprise , as constituent ( a ), at least one aliphatically unsaturated linear organosilicon compound , and it is possible here to use any of the aliphatically unsaturated linear organosilicon compounds used hitherto in addition - crosslinking compositions . organosilicon compounds ( a ) used which have sic - bonded moieties having aliphatic carbon - carbon multiple bonds are preferably linear organopolysiloxanes made of units of the general formula ( ii ) r are mutually independently identical or different organic or inorganic moieties free from aliphatic carbon - carbon multiple bonds , r 1 are mutually independently identical or different monovalent , substituted or unsubstituted , sic - bonded hydrocarbon moieties having at least one aliphatic carbon - carbon multiple bond , a is 1 , 2 , or 3 , and b is 1 or 2 , with the proviso that the sum a + b is less than or equal to 3 , and at least 2 moieties r 1 are present in each molecule . moiety r can be mono - or polyvalent moieties , and the polyvalent moieties , for example bivalent , trivalent , and tetravalent moieties , then bond a plurality of siloxy units of the formula ( ii ) to one another , for example 2 , 3 , or 4 siloxy units . other examples of r are the monovalent moieties — f , — cl , — br , — or 2 , — cn , — scn , — nco , and sic - bonded substituted or unsubstituted hydrocarbon moieties which can be interrupted by oxygen atoms or by the group — c ( o )—; other examples of r are divalent moieties si - bonded on both sides as in formula ( ii ). if moiety r is an sic - bonded , substituted hydrocarbon moiety , preferred substituents are halogen atoms , phosphorus - containing moieties , cyano moieties , — or 2 , — nr 2 —, — nr 2 2 , — nr 2 — c ( o )— nr 2 2 , — c ( o )— nr 2 2 , — c ( o ) r 2 , — c ( o ) or 2 , — so 2 — ph , and — c 6 f 5 . r 2 are mutually independently , identical or different , and are hydrogen or monovalent hydrocarbon moieties having from 1 to 20 carbon atoms . ph is the phenyl moiety . examples of moieties r are alkyl moieties , for example the methyl , ethyl , n - propyl , isopropyl , n - butyl , isobutyl , tert - butyl , n - pentyl , isopentyl , neopentyl , and tert - pentyl moieties , hexyl moieties such as the n - hexyl moiety , heptyl moieties such as the n - heptyl moiety , octyl moieties such as the n - octyl moiety and isooctyl moieties such as the 2 , 2 , 4 - trimethylpentyl moiety , nonyl moieties such as the n - nonyl moiety , decyl moieties such as the n - decyl moiety , dodecyl moieties such as the n - dodecyl moiety , and octadecyl moieties such as the n - octadecyl moiety , cycloalkyl moieties such as the cyclopentyl , cyclohexyl , cycloheptyl , and methylcyclohexyl moieties ; aryl moietiese such as the phenyl , naphthyl , anthryl , and phenanthryl moieties ; alkaryl moieties such as the o -, m -, p - tolyl moieties , xylyl moieties , and ethylphenyl moieties ; and aralkyl moieties , for example the benzyl moiety , and the α - and the β - phenylethyl moieties . examples of substituted moieties r are haloalkyl moieties , for example the 3 , 3 , 3 - trifluoro - n - propyl moiety , the 2 , 2 , 2 , 2 ′, 2 ′, 2 ′- hexafluoroisopropyl moiety , and the heptafluoroisopropyl moiety ; haloaryl moieties , for example the o -, m -, and p - chlorophenyl moieties , —( ch 2 )— n ( r 2 ) c ( o ) nr 2 2 , —( ch 2 ) n — c ( o ) nr 2 2 , —( ch 2 ) n — c ( o ) r 2 , —( ch 2 ) n — c ( o ) or 2 , —( ch 2 ) n — c ( o ) nr 2 2 , —( ch 2 )— c ( o )—( ch 2 ) m c ( o ) ch 3 , —( ch 2 )— o — co — r 2 , —( ch 2 )— nr 2 —( ch 2 ) m — nr 2 2 , —( ch 2 ) n — o —( ch 2 ) m ch ( oh ) ch 2 oh , —( ch 2 ) n ( och 2 ch 2 ) m or 2 , —( ch 2 ) n — so 2 — ph , and —( ch 2 ) n — o — c 6 f 5 , where r 2 and ph are defined as above , and n and m are identical or different integers from 0 to 10 . examples of r as a divalent moiety si - bonded on both sides as in formula ( ii ) are moieties derived from the monovalent examples of moiety r above in that an additional bond replaces a hydrogen atom , examples of moieties of this type being —( ch 2 )—, — ch ( ch 3 )—, — c ( ch 3 ) 2 —, — ch ( ch 3 )— ch 2 —, — c 6 h 4 —, — ch ( ph )— ch 2 —, — c ( cf 3 ) 2 —, —( ch 2 ) n — c 6 h 4 —( ch 2 ) n —, —( ch 2 ) n — c 6 h 4 — c 6 h 4 —( ch 2 ) n —, —( ch 2 o ) m , ( ch 2 ch 2 o ) m , —( ch 2 ) n — o x — c 6 h 4 — so 2 — c 6 h 4 — o x —( ch 2 ) n —, where x is 0 or 1 , and ph , m , and n are defined as above . it is preferable that moiety r is a monovalent , sic - bonded , optionally substituted hydrocarbon moiety having from 1 to 18 carbon atoms and free from aliphatic carbon - carbon multiple bonds , particularly a monovalent , sic - bonded , hydrocarbon moiety having from 1 to 6 carbon atoms and free from aliphatic carbon - carbon multiple bonds , in particular the methyl or phenyl moiety . moiety r 1 can be any desired group amenable to an addition reaction ( hydrosilylation ) with an sih - functional compound . if moiety r 1 is an sic - bonded , substituted hydrocarbon moiety , preferred substituents are halogen atoms , cyano moieties , and — or 2 , where r 2 is as defined above . it is preferable that moiety r 1 is an alkenyl or alkynyl group having from 2 to 16 carbon atoms , for example vinyl , allyl , methallyl , 1 - propenyl , 5 - hexenyl , ethynyl , butadienyl , hexadienyl , cyclopentenyl , cyclopentadienyl , cyclohexenyl , vinylcyclohexylethyl , divinylcyclohexylethyl , norbornenyl , vinylphenyl , and styryl moieties , and it is particularly preferable here to use vinyl , allyl , and hexenyl moieties . the molar mass of the constituent ( a ) can vary widely , for example from 10 2 to 10 6 g / mol : the constituent ( a ) can by way of example be a relatively low - molecular - weight alkenyl - functional oligosiloxane , for example 1 , 2 - divinyltetramethyldisiloxane but can also be a high - polymeric polydimethylsiloxane having si - bonded vinyl groups within the chain or at chain ends , and having a molar mass of , for example , 10 5 g / mol ( number average determined by means of nmr ). the addition - crosslinking silicone composition of the invention preferably comprises from 30 to 80 % by weight of ( a ), more preferably from 40 to 70 % by weight of ( a ). organosilicon compound ( b ) used can be any of the hydrogen - functional organosilicon compounds used hitherto in addition - crosslinkable compositions . organopolysiloxanes ( b ) used which have si - bonded hydrogen atoms are preferably linear organopolysiloxanes made of units of the general formula ( iii ) r is defined as above , c is 0 , 1 , 2 or 3 , and d is 0 , 1 , or 2 , with the proviso that the sum c + d is less than or equal to 3 , and at least two si - bonded hydrogen atoms are present in every molecule . it is preferable that the organopolysiloxane ( b ) used in the invention comprises a quantity in the range from 0 . 02 to 1 . 7 % by weight of si - bonded hydrogen , based on the total weight of the organopolysiloxane ( b ). the molar mass of the constituent ( b ) can likewise vary widely , for example from 10 2 to 10 6 g / mol : the constituent ( b ) can by way of example be a relatively low - molecular - weight sih - functional oligosiloxane , for example tetramethyldisiloxane but can also be a high - polymeric polydimethylsiloxane having sih groups within the chain or at chain ends , or a silicone resin having sih groups . there is moreover no defined structure of the molecules forming the constituent ( b ); in particular , the structure of a relatively high - molecular - weight , i . e . oligomeric or polymeric , sih - containing siloxane can be linear . linear polysiloxanes ( b ) are preferably composed of units of the formula r 3 sio 1 / 2 , hr 2 sio 1 / 2 , hrsio 2 / 2 , and r 2 sio 2 / 2 , where r is defined as above . it is also possible , of course , to use mixtures of different siloxanes complying with the criteria for the constituent ( b ). in particular , the molecules forming the constituent ( b ) can optionally also simultaneously comprise aliphatically unsaturated groups in addition to the obligatory sih groups . particular preference is given to the use of low - molecular - weight sih - functional compounds such as tetrakis ( dimethylsiloxy ) silane and tetramethylcyclotetrasiloxane , and also of relatively high - molecular - weight , sih - containing siloxanes , for example poly ( hydrogenmethyl ) siloxane and poly ( dimethylhydrogenmethyl ) siloxane with viscosity of from 10 to 10 , 000 mpa · s at 25 ° c ., or analogous sih - containing compounds in which some of the methyl groups have been replaced by 3 , 3 , 3 - trifluoropropyl or phenyl groups . the addition - crosslinking silicone composition of the invention preferably comprises from 0 . 5 to 20 % by weight of ( b ), particularly from 1 to 15 % by weight of ( b ). the quantity of constituent ( b ) in the crosslinkable silicone compositions of the invention is preferably such that the molar ratio of sih groups to aliphatically unsaturated groups from ( a ) is from 0 . 1 to 20 , particularly from 0 . 2 to 2 . 0 . components ( a ) and ( b ) used in the invention are commercially available products or can be produced by processes that are commonly used in chemistry . the silicone compositions of the invention can comprise , instead of component ( a ) and ( b ), linear organopolysiloxanes ( c ) which simultaneously have aliphatic carbon - carbon multiple bonds and si - bonded hydrogen atoms . the silicone compositions of the invention can also comprise all three of components ( a ), ( b ), and ( c ). if siloxanes ( c ) are used , these are preferably those made of units of the general formulae ( iv ), ( v ), and ( vi ) f is 1 , 2 , or 3 , g is 1 or 2 , and h is 1 or 2 , with the proviso that at least 2 moieties r 1 and at least 2 si - bonded hydrogen atoms are present in every molecule . the addition - crosslinking silicone composition of the invention preferably comprises from 30 to 80 % by weight of ( c ), particularly from 40 to 70 % by weight of ( c ). it is preferable that the average viscosity of the organopolysiloxanes ( c ) is from 0 . 01 to 500 , 000 pa · s , particularly from 0 . 1 to 100 , 000 pa · s , in each case at 25 ° c . organopolysiloxanes ( c ) can be produced by methods commonly used in chemistry . hydrosilylation catalyst ( d ) used can be any of the catalysts useful in hydrosilylation reactions . component ( d ) can be a platinum group metal , for example platinum , rhodium , ruthenium , palladium , osmium , or iridium , an organometallic compound , or a combination thereof . examples of component ( d ) are compounds such as hexachloroplatinic acid , platinum dichloride , platinum acetylacetonate , and complexes of said compounds , encapsulated within a matrix or within a core - shell - type structure . among the platinum complexes with organopolysiloxanes of low molecular weight are platinum 1 , 3 - diethenyl - 1 , 1 , 3 , 3 - tetramethyldisiloxane complexes . other examples are platinum phosphite complexes , platinum phosphine complexes , and alkylplatinum complexes . these compounds can have been encapsulated within a resin matrix . the quantity of component ( d ) can be from 0 . 1 to 1000 parts per million ( ppm ), from 0 . 5 to 100 ppm , or from 1 to 25 ppm , of the platinum group metal , based on the total weight of the components . the curing rate can be low when the platinum group metal constituent is below 1 ppm . use of more than 100 ppm of the platinum group metal is uneconomical , or can reduce the stability of the composition . in the filler made of porous glass particles ( e ), the density of the lattice of the glass matrix of these glasses that , for the purposes of the invention are porous , is from 1 . 0 to 3 . 0 g / cm 3 . the associated pore diameter is from 1 . 0 × 10 − 10 m to 20 × 10 − 10 m , i . e . from 1 to 20 angstroms . the doped glass particles ( e ) are produced via comminution of foamed glass until the average particle size is from 1 to 50 μm , preferably from 2 to 15 μm , and subsequent mixing with a dissolved silver salt , preferably silver nitrate solution . quantities of the silver salt solution incorporated into the mixture , based on the glass particles , are from 1 to 15 % by weight , preferably from 4 to 7 % by weight . the porosity of the glass particles causes these to absorb the silver solution . no clumping of the glass particles occurs here . a conditioning / drying process then takes place in order to fix some of the silver ions on the pore walls of the glass particles by way of ionic bonding , and to reduce the moisture content of the silver - containing porous glass particles . the silver content of the porous glass particles is from 0 . 5 to 30 % by weight , preferably from 1 to 10 % by weight , based on ( e ). the amount of the introduced silver in ionic form which is present as silver ions , is preferably from 5 to 50 % by weight , more preferably from 15 to 35 % by weight . the silicone elastomer composition of the invention can , if desired , comprise a proportion of from 0 up to 70 % by weight , preferably from 1 to 40 % by weight , of other additives ( f ) as constituents . these additives can be reinforcing and inert fillers differing from ( e ), rheology - modifying additives , flame retardants , agents for influencing electrical properties , dispersing agents , solvents , adhesion promoters , pigments , dyes , plasticizers , organic polymers , heat stabilizers , etc . examples of adhesion promoters that can be used as additional substances ( f ) are silanes having hydrolyzable groups and sic - bonded vinyl , acryloxy , methacryloxy , epoxy , anhydride , acid , ester , or ether groups ; other examples of these adhesion promoters are partial hydrolyzates and cohydrolyzates , preference being given here to silanes having vinyl groups and silanes having epoxy groups which comprise ethoxy or acetoxy groups as hydrolyzable moieties , particular preference being given here to vinyltriethoxysilane , vinyltriacetoxysilane , epoxypropyltrimethoxysilane , and their partial hydrolyzates and cohydrolyzates . quantities of adhesion promoters ( f ) in the silicone composition of the invention are preferably from 0 to 5 % by weight , with preference from 0 . 3 to 3 % by weight . the combination of porous surface structure with silver doping which provides the silver predominantly in ionic form in order to bind the sulfur - containing pollutant gases has proven to be particularly effective for protecting encapsulated electronic components from sulfur - containing pollutant gases . by virtue of component ( e ) with its porous surface structure , the addition - crosslinking silicone compositions of the invention provide a markedly larger effective surface area for the adsorption of pollutant gases . the silver predominantly present in ionic form has also proven to be particularly advantageous , alongside the increased surface area of said fillers , for the protection of metallic surfaces from sulfur - containing pollutant gas . the compositions of the invention are used for the encapsulation of electrical or electronic components . the present invention therefore further provides encapsulated electrical or electronic components characterized in that the encapsulation material is a polymerized silicone composition of the invention . unless otherwise stated in the examples described below , all parts and percentages stated are based on weight . unless otherwise stated , the examples below are carried out at the pressure of the ambient atmosphere , i . e . at about 1000 hpa , and at room temperature , i . e . at about 20 ° c ., or at a temperature that becomes established when the reactants are combined at room temperature without additional heating or cooling . all viscosities below relate to dynamic viscosity at a temperature of 20 ° c . and at a shear rate of 1 s − 1 . the examples below illustrate the invention , but without any resultant restrictive effect . all of the examples give the overall composition of the crosslinked products , irrespective of whether these are formulated as single - or two - component compositions . vinylpolymers 1 and 2 : these are vinyldimethylsiloxy - terminated dimethylpolysiloxanes with different viscosities , produced by conventional processes . sih crosslinking agent h018 : this is a trimethylsilyl - terminated dimethyl / methylhydrocopolysiloxane with viscosity 180 mpa · s and 0 . 17 % by weight h content . h polymer : this is an h - dimethylsiloxy - terminated dimethylpolysiloxane with viscosity 65 mpa · s . catalyst masterbatch ep : karstedt catalyst with 1 % by weight of platinum in pdms . filler 1 : amorphous , porous silicate glass particles , typical particle diameter about 10 μm , silver content 3 . 1 % by weight , silver ion content 0 . 26 mg / l filler 2 : amorphous , porous silicate glass particles , typical particle diameter about 10 μm , silver content 3 . 1 % by weight , silver ion content 0 . 37 mg / l filler 3 : amorphous , porous silicate glass particles , typical particle diameter about 10 μm , silver content 7 . 6 % by weight , silver ion content 2 . 4 mg / l filler 4 : spherical silicate glass particles coated with metallic silver , particle diameter from 15 to 50 μm , density 2 . 6 g / cm 3 , silver content 8 . 0 % by weight . filler 5 : spherical copper metal particles coated with metallic silver , particle diameter from 10 to 30 μm , silver content 17 . 0 % by weight the compositions were mixed in suitable mixers . after mixing , the silicone compositions were degassed for 5 min at 10 mbar . filler content ( fillers 1 to 5 ) was always 50 % by weight , based on the entire formulation . corrosion test : the test substrates were composed of aluminum oxide ceramic of thickness 1 mm onto which undulating silver conductor tracks were printed . the track width of the conductor tracks was 0 . 5 mm . the flowable mixtures 1 - 6 are applied at a layer thickness of 2 mm to the test substrates , degassed , and hardened at 150 ° c . for 60 min . soft silicone gels are obtained . the test substrates were placed in a 1 l desiccator together with 1 g of elemental sulfur powder . the desiccator was sealed and heated to 80 ° c . for a total of 14 days . at defined intervals , the test substrates were removed , the silicone gel was removed , and the silver conductor track was checked visually for corrosion . the test sample was assessed as good ( g ) if the silver track had not discolored and had metallic luster . the test sample was assessed as poor ( p ) if the silver track had discolored to become dark or black , indicating corrosion . table 1 shows the composition of examples 1 - 6 , and also the corrosion test results . examples 1 - 4 of the invention : silicone compositions with fillers made of amorphous , porous silicate particles and of predominantly ionic silver coating . example 5 , not of the invention , with spherical silicate glass particles and metallic silver coating . example 6 , not of the invention , with spherical copper metal particles and metallic silver coating by analogy with ep1295905a1 . examples 1 - 4 of the invention show that only the silicone compositions of the invention with amorphous , porous silicate particles and with predominantly ionic silver doping can provide durable and lasting protection of the substrates to be protected , and therefore of the electronic components . | 2 |
the imaging lens of the present invention has a two - group , two - lens - element construction . more specifically , it includes , in order from the object side : an aperture stop , a first lens element , and a second lens element . the first lens element has positive refractive power near the optical axis , with an object - side surface that is aspherical and convex near the optical axis . the surface on the image side is aspherical and either convex or concave near the optical axis . the second lens element has positive refractive power with its surface on the object - side being aspherical and convex near the optical axis . the surface of the second lens element oil the image side is aspherical and concave near the optical axis , but becomes convex in its peripheral region . in addition , the following conditions ( 1 ) and ( 2 ) are satisfied : d2 is the distance on the optical axis between the image - side surface of the first lens element and the object - side surface of the second lens element , in the imaging lens of the present invention , because it has the referenced construction , miniaturization is achieved , the various aberrations are favorably corrected , and thus the optical performance is enhanced compared with prior art imaging lenses of one - piece construction . by satisfying condition ( 1 ) curvature of field is suppressed and distortion is favorably corrected , and by satisfying condition ( 2 ) it becomes especially easy to correct on - axis chromatic aberration . in the imaging lens of the present invention , it is further desirable that it is constructed to satisfy the following condition ( 3 ): bf is the back focal length of the imaging lens , namely , the distance from the image - side surface of the second lens element to the image plane . by satisfying condition ( 3 ), it becomes easier to secure a sufficient space between the final lens element surface and the image plane , and the curvature of field is suppressed . in the imaging lens of the present invention , it is desirable that the aspherical shape of the object - side surface and the image - side surface of the second lens element be defined using at least one non - zero , odd - order coefficient ai , where the aspherical shape of the surface is defined using the following equation ( a ): z = cρ 2 /( 1 +( 1 − k c 2 ρ 2 ) 1 / 2 )+ σ a i · ρ i equation ( a ) z is the length of a perpendicular line drawn from a point on an aspherical surface at a height p from the optical axis to the contact plane ( a plane perpendicular to the optical axis ) of the apex of the aspherical surface , c is the paraxial curvature of the aspherical surface (= 1 / r , where r is the radius of curvature of the aspherical surface on - axis ), and a i is the i th order aspherical coefficient , where i equals 3 through 10 . by defining the shapes of the object - side surface and the image - side surface of the second lens element using at least one non - zero , odd - order coefficient a i in equation ( a ) above , curvature of field is suppressed and distortion is more easily corrected . the properties of the imaging lens of the present invention will vary somewhat depending on the particular image detecting device used . thus , optimal optical performance for a given application will require selecting the lens element construction that is best suited for a given application . the invention will first be discussed in general terms with reference to the drawings . fig1 - 4 show construction examples of the imaging lens according to embodiments 1 - 4 , respectively , of the present invention . it should be noted that fig1 - 4 are for purposes of explanation and are not drawn to scale . in fig1 - 4 , the labels ( r 1 )-( r 4 ) indicate the paraxial radius of curvature of the lens element surfaces s 1 - s 4 , in order from the object side , of the two lens elements l 1 and l 2 , and the labels d 1 - d 4 indicate the surface spacings along the optical axis z 1 , as illustrated . d 0 indicates the on - axis surface spacing of a stop st that is placed to the object side of the lens element surface s 1 of lens element l 1 . shown in broken lines in each of fig1 - 4 is a plane - parallel plate sg , such as a cover glass . the image plane is indicated by simg . referring to fig1 which is specifically representative of embodiment 1 but also illustrates the following general features of the invention , the present invention is an imaging lens having a two - lens - element construction . in order from the object side along an optical axis z 1 , there are : an aperture stop st , a first lens element l 1 and a second lens element l 2 . an image detector such as a ccd , not shown , may be positioned at the image plane simg of the imaging lens in order to capture the images of the imaging lens , and a plane - parallel plate sg such as a cover glass may be inserted between the second lens element l 2 and the image plane simg so as to protect optical filters and imaging elements that may also be inserted in this region . for the imaging lens embodiment shown in fig1 the first lens element l 1 has positive refractive power , an object - side surface s 1 that is aspherical and convex , and an image - side surface s 2 that is aspherical . the image - side surface s 2 is concave near the optical axis but the curvature becomes convex in its peripheral region . the second lens element l 2 has positive refractive power , an object - side surface s 3 that is aspherical and convex near the optical axis but the curvature becomes concave in its peripheral region , and an image - side surface s 4 that is aspherical and concave near the optical axis but the curvature becomes convex near in its peripheral region . on the other hand , for the imaging lens embodiments shown in fig2 - 4 , the first lens element l 1 of positive refractive power has an object - side surface s 1 that is aspherical and convex near the optical axis but the curvature may become concave in its peripheral region , and an image - side surface s 2 that is aspherical and convex near the optical axis , but the curvature may become concave in its peripheral region . the imaging lenses shown in fig1 - 4 are further constructed so as to satisfy the above conditions ( 1 ) and ( 2 ). in addition , it is desirable that the imaging lens be constructed to satisfy the above condition ( 3 ). furthermore , it is desirable that the aspherical shapes of the object - side surface s 3 and the image - side surface s 4 of the second lens element l 2 are expressed using at least one odd - order aspherical coefficient ai when the aspherical shape of the surface is expressed using equation ( a ) above . for the shapes of the first lens element l 1 and the second lens element l 2 , one of the constructions shown in fig1 - 4 can be selected according to the particular application . the actions and effects of the imaging lens of the present invention will now be discussed . in the imaging lens of the present invention , because all four of the lens surfaces that constitute the two - group , two - lens - element construction are made to be aspherical in shape , various aberrations can be favorably corrected while achieving miniaturization . also , because the aperture stop st is positioned at the most object side of the imaging lens , the overall length of the imaging lens can be shortened , and the light that is incident onto the image plane simg can be made to be almost parallel to the optical axis z 1 . in other words , the imaging lens can be made to be substantially telecentric while also providing for a compact construction . the reason it is desirable that the light that is incident onto the image plane be almost parallel to the optical axis z 1 is for more efficient detection of the light at the image plane when capturing images using an image detector , such as a ccd . having the object - side surface s 1 of the first lens element l 1 convex near the optical axis allows for the overall length of the imaging lens to be shortened as compared with the case where this surface is concave near the optical axis . furthermore , having the image - side surface s 4 of the second lens element l 2 be an aspherical shape that is concave near the optical axis and becomes convex toward the periphery enables the curvature of field to be especially favorably suppressed . furthermore , because the constructions in fig1 - 4 satisfy condition ( 1 ), distortion can be favorably corrected while suppressing the curvature of field . if the upper limit of condition ( 1 ) is exceeded , the curvature of field becomes large in the positive direction , making it impossible to obtain good optical performance . on the other hand , if the lower limit of condition ( 1 ) is not satisfied , although the distortion is advantageously reduced , the curvature of field becomes negative , making it impossible to obtain good optical performance . also , because the thickness of the second lens element l 2 becomes too thin , it becomes difficult to manufacture this lens element . in addition , for the constructions shown in fig1 - 4 , because condition ( 2 ) relating to the abbe numbers is satisfied , the on - axis chromatic aberration can be especially well corrected . however , because each of the first lens element l 1 and the second lens element l 2 have positive refractive power , if the lower limit of condition ( 2 ) is not satisfied , it becomes difficult to correct the on - axis chromatic aberration of the imaging lens . furthermore , for the constructions shown in fig1 - 4 , by satisfying condition ( 3 ), a sufficient space between the final lens element surface s 4 and the image plane simg is assured , while shortening the overall length of the imaging lens . satisfying condition ( 3 ) also enables the curvature of field to be reduced . if the lower limit of condition ( 3 ) is not satisfied , the distance between the final lens element surface s 4 and the image plane simg decreases to the extent that it becomes difficult to insert other optical components such as a lowpass filter , an 1r - blocking filter , etc . on the other hand , if the upper limit of condition ( 3 ) is not satisfied , the back focal length bf becomes too large , causing the overall length of the imaging lens to be excessive . in addition , when the upper limit of condition ( 3 ) is exceeded , it becomes impossible to sufficiently correct the curvature of field . in addition , for the constructions shown in fig1 - 4 , when the aspherical shapes of the object - side surface s 3 and the image - side surface s 4 of the second lens element l 2 are expressed using at least one odd - order aspherical coefficient ai , it is easy to favorably correct distortion while suppressing the curvature of field . furthermore , when the aspherical shapes of the object - side surface s 3 and the image - side surface s 4 of the second lens element l 2 are expressed using only even - order aspherical coefficients ai , correction of the curvature of field , especially in the tangential plane , tends to become insufficient . in this way , because the imaging lens of the present invention is equipped with , in order from the object side , an aperture stop st , a first lens element l 1 , and a second lens element l 2 , with all four lens element surfaces being aspherical in shape , an optical image is produced having a quality sufficient for capture using a high - pixel image detecting device . also , by selecting from among the constructions shown in fig1 - 4 according to the properties of the image detecting element used , an optical performance optimally matched to the properties of that image detecting element can be provided . four embodiments of the imaging lens of the invention will now be discussed in detail . [ 0052 ] fig1 shows a cross section of an imaging lens of the invention according to embodiment 1 . table 1 below lists the surface number #, in order from the object side , the radius of curvature r near the optical axis ( in mm ), the on - axis surface spacing d ( in mm ), as well as the index of refraction n d and the abbe number υ d ( both at the d - line of 587 . 6 nm ) of each lens element according to embodiment 1 . those surfaces that are aspheric are listed with a * to the right of the surface number , and the aspheric surface shape is defined using equation ( a ) above . table 2 below lists the values of the constant k and of the aspherical coefficients a 3 - a 10 used in equation ( a ) above for each of the aspherical surfaces indicated in table 1 . an “ e ” in the data indicates that the number following the “ e ” is the exponent to the base 10 . for example , “ 1 . 0e - 02 ” represents the number 1 . 0 × 10 − 2 . fig5 a - 5 c show the spherical aberration , astigmatism , and distortion , respectively , of the imaging lens of embodiment 1 . these aberrations are based on the d - line ( wavelength = 587 . 6 nm ). in fig5 b , the astigmatism is shown for both the sagittal s and the tangential t image planes . [ 0056 ] fig2 shows a cross section of an imaging lens of the invention according to embodiment 2 . table 3 below lists the surface number #, in order from the object side , the radius of curvature r near the optical axis ( in mm ), the on - axis surface spacing d ( in mm ), as well as the index of refraction n d and the abbe number υ d ( both at the d - line of 587 . 6 nm ) of each lens element according to embodiment 2 . those surfaces that are aspheric are listed with a * to the right of the surface number , and the aspheric surface shape is defined using equation ( a ) above . table 4 below lists the values of the constant k and of the aspherical coefficients a 3 - a 10 used in equation ( a ) above for each of the aspherical surfaces indicated in table 3 . an “ e ” in the data indicates that the number following the “ e ” is the exponent to the base 10 . for example , “ 1 . 0e - 02 ” represents the number 1 . 0 × 10 − 2 . fig6 a - 6 c show the spherical aberration , astigmatism , and distortion , respectively , of the imaging lens of embodiment 2 . these aberrations are based on the d - line ( wavelength = 587 . 6 nm ). in fig6 b , the astigmatism is shown for both the sagittal s and the tangential t image planes . [ 0060 ] fig3 shows a cross section of an imaging lens of the invention according to embodiment 3 . table 5 below lists the surface number #, in order from the object side , the radius of curvature r near the optical axis ( in mm ), the on - axis surface spacing d ( in mm ), as well as the index of refraction n d and the abbe number υ d ( both at the d - line of 587 . 6 nm ) of each lens element according to embodiment 3 . those surfaces that are aspheric are listed with a * to the right of the surface number , and the aspheric surface shape is defined using equation ( a ) above . table 6 below lists the values of the constant k and of the aspherical coefficients a 3 - a 10 used in equation ( a ) above for each of the aspherical surfaces indicated in table 5 . an “ e ” in the data indicates that the number following the “ e ” is the exponent to the base 10 . for example , “ 1 . 0e - 02 ” represents the number 1 . 0 × 10 − 2 . fig7 a - 7 c show the spherical aberration , astigmatism , and distortion , respectively , of the imaging lens of embodiment 3 . these aberrations are based on the d - line ( wavelength = 587 . 6 nm ). in fig7 b , the astigmatism is shown for both the sagittal s and the tangential t image planes . [ 0064 ] fig4 shows a cross section of an imaging lens of the invention according to embodiment 4 . table 7 below lists the surface number #, in order from the object side , the radius of curvature r near the optical axis ( in mm ), the on - axis surface spacing d ( in mm ), as well as the index of refraction n d and the abbe numbered ( both at the d - line of 587 . 6 nm ) of each lens element according to embodiment 4 . those surfaces that are aspheric are listed with a * to the right of the surface number , and the aspheric surface shape is defined using equation ( a ) above . table 8 below lists the values of the constant k and of the aspherical coefficients a 3 - a 10 used in equation ( a ) above for each of the aspherical surfaces indicated in table 7 . an “ e ” in the data indicates that the number following the “ e ” is the exponent to the base 10 . for example , “ 1 . 0e - 02 ” represents the number 1 . 0 × 10 − 2 . fig8 a - 8 c show the spherical aberration , astigmatism , and distortion , respectively , of the imaging lens of embodiment 4 . these aberrations are based on the d - line ( wavelength = 587 . 6 nm ). in fig8 b , the astigmatism is shown for both the sagittal s and the tangential t image planes . table 9 below lists the values of the ratios of conditions ( 1 ) and ( 3 ) for each embodiment . as is apparent from comparing the values listed in table 9 with the acceptable ranges given in conditions ( 1 ) and ( 3 ), each embodiment satisfies conditions ( 1 ) and ( 3 ). furthermore , as shown in tables 1 , 3 , 5 , and 7 , the abbe numbers υ1 and υ2 of the first and second lens elements l 1 and l 2 , respectively , satisfy condition ( 2 ). as shown in tables 2 , 4 , 6 , and 8 , in embodiments 1 - 4 , the aspherical shapes of the surfaces s 3 and s 4 of the second lens element l 2 are defined using multiple odd - order terms ( i = 3 , 5 , 7 , and 9 ) and multiple even - order terms ( i = 4 , 6 , 8 , and 10 ) as the aspherical coefficients ai . on the other hand , the aspherical shapes of the surfaces s 1 and s 2 of the first lens element l 1 are defined using only the even - order terms ( i = 4 , 6 , 8 , and 10 ) since the odd - order terms have coefficients ai that are zero . as seen from the above lens data and aberration plots , the various aberrations are favorably corrected for each embodiment , and performance that is optimal for mounting the imaging lens of the present invention within compact imaging devices such as portable devices , etc ., is obtained . the invention being thus described , it will be obvious that the same may be varied in many ways . for example , the present invention is not limited to the above embodiments , as various modifications are possible . for example , the values for the radii of curvature r , on - axis surface spacings d , index of refraction n d , and abbe number υ d of each lens element are not limited to those shown above for each embodiment , as other values can be adopted . also , although the aspherical shapes of the surface s 3 and the surface s 4 of the second lens element l 2 have been expressed using multiple odd - order terms as the aspherical coefficients ai in the present embodiments it is also possible to use only one , or more than one , odd - order term ( s ). such variations are not to be regarded as a departure from the spirit and scope of the invention . rather , the scope of the invention shall be defined as set forth in the following claims and their legal equivalents . all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims . | 6 |
an objective lens adapter according to an embodiment of the present invention will be described below referring to fig1 to 5 . as shown in fig2 , an objective lens adapter 1 according to this embodiment , which is an objective lens adapter 1 that is attachably / detachably attached to an objective lens 3 for in vivo observation and that has a small - diameter distal - end portion 2 , is provided with a fixed member 5 that is fixed to a lens tube 4 of the objective lens 3 , a distal - end member 6 that is disposed so as to cover the small - diameter distal - end portion 2 of the objective lens 3 , and a compression coil spring ( elastic member ) 7 that is disposed between the distal - end member 6 and the fixed member 5 . the fixed member 5 is formed substantially cylindrically , has an inside diameter that allows it to fit on the lens tube 4 of the objective lens 3 , and has an inner - rib like inner flange portion 5 a on one end extending radially inward . the inner flange portion 5 a is provided with a through - hole 5 b that penetrates in the axial direction . the fixed member 5 can be fixed onto the lens tube 4 of the objective lens 3 by friction from pressing the distal end of a set screw 8 , which is screwed into a threaded hole 5 c penetrating in the radial direction thereof , against the external surface of the lens tube 4 of the objective lens 3 . the distal - end member 6 is provided with a substantially cylindrical tubular portion 6 a , a prism ( optical element ) 9 fixed on one end of the tubular portion 6 a , and an outer - rib like outer flange portion 6 b that extends radially outward on the other end of the tubular portion 6 a . the tubular portion 6 a has an outside diameter slightly smaller than the inside diameter of the through - hole 5 b of the inner flange portion 5 a . in addition , the outer flange portion 6 b has an outside diameter sufficiently larger than the inside diameter of the through hole 5 b . reference sign 6 d in the drawings is a stopper that sets the position of the distal - end member 6 to a predetermined position with respect to the fixed member 5 . the tubular portion 6 a has a sharp portion 6 c whose distal end is in a cut - off configuration at a 45 ° angle with respect to the axis line . the prism 9 is formed in a columnar shape as shown in fig3 and has a reflection surface 9 a inclined at 45 ° with respect to the axis line . the prism 9 is fittingly accommodated in the sharp portion 6 c at the distal end of the tubular portion 6 a . as shown in fig3 and 4 , a ring shaped spacer 10 whose thickness is controlled is disposed on the surface of the prism 9 inside the tubular portion 6 a . by inserting the spacer 10 , direct contact between the prism 9 and a lens ( not shown ) at the distal end of the objective lens 3 is avoided , thereby preventing damage to the prism 9 and the lens at the distal end of the objective lens 3 . in addition , as shown in fig4 and 5 , a part of the side wall of the tubular portion 6 a is cut away on the side of the sharp portion 6 c , exposing the prism 9 accommodated inside . in addition , so as not to form a large level difference between the surface of the prism 9 exposed to the outside and the tubular portion 6 a , the side wall of the tubular portion 6 a is also cut away in an area continuous with the prism 9 and is sealed by bonding a plate portion 11 whose plate thickness gradually increases . the reflection surface 9 a is covered by a cover member 12 , and , as shown in fig1 to 3 , the surface of the cover member 12 opposing the reflection surface 9 a is provided with a concave portion 12 a close to the center position thereof . by disposing the concave portion 12 a opposite the reflection surface 9 a of the prism 9 , an air layer can be formed on the back surface side of the reflection surface 9 a , and thus total reflection of light at the reflection surface 9 a is possible . by having the tubular portion 6 a penetrate the through - hole 5 b , the compression coil spring 7 is disposed in a position sandwiched in the axial direction between the outer flange portion 6 b disposed inside the fixed member 5 and the inner flange portion 5 a of the fixed member 5 . thus , by relatively moving the fixed member 5 and the distal - end member 6 in the axial direction , the amount of elastic deformation of the compression coil spring 7 is changed , causing mutual elastic forces to act . the operation of the thus - configured objective lens adapter 1 according to this embodiment will be described below . to attach the objective lens adapter 1 according to this embodiment to the distal end of the objective lens 3 having the small - diameter distal - end portion 2 , the fixed member 5 and the distal - end member 6 of the objective lens adapter 1 are placed thereon from the small - diameter distal - end portion 2 side of the objective lens 3 to bring the prism 9 into contact with the distal - end surface of the small - diameter distal - end portion 2 via the spacer 10 . from this state , the fixed member 5 is moved with respect to the distal - end member 6 , in a direction indicated by an arrow a in fig2 , toward the proximal end of the objective lens 3 ; thereby the compression coil spring 7 sandwiched between the outer flange portion 6 b of the distal - end member 6 and the inner flange portion 5 a of the fixed member 5 is compressed , generating an elastic force . then , the set screw 8 provided on the fixed member 5 is screwed into the threaded hole 5 c in a state wherein the compression coil spring 7 is elastically deformed enough to obtain a predetermined elastic force ; the fixed member 5 can be fixed in that position by pressing the distal end of the set screw 8 against the external surface of the lens tube 4 of the objective lens 3 . by doing so , the prism 9 can be precisely positioned with respect to the objective lens 3 because the state in which the prism 9 is pressed onto the distal end of the small - diameter distal - end portion 2 via the spacer 10 is maintained by means of the elastic force of the compression coil spring 7 . in addition , generation of an excessive pressing force is prevented because the pressing is achieved by means of the elastic force of the compression coil spring 7 , and thus occurrence of the problem of the small - diameter distal - end portion 2 of the objective lens 3 and the prism 9 being damaged can be proactively prevented . in particular , in the case of the objective lens 3 for observing the internal condition of brain tissue , the small - diameter distal - end portion 2 is extremely thin , and therefore , attachment / detachment by screws tends to apply an excessive pressing force ; however , an advantage of this embodiment is that there is no such problem . with the objective lens adapter 1 according to this embodiment , attached to the distal end of the objective lens 3 in this way , it is possible to simplify the procedure of piercing biological tissue with the sharp portion 6 c provided on the distal end . in other words , whereas a part of the biological tissue is crushed when piercing with the small - diameter distal - end portion 2 of an objective lens 3 with a flat distal end as it is , causing severe damage , according to this embodiment , there is an advantage in that , due to the sharp portion 6 c , the objective lens 3 can pierce the biological tissue without inflicting damage . in addition , because the side wall adjacent to the sharp portion 6 c is cut away to expose a part of the prism 9 , when piercing the biological tissue , the biological tissue can be brought into contact with the exposed surface of the prism 9 . furthermore , because the objective lens adapter 1 is configured so as not to form a level difference between the surface of the prism 9 and the external surface of the tubular portion 6 a , when piercing the biological tissue , the problem of the biological tissue being scraped by the level difference thereby inflicting damage can be prevented . then , the illumination light guided from the objective lens 3 side is emitted from the small - diameter distal - end portion 2 , is incident on the prism 9 , is deflected 90 ° at the reflection surface 9 a of the prism 9 , and thus the illumination light is radiated onto the biological tissue in contact with the surface of the prism 9 from a notch 6 e provided in the tubular portion 6 a . in the case where the illumination light is excitation light , the illumination light excites a fluorescent substance that exists in the biological tissue , generating fluorescence , and the generated fluorescence returns along the same path to be collected by the objective lens 3 . in this case , because the cover member 12 , disposed so as to cover the reflection surface 9 a of the prism 9 , has the concave portion 12 a that forms the air layer with the prism 9 , it is possible to bring about total reflection of light at the reflection surface 9 a . as a result , reduction of the intensity of the illumination light radiated onto the biological tissue and the detected light , such as fluorescence obtained from the biological tissue , is prevented ; the illumination efficiency and the detection efficiency are improved ; and it is thus possible to conduct observation with a bright image . in addition , with the objective lens adapter 1 according to this embodiment , when conducting multiple observations of the same site with time intervals therebetween , after conducting an observation with the objective lens 3 , having the objective lens adapter 1 attached thereto , piercing biological tissue , the set screw 8 is loosened to release the fixing of the fixed member 5 to the lens tube 4 of the objective lens 3 , thereby making it possible to withdraw the objective lens 3 from the objective lens adapter 1 while leaving the objective lens adapter 1 piercing the biological tissue . then , to resume observation , the objective lens 3 may be inserted into and fixed to the objective lens adapter 1 that pierces the biological tissue . note that , in this embodiment , the sharp portion 6 c , which is shaped as if the distal end of the tubular portion 6 a is cut off at an angle , is provided , and the prism 9 , having the reflection surface 9 a inclined at 45 °, is disposed inside ; however , instead , a prism 9 having a reflection surface 9 a inclined at an angle other than 45 ° may be adopted . although the cover member 12 having the concave portion 12 a opposing the reflection surface 9 a of the prism 9 is provided , instead , a metallic thin film , a dielectric multilayer film , etc ., may be formed on the reflection surface 9 a . in this case , the reflection efficiency becomes lower than in the case of total reflection , but it is advantageous in that the cover member 12 and the concave portion 12 a are not necessary . in addition , although the prism 9 having the reflection surface 9 a is adopted as an optical element in this embodiment , instead , a glass flat plate member that transmits light in the optical axis direction may be adopted . by doing so , the working distance can be adjusted to the optimal position . in addition , although the columnar prism 9 is accommodated in the cylindrical tubular portion 6 a , instead , a triangular prism ( not shown ) may be employed , and an accommodation portion may be formed at the distal end of the tubular portion 6 a in such a shape that the triangular prism can be accommodated therein . further , when using the triangular prism , as shown in fig6 , the plate member 11 may be omitted by providing a thick - walled tubular portion 6 a . additionally , as shown in fig7 , the plate member 11 may be omitted while keeping the outside diameter small by decentering the inside diameter and outside diameter of the tubular portion thereby forming a thick - walled portion . | 0 |
the present invention relates to a system and method for reducing the time and power consumption required for reading data from a cache such as a trace cache . with the use of an abridged code referred to as a “ mini - tag ,” a trace cache read operation avoids the need to arrive at the desired information by first reading out an entire collection of data entries for an addressed row and then multiplexing out the desired data entry . moreover , by performing a victim selection operation to select which portion of a trace cache is to be written over with data that a prior read operation revealed as being absent from the cache , each mini - tag within each addressed row of the trace cache is ensured to be unique and can thereby serve as a basis for a trace cache reading operation . fig3 shows an embodiment of an arrangement of information in a trace cache 300 . in this example , a trace cache 300 is illustrated as containing 256 rows of addressable data entries ( rows 1 , 2 , and 256 are shown in fig1 with dots indicating that the same pattern continues with the rows that are not displayed ). within each row 310 is an alternating sequence of tags 320 , shown represented by “ t ,” and associated data entries 315 , shown represented by “ d .” as shown in fig1 the term “ way ” refers to each vertical column 305 of tags 320 in the trace cache 300 . in the embodiment shown in fig3 each row contains eight ways . each data entry 315 is addressable via its associated tag 320 ( e . g ., a 24 bit identifier ), and each row in the trace cache may be identified and accessed using a row or “ set ” address . a “ mini - tag ” is an abridged version of the full tag discussed above . in the example of a 32 bit address scheme , a mini - tag may be implemented , for example , by designating bits 2 - 4 and 12 - 14 of a tag address as the bits of the mini - tag . the mini - tag can thus be realized by taking , for example , six bits from the full tag to make a partial tag . by using a mini - tag in the trace cache reading operations , it is not required to read out every data entry of an accessed row 310 . therefore , for example , a 32 - bit address is not required to perform the data accessing operations , and the mini tag can be compared to only a portion of a requested address . by avoiding the need to perform a tag comparison operation that requires the reading out of every data entry in a particular trace cache row , the time and power required to perform trace cache read operations may be reduced . fig4 illustrates a flow diagram representing the steps of a trace cache read operation , according to an embodiment of the invention . the process is initiated , for example , when the processor of a computer system is required to perform a data read operation . this “ requested data ” may be identified by a “ requested address .” the requested address may include , for example , a set address used to identify a row of the trace cache , and a requested tag used to identify the location of the requested data within the identified row . as with prior read operation techniques , in step 400 the read operation according to the present invention begins with the use of the set address to access one of the rows 310 in the trace cache 300 . in step 405 , the full tag for each way in the accessed row 310 is read . for example , all eight ways , but not the associated data entries , may be read from the accessed row 310 . in step 410 , the mini - tags of the accessed ways are read from the accessed row . these read operations ( steps 405 , 410 ) may , for example , be performed in parallel ( i . e ., at the same time ). when read from the trace cache 300 , the tags and mini - tags may be stored , for example , in a latch before being sent to a comparator . in step 415 , the mini - tags are compared against the selected portions of the requested address . the mini - tags may be used to estimate the particular one of the , for example , eight ways in the trace cache identifying where the desired data entry is located . in step 420 , it is determined whether a “ hit ” occurs with a mini - tag of the row 310 being tested ( i . e ., whether the mini - tag matches the select portion of the requested address ). if no mini - tag hit occurs in a row 310 , a true “ least recently used ” (“ lru ”) victim selection and write operation is performed in step 425 . this technique will be described in more detail below , in connection with fig8 . if a mini - tag hit occurs in step 420 , the data entry identified by the mini - tag is read out ( e . g ., to a latch ) in step 430 , since the presence of the desired information in the selected row 310 , though not yet assured , may be determined as more likely . a full tag comparison is performed in step 435 , in order to ensure that the desired information is in fact in this row 310 . this step may be performed , for example , in parallel with the read out of the data entry performed in step 430 . therefore , time ( and consequently power ) may be saved . in step 440 , it is determined whether the full tag hit . if both the full tag and the mini - tag have hit , then the previously read out data entry is validated ( e . g ., by setting a validation bit ) in step 450 and the data is allowed to pass through to the processor . the processor may then proceed to the next trace cache read operation . if the full tag misses , then a “ full tag miss ” victim selection and write operation is performed in step 445 . this operation will be explained below in connection with fig9 . the trace cache read operation terminates in step 455 . fig5 is a time flow diagram showing elements of the trace cache read operation of fig4 . certain steps of the process of fig4 are shown , along with a representation of a clock cycle 500 of a processor to illustrate the time sequence of an embodiment of the invention . as shown in the embodiment of fig5 the mini - tag read operation 410 and the mini - tag compare operation 415 are performed in parallel with the full tag read operation 405 , as described in connection with fig4 . these operations may be performed , for example , in the first half of a processor clock cycle . in the second half of the processor clock cycle 500 , for example , the data read out operation 430 may be performed in parallel with the full tag compare operation 435 . the data validation operation 450 is performed after the full tag compare , if the full tag compare returns a hit . in this embodiment as shown in fig5 the system does not need to wait for a time consuming full tag read to read out the data entry . furthermore , the system does not need to perform a power - consuming read out of all the data entries for the selected row of the trace cache . therefore , both time and power consumption may be reduced . according to the embodiment described above , each mini - tag is unique . in order to ensure the uniqueness of each mini - tag , a “ victim selection ” operation may be performed . when a processor performs the trace cache read operation as discussed above , it continues to do so as long as the mini - tags and full tags involved in the operation continue to hit . when a full tag miss occurs , however , the processor fetches the desired data from another data storage resource ( e . g ., main memory , disk drive , cd rom ) and writes the data into the trace cache . since the trace cache most likely will not have an empty storage location for this new data , some portion of the data in the trace cache will need to be written over . the “ victim selection ” process determines which data entry (“ victim ”) is to be written over with the new data entry . one way to perform a victim selection is to overwrite the least recently used (“ lru ”) way . the trace cache may include , for example , in the trace cache that keeps track of the lru way by mapping not only the lru way for each row , but also the most recently used (“ mru ”) way as well . in order to better explain this operation , reference is made to the diagram of fig6 a and 6 b . these figures show a logical representation of the contents of an lru / mru unit 600 . each circled number in this diagram represents a particular way . for simplicity , only three ways are illustrated . in fig6 a , the lru is way 3 and the mru is way 1 . each line between the ways is an edge 605 representing a relationship . for an edge 605 between two particular ways , the arrow for the edge 605 points away from the more recently used and toward the lesser recently used . therefore , for the lru 3 , the arrow of each edge 605 emanating therefrom points away from way 1 and way 2 and for the mru , the arrows of each edge 605 emanating therefrom points to way 2 and way 3 . in a logic diagram such as fig6 a , an arrow pointed in one direction may be represented , for example , by a binary digit 1 , and an arrow pointed in the opposite direction may be represented by a binary digit 0 . thus , in fig6 a , since the edges 605 of way 1 all point away from way 1 , it can be identified as the mru , and since the edges of way 3 all point to way 3 , it can be identified as the lru . if a hit is received on way 2 , however , way 1 is no longer the most recently used way . consequently , the processor adjusts the mapping in the lru component of the trace cache . in particular , the edge 605 pointing in fig6 a from way 1 to way 2 is reversed , so that way 2 can be identified as the mru way . this situation is shown in fig6 b with ways 1 ′, 2 ′, and 3 ′. if the number of ways is increased to eight , then 28 edges would be required to characterize the relationships existing among the ways of each row in the trace cache . by constantly adjusting these relationships for each hit and maintaining them mapped in the lru component of the trace cache , the processor will be able to access the information necessary to perform a victim selection . for a trace cache that , for example , contains 8 ways for each row , the lru component stores , for example , 28 bits for each such row . a write operation may be performed when a tag operation misses and an instruction is fetched from a source other than the trace cache . this can happen in two situations : first , when the mini - tag misses ( and , therefore the full tag would also miss ), and second , when the mini - tag hits but the full tag misses . before writing into the trace cache , a victim selection must be performed in order to determine which way will have its associated data entry written over . if the mini - tag hits but the full - tag misses , the victim will be the way that the mini - tag hit on , according to the “ full tag miss ” victim selection procedure . the mini - tag is selected as the victim in this situation in order to maintain the uniqueness of the mini - tags . in order to illustrate the principle , reference is made to fig7 . fig7 illustrates a logical example of a row 700 of a trace cache containing only three ways 10 , 11 , 12 . for the purposes of this illustration , the full number shown in each way 10 , 11 , 12 represents a full tag and the second digit of this number 10 , 11 , 12 corresponds to a mini - tag . if a requested address 20 is used as the basis of a multi - tag comparison , there will be a mini - tag hit with respect to way 10 , because the second digits of both this way and the requested address are the same . nevertheless , a full tag miss will occur because the first digits of these addresses ( the numbers 1 and 2 ) do not match . according to an embodiment of the invention , way 10 will , therefore , be selected as the victim and will be written over with requested address and data corresponding to requested address 20 will be written into the data entry identified by the way 10 that is overwritten . the uniqueness of the mini - tags will be ensured because after the writing operation is performed , there will still only be one way with a mini - tag of zero . had the address 20 been written into any other location , the mini - tag would have been duplicated and its uniqueness eliminated . fig8 shows the true lru victim selection and write step 425 of fig4 in more detail . this lru victim selection and write method is a true lru method , as opposed to the pseudo lru method described in association with the prior art . when a miss occurs because both the mini - tag and the full tag missed , then the victim to be written over corresponds to the lru way 3 for that row , which can be determined by looking it up in the lru / mru unit 600 of the trace cache in step 800 . once the lru way 3 is determined , it is selected in step 805 , and overwritten in step 810 , for example , with the requested address that the mini - tags were being compared to . in step 815 , the data entry corresponding to the lru way is overwritten with the data corresponding to the requested address that was written into the lru way 3 . the lru victim selection and write operation terminates in step 820 . fig9 shows the “ full tag miss ” victim selection and write operation step 445 of fig4 in more detail . in step 900 , the way representing the mini - tag that was a hit , but having a full tag that was a miss is selected . the selected way is overwritten with the requested address being used to compare to the tags to determine a hit or a miss in step 905 . in step 910 , the data entry corresponding to the selected way is overwritten with the data corresponding to the requested address that was written into the selected way . the “ full tag miss ” victim selection and write operation terminates in step 915 . thus , by maintaining the uniqueness of each mini - tag , the processor may rely on the mini - tags to perform the read operation described above and thereby conserve time and power when accessing the trace cache . although an embodiment is specifically illustrated and described herein , it is to be appreciated that modifications and variations of the present invention are covered by the above teachings and are within the purview of the appended claims , without departing from the spirit and intended scope of the invention . it is to be understood , for example , that elements of the present invention may be implemented in hardware , software , or any combination thereof . one skilled in the art will also appreciate that the term “ data ” used throughout the application can include control information , address information , instructions , micro - operations (“ micro - ops ”), and other such information . furthermore , although an embodiment is described for a trace cache , the invention can be implemented with any type of cache in a processor / cache system . | 6 |
as those in the art will appreciate , the foregoing detailed description describes certain preferred embodiments of the invention in detail , and is thus only representative and does not depict the actual scope of the invention . before describing the present invention in detail , it is understood that the invention is not limited to the particular aspects and embodiments described , as these may 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 limit the scope of the invention defined by the appended claims . as used herein , “ cosmetics ” is defined as articles intended to be rubbed , poured , sprinkled , or sprayed on , introduced into , or otherwise applied to the human body . . . for cleansing , beautifying , promoting attractiveness , or altering the appearance [ fd & amp ; c act , sec . 201 ( i )]. such products include , e . g ., skin moisturizers , perfumes , lipsticks , fingernail polishes , eye and facial makeup preparations , shampoos , permanent waves , hair colors , toothpastes , and deodorants , as well as any material intended for use as a component of a cosmetic product . as used herein , a “ pharmaceutical ” is defined as a medicinal drug . the term “ cosmeceutical ”, as used herein , is a hybrid of the terms cosmetics and pharmaceutical and is understood to define an active ingredient in a cosmetically or pharmaceutically acceptable ( suitable for use in a human or other mammal ) excipient , carrier or vehicle . the active ingredient is typically one which has been approved for a non - cosmetic use and has been re - formulated for a new consumer use ( e . g ., uses a lower concentration of the active ingredient than the approved use ). active ingredients contemplated for use in the improved formulations and / or cosmeceuticals of the present invention include naturally - occurring prostaglandins and / or synthetic prostaglandin analog ( s ) ( pg analogs ) described in the art and discussed herein . prostaglandins are unsaturated carboxylic acids , consisting of a 20 carbon skeleton that also contains a five member ring and are based upon the fatty acid , arachidonic acid . there are a variety of structures : one , two , or three double bonds . on the five member ring there may also be double bonds , a ketone , or alcohol groups . methods of obtaining and isolating naturally - occurring prostaglandins and / or synthesizing synthetic pg analogs contemplated for use in the present invention are well documented and understood by those skilled in the art . the present invention relates to the use of at least one prostaglandin analog as an active ingredient for the manufacture of an improved formulation and / or cosmeceutical suitable for topical administration , i . e ., applied at a targeted site for exertion of local action , and intended to promote eyelash growth . accordingly , the formulations and / or cosmeceuticals of the present invention may be presented in the form of aqueous solutions , creams , ointments or oils exhibiting physiologically acceptable osmolarity by addition of pharmacologically acceptable buffers and salts . importantly , in view of the known effects and various side effects associated with the current use of pg analogs as intraocular pressure ( iop )- lowering drugs , the improved formulations and / or cosmeceuticals of the present invention have viscosity greater than that of simple aqueous solutions so as to decrease variability in delivery the formulations and provide for application in a accurate , specific , targeted manner . as such , the formulations will comprise a pharmaceutically acceptable viscosity building agent . viscosity building agents contemplated for use in the present invention include , e . g ., polyvinyl alcohol , polyvinyl pyrrolidone , and water - soluble cellulosic polymers such as methyl cellulose , hydroxy propyl methylcellulose , hydroxyethyl cellulose , carboxymethylcellulose ( cmc ), hydroxy propyl ethyl cellulose or other agents known to those skilled in the art . additional viscosity enhancers contemplated for use include : natural hydrocolloids such as acacia , tragacanth , alginic acid , carrageenan , locust bean gum , guar gum , gelatin , and hyaluronic acid ; and , synthetic hydrocolloids such carbopol ®, peg , pvp , pva , pluronics , dextran sulfate . such agents are typically employed at a concentration between about 0 . 01 % and about 3 % by weight . in a preferred embodiment of the present invention , the viscosity building agent was cmc at a concentration of 0 . 5 - 1 %. multi - dose forms of the improved formulations and / or cosmeceuticals of the present invention are also contemplated for use . as such , the formulations may require the addition of preservatives to prevent microbial contamination during use . suitable preservatives include : benzl alcohol , phenol , cresol , meta - cresol / prophyl cresol , benzalkonium chloride , thimerosal , chlorobutanol , methyl paraben , propyl paraben , phenylethyl alcohol , edetate disodium , sorbic acid , onamer m ®, phenylmercuric acetate , phenylmercuric nitrate or other agents known to those skilled in the art . such preservatives are typically employed at a concentration between about 0 . 001 % and about 1 . 0 % by weight . due to the limited solubility in water of several prostaglandins and their derivatives , the formulations may require a surfactant or other appropriate co - solvent in the composition . such surfactants include anionic surfactants chosen , e . g ., from optionally unsaturated fatty acid salts having from 12 to 18 carbon atoms , alkali metal salts of salts of organic bases with ( c 2 - c 18 ) alkylsulfuric acids , alkali metal salts of salts of organic bases with ( c 12 - c 18 ) alkylsulfonic acids , alkali metal salts of salts of organic bases with ( c 6 - c 18 ) alkylarylsulfonic acids , and ether sulfates ; nonionic surfactants , chosen , e . g ., from polyalkoxylated surfactants and polyglycerolated surfactants , such as fatty acids , fatty acid amides , fatty alcohols , alkylphenols ; esters of fatty acids and polyols , alkanediols , alkyl ethers of alkanediols ; and at least one compound chosen from alkyl carbamates of triglycerol , oxyethylenated derivatives of lanolin alcohols , propoxylated derivatives of lanolin alcohols , and lanolin fatty acids ; and cationic surfactants , chosen , e . g ., from quaternary ammonium derivatives . such co - solvents include : polysorbate 20 , 60 and 80 ; pluronic f - 68 , f - 84 and p - 103 ; tyloxapol ®; cremophor ® el ; sodium dodecyl sulfate ; glycerol ; peg 400 ; propylene glycol ; cyclodextrins ; or other agents known to those skilled in the art . the preparations of the present invention may contain additional pharmaceutically acceptable auxiliary substances as required to approximate physiological conditions and as necessary to prepare compositions for convenient administration , such as ph adjusting and buffering agents , and delivery vehicles . for example , tonicity adjustors may be added as needed or convenient . they include , but are not limited to , salts , particularly sodium chloride , potassium chloride , mannitol and glycerin , or any other suitable tonicity adjustor . various buffers and means for adjusting ph may be used so long as the resulting preparation is pharmaceutically acceptable . such buffers include acetate buffers , citrate buffers , phosphate buffers and borate buffers . actual methods for preparing pharmaceutically administrable compounds will be known or apparent to those skilled in the art and are described in detail in , for example , remington &# 39 ; s pharmaceutical science , mack publishing co ., easton , pa . ( 1985 ), which is incorporated herein by reference . additional ingredients may be added according to the understanding of those familiar with the art in order to vary the texture , consistency , viscosity , and appearance of the formulation . these additional ingredients include emulsifying agents such as non - ionic ethoxylated and nonethoxylated surfactants , fatty alcohols , fatty acids , organic or inorganic bases , preserving agents , wax esters , steroid alcohols , triglyceride esters , phospholipids such as lecithin and cephalin , polyhydric alcohol esters , fatty alcohol ethers , hydrophilic lanolin derivatives , hydrophilic beeswax derivatives , hydrocarbon oils such as palm oil , coconut oil , mineral oil , cocoa butter waxes , silicon oils , ph balancers and cellulose derivatives . the cosmeceutical may also contain amino acids , polyols , urea , allantoin , sugars and sugar derivatives , water - soluble vitamins , plant extracts ( those from iridacea plants or from soybean ) and hydroxy acids ( fruit acids or salicylic acid ); or lipophilic and chosen from retinol ( vitamin a ) and its derivatives , especially an ester ( retinyl palmitate ), tocopherol ( vitamin e ) and its derivatives ( tocopheryl acetate ), essential fatty acids , ceramides , essential oils , salicylic acid derivatives , for instance 5 - n - octanoyl salicylic acid , hydroxy acid esters , and phospholipids , for instance lecithin , and mixtures thereof . the improved preparations of the present invention may further comprise at least one additional agent commonly used in cosmetics , chosen , for example , from trace elements , demulcents , sequestrants , perfumes , oils , silicones , thickeners , vitamins , proteins , ceramides , plasticizers , coalescing agents , cohesion agents , alkalinizing agents , acidifying agents , and emollients . the improved preparations of the present invention may be combined with one or more known agents for the promotion of hair growth . specifically , the compounds of the present invention may be combined with : i ) minoxidil ( pharmacia ) and minoxidil - type compounds ; ii ) finasteride ( merck ) and finasteride - type compounds ( dihydrotestosterone ( dht ) blockers ); and iii ) copper - peptides or retinoic acid related compounds . the improved preparations of the present invention may be in the form of a pigmented or unpigmented wax - in - water dispersion , wax - in - oil dispersion , a gelled oil or an aqueous gel mascara , to be applied with an improved device of the present invention . examples of mascara formulations may be found in u . s . pat . no . 6 , 274 , 131 , and references cited therein . the present invention further relates to providing an improved delivery device for the application of the improved preparations of the present invention . importantly , the delivery devices provide for easy , accurate and targeted application of the preparations only to the area to be treated . the delivery device may be a pen - shaped device having a barrel with a reservoir containing the preparation and comprising a slidable push button located on one end of the barrel and an application element at the other end of the barrel . the pen is actuated by depression of the slidable push button which then drives a shaft connected to a piston located within the barrel to drive forward the preparation out of the reservoir and through the application element whereby it is dispensed specifically and directly to the desired area . the delivery device may comprise a receptacle containing the preparation and an applicator comprising a stem ( e . g ., a wand ) having a application element on one end of the stem and a cap on the other which is intended to cover the receptacle and is attached to the receptacle via the applicator . manipulation of the applicator is accomplished by simultaneously holding the cap and the receptacle , preferably with both hands , one in each hand . the application element is specifically designed for fine and precise application , preferably for the purpose of creating lines . the delivery device may be a pen and / or pencil apparatus comprising a first end containing lead or ink for writing , and a second end containing the preparation to be applied and comprising an application element for applying the preparation . the application element may be a tip that is flat , rounded or brush shaped for applying the preparation . the first and second ends of the pen and / or pencil may have caps to cover the ink / lead , or preparation when not in use . the delivery device may be a pen comprising a pen body having a cavity to contain the preparation ; a head portion located at one end of the pen body and having a brush partially protruded out to the exterior thereof , a cap body mounted at one end of the pen body for the capping of the head portion ; a application element including a rotational cap , a driving rod , a compression spring , a ratchet wheel , a securing seat , a piston rod and a piston , wherein the rotational cap is mounted at the other end of the pen body and has one end extended to the driving rod within the pen body , and the compression spring and the ratchet wheel are mounted onto the driving rod , and the securing seat is mounted to the pen body with the end of the driving rod , and the bottom face of the securing seat and the top face of the ratchet wheel are provided with mutually engaged teeth , and the end portion of the driving rod has a screw hole and the piston rod is mounted within the screw hole and passes through the securing seat , and the end portion of the piston rod is provided with the piston ; and a specified amount of the preparation at the lower section of the head portion of the pen body and the cavity located above the application element . the delivery device may be a hollow eyeliner brush that , in a manner similar to that of a ball point pen , dispenses with one click a precise quantity of the preparation into the brush - bristles at the tip if the eyeliner brush . this device would provide : ( 1 ) precision , because the eyeliner brush itself permits the preparation to be applied in a very precise fashion only to the base of the eyelashes ; and ( 2 ) quantitative control , thereby reducing the risk of excess active ingredient going into the eye ( where it can effect the intraocular pressure , cause redness , and / or change the color of the iris ) or onto the skin of the eyelids ( where it can cause a darkening of the skin ). as such , the device is more economical and user friendly in that the user will feel more confident that they are using the exact amount of the preparation intended to be delivered , with no waste . referring now in more detail to the drawings , fig1 shows a delivery device 100 contemplated for use . the delivery device 100 comprises a receptacle body 110 having a rollerball tip applicator 120 at one end , and capable of receiving a cartridge 130 and a mascara brush 140 at the other end . the rollerball tip applicator 120 has a removable cap 150 . the cartridge 130 has an open end 160 which receives the preparation , and has a removable cap 170 . the mascara brush 140 has an attached cap 180 . fig2 shows a delivery device 200 contemplated for use . the delivery device 200 comprises a receptacle body 210 having an eyelash curling device 220 at one end , and capable of receiving a cartridge 230 and a mascara brush 240 at the other end . the eyelash curling device 220 has a retractable scissor arm 250 attached thereto which together function to dispense the preparation from the cartridge 230 . the cartridge 230 has an open end 260 which receives the preparation , and has a removable cap 270 . the mascara brush 240 has an attached cap 280 . fig3 shows a delivery device 300 contemplated for use . the delivery device 300 comprises a receptacle body 310 having a finger hole attachment 320 , and having an eyelash curling device 330 at one end , and capable of receiving a cartridge 340 at the other end . the eyelash curling device 330 has a retractable scissor arm 350 attached thereto which together function to dispense the preparation from the cartridge 340 . the cartridge 340 has an open end 360 which receives the preparation , and has a removable cap 370 . the present invention further provides a method of administering to the skin in the area in which hair growth is desired , an amount effective for achieving said desired effect , of the formulations and / or cosmeceuticals of the present invention using a delivery device as described in the preceding paragraphs . depending on the actual formulation and prostaglandin analogue to be used , various amounts of the drug and different dose regimens may be employed . typically , the daily amount of prostaglandin for treatment of the eyelid may be about 0 . 1 ng to about 100 mg per eyelid , more preferably about 1 ng to about 100 μg per eyelid . effective amounts of the active derivatives will vary depending on the derivative employed , frequency of application and desired result , but will generally range from about 0 . 0000001 % to about 50 % by weight of the dermatological preparation . the actual dose of the active ingredients of the present invention depends on the specific compound , and on the condition to be treated . determination and selection of such appropriate dose is well within the knowledge of the skilled artisan . in this example , various preparations were prepared and used in studies conducted to demonstrate the efficacy of targeted application of the improved formulations and / or cosmeceuticals of the present invention in promoting eyelash growth . the preparations were prepared in accordance with methods and procedures known and understood by those skilled in the art . the following preparations were prepared : preparation a — xalatan ® ( latanoprost 0 . 005 %), 0 . 5 % carboxymethylcellulose ( cmc ); preparation b — travatan ® ( travoprost 0 . 004 %), 0 . 5 % carboxymethylcellulose ( cmc ); and preparation c — lumigan ® ( bimatoprost 0 . 03 %), 0 . 5 % carboxymethylcellulose ( cmc ). protocol . patients were treated and studied using the following protocol : the preparation was applied to eyelids of the patient once a day for nine weeks . importantly , the preparations were carefully applied only to the base of the eyelashes using a specialized eyeliner brush . measurements of the length of each patient &# 39 ; s eyelashes were taken prior to treatment (“ baseline ”), and at time intervals of approximately 3 weeks , 6 weeks , and 9 weeks thereafter . in the studies , ten patients were treated with preparation a , three patients were treated with preparation b , and six patients were treated with preparation c . results . preparation a : with specific reference to the increase in length of the eyelashes above the baseline starting point , the average amount of eyelash growth was not measurable ( i . e ., no growth beyond baseline starting point ) at 3 weeks or at 6 weeks . average eyelash growth was measured at an average of 0 . 5 mm ( range of 0 mm - 1 mm ) at 9 weeks . no thickening or darkening of the eyelashes was observed in any of the patients . preparation b : with specific reference to the increase in length of the eyelashes above the baseline starting point , the average amount of eyelash growth was measured at 2 . 5 mm ( range : 2 mm - 3 mm ) at 3 weeks . average eyelash growth was measured at 7 . 0 mm ( range 4 . 0 mm - 9 . 0 mm ) at 6 weeks . average eyelash growth was measured at an average of 10 . 5 mm ( range : 8 mm - 12 mm ) at 9 weeks . all 3 patients experienced a significant and noticeable increase in the length of their eyelashes . in addition , all 3 patients noted both a thickening of their eyelashes as well as a darkening of the lashes , and 2 patients also reported an actual increase in the number of eyelashes along the lid margin . preparation c : with specific reference to the increase in length of the eyelashes above the baseline starting point , the average amount of eyelash growth was measured at 2 mm ( range : 1 mm - 3 mm ) at 3 weeks . average eyelash growth was measured at 6 mm ( range from 3 mm - 8 mm ) at 6 weeks . average eyelash growth was measured at an average of 10 mm ( range of 8 mm - 12 mm ) at 9 weeks . all 6 patients experienced a significant and noticeable increase in the length of their eyelashes . in addition , all 6 patients noted both a thickening of their eyelashes as well as a darkening of the lashes , and 3 patients also reported an actual increase in the number of eyelashes along the lid margin . importantly , one of the patients in the preparation c treatment group had recently undergone aggressive chemotherapy for a recurrence of metastatic breast cancer . after her chemotherapy , 90 % of her previously long eyelashes fell out . the few remaining eyelashes were noted to be sparse , short , light in coloration , and narrow in diameter . after treatment with preparation c , a remarkable increase in the number , length , and thickness of the eyelashes was noted . these lashes were also noted to be darker in color . in addition , the response to preparation c was rapid ; that is , after 3 weeks , several new eyelashes had begun to sprout , and the remaining eyelashes had grown ˜ 3 mm . after 6 weeks , many additional new growth sprouts were noted , and there was a significant increase in the length of the existing lashes ( 8 mm of growth ). after 9 weeks , the increased length of the existing lashes was 12 mm . this result suggests the possibility that stimulation of eyelash growth with a prostaglandin analogue , in individuals who have lost their eyelashes due to aggressive chemotherapy , may be an especially effective and helpful treatment , both cosmetically and in terms of helping their self - image . in this example , a study was performed wherein one patient was treated using preparation b and preparation c , alternating daily for a period of nine weeks . preparation b was applied to the base of the eyelashes once a day on the “ even ” days of the month , and preparation c applied to the base of the eyelashes once a day on the “ odd ” days of the month . with specific reference to the increase in length of the eyelashes above the baseline starting point , the average amount of eyelash growth was measured at 3 . 5 mm at 3 weeks . average eyelash growth was measured at 8 . 5 mm at 6 weeks . average eyelash growth was measured at an average of 11 . 5 mm at 9 weeks . in addition , at 3 weeks the patient noted a significant increase in the number of eyelashes along the lid margin , as well as a darkening and thickening of the new eyelashes . the results of this study suggest that a regime of daily alternating applications of preparation b and preparation c to the eyelid margins may be more effective in stimulating new eyelash growth than either preparation by itself . all of the articles and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure . while the articles and methods of this invention have been described in terms of preferred embodiments , it will be apparent to those of skill in the art that variations may be applied to the articles and methods without departing from the spirit and scope of the invention . all such variations and equivalents apparent to those skilled in the art , whether now existing or later developed , are deemed to be within the spirit and scope of the invention as defined by the appended claims . all patents , patent applications , and publications mentioned in the specification are indicative of the levels of those of ordinary skill in the art to which the invention pertains . all patents , patent applications , and publications are herein incorporated by reference in their entirety for all purposes and to the same extent as if each individual publication was specifically and individually indicated to be incorporated by reference in its entirety for any and all purposes . the invention illustratively described herein suitably may be practiced in the absence of any element ( s ) not specifically disclosed herein . thus , for example , in each instance herein any of the terms “ comprising ”, “ consisting essentially of ”, and “ consisting of ” may be replaced with either of the other two terms . the terms and expressions which have been employed are used as terms of description and not of limitation , and there is no intention that 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 invention claimed . thus , it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features , modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art , and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims . | 0 |
referring to fig1 a graph 90 resulting from the trivial example discussed in the summary of the invention section is illustrated . blocks 10 , 20 , 30 , and 40 represent the nodes . block 10 represents the choice of the one bit quantizer used to encode the bits on the left side and block 20 , the choice of the one bit quantizer to encode the bits on the right side . block 30 represents the choice of the two bit quantizer used to encode the bits on the left side and block 40 , the choice of the two bit quantizer to encode the bits on the right side . a starting node s and an end node e are also defined to indicate the starting node and the ending node of the optimization problem respectively . each node , including 10 - 40 , s and e is linked with another node by a directed line segment , also called a “ transition ” in some of the art . the lines indicating transitions 45 , 50 , 55 , 60 , 65 , 70 , 75 , and 80 are directed such that progress is only permitted in the left - to - right direction as indicated by the arrows . each node 10 - 40 has associated with it a distortion cost . as discussed in the summary section , each node 10 - 40 also has associated with it a bit requirement for encoding the corresponding image portion ( l , r ). the total bits required so far are also stored within the node . after initializing the graph 90 and a heap ( not shown ) ( with the starting node s , s having zero distortion ( cost ) and zero “ bit requirement ”), the a * algorithm begins by calculating the distortion and bit requirement ( i . e ., sum of distortion from s to the node ) for each of the neighboring nodes 10 and 30 . if the total bit requirement for a node is below the stipulated ceiling , then the total distortion ( and pointer to the node ) is placed in the heap , with the one corresponding to the lower total distortion rising to the top . if the node corresponding to the lower distortion is node 10 , then its neighbors 20 and 40 will be expanded next ; that is , the distortion and bit rates corresponding to each calculated and added to the base distortion and bit rate corresponding to node 10 . thus , node 20 will have a distortion which is the total of nodes 10 and 20 and s and similarly for node 40 . also , the totals for the bit rates will be calculated as well . if both are below the bit rate budget , the values of the total distortions will be placed on the heap . if not , only the distortion value that corresponds to the path within the bit budget will be placed in the heap . within each node , a pointer to the best “ parent ” node is maintained . the parent is the node that imparted the lowest cost . in this example , parents are to the left of each node , and are indicated as 81 to 85 . the final path is traced from e to s and is then reversed to give the optimal path . the lower of the two final results , assuming both are within the bit budget , will be the provisional optimized path . recall that the optimization problem can have a time limit for the compression operation . if there is time left in the time limit , then the neighborhood of node 30 may be expanded if this total distortion is less than the distortion at e . in the hypothetical example , the rate and distortion corresponding to the transitions 70 and 80 are identical to those for the transitions 50 and 75 , but in general this may not be the case , depending on the compression problem . the process would continue as for node 10 with the result that the values at nodes 20 and 40 are not improved , and therefore they are not added to the heap . the lower total distortion node — let node 40 be lower for this example — will be next to expand . since 60 has transition cost ( zero ), then e is reached . this may signal the end of the search . if there were other values in the heap , having values less than node 40 , the search could proceed further . note that in this case , the end node is a stand - in and transitions 55 and 60 are not be associated with any incremental rate or distortion , so the search goes directly to e when either node 20 or 40 is reached . after as many searches as can be done — in the present case there is only one expansion possible for each of the two possible beginning transitions — the parent node giving the lowest total distortion cost is chosen . referring to fig2 which is from u . s . pat . no . 5 , 778 , 192 for “ method and device for optimal bit allocation between different sources of information in digital video compression ,” the entirety of which is hereby incorporated by reference as if fully set forth herein , a lowest cost path search problem identified with video compression is illustrated . the diagram of fig2 represents a multi - level trellis that represents the allowed choices of quantizers for a 32 pixel by 32 pixel image block in which the block is segmented using a quadtree structure that is permitted to be developed down to level 3 . that is , segments of 8 by 8 , 16 by 16 , and 32 by 32 are permitted . the quadtree structure corresponds to the white ovals 115 , 120 , and 125 , each of which designates a set of nodes , for example 110 , 130 , and 140 , which are indicated by the black dots . note that only representative ones of the ovals and nodes are labeled with reference numerals to keep the drawing from being overly busy . although only two nodes 110 , 111 , 112 , 130 , and 140 are shown in each set , the number can be any number of nodes , each corresponding to the number of admissible state values for the individual blocks at different levels . in other words , each node corresponds to a choice of quantizer for a particular aspect of the video stream . the scheme discussed in the above - identified patent is a motion compensation scheme . in that scheme , the auxiliary nodes , start s , and termination z , are used to initialize the differential pulse code modulation ( dpcm ) of the motion vectors and to select the path with the smallest total cost from a rate / distortion standpoint . as discussed in the above patent , the goal is to identify a path through the trellis that corresponds to the lowest total rate / distortion cost . the path must be made up of allowed transitions , e . g ., 100 , 101 , and 102 . this amounts to the problem of allocating an available bit budget among various different kinds of data . in the example from the above - mentioned patent , there are three critical types of data involved in a particular kind of compression scheme : segmentation , motion vectors , and prediction error . for purposes of understanding the invention , the details of the compression scheme are not important because many compression schemes give rise to such graph search problems , even though many may not be representable as a trellis . the complex optimization problem in all cases results because of the difficulty presented by the fact that the amount of distortion suffered by forsaking one bit for a particular type of data is not equivalent to that suffered by the forsaking of another bit representing some other type of data . the basic objective is to optimally encode a given frame or video sequence in the rate - distortion sense . that is , optimally allocate bits , given bit budget of a given the encoding scheme , that will result in the smallest possible distortion or vice versa . for purposes of the invention , the particulars of the encoding scheme and the particulars of the graph search problem resulting from it are unimportant as long as the graph search problem has the following characteristics : 1 . the topology of the path space defines a directed graph consisting of a set of nodes with some allowed transitions therebetween . some nodes may not be reachable from other nodes and cyclic connections are permissible . 2 . a cost , to be optimized , can be defined for each transition . the cost must be non - negative . 3 . the cost at each node may be a function of prior nodes included in the path . there must be a start and at least one goal or terminating condition , but these can be arbitrarily defined as in the simple example discussed above . referring now to fig3 the neighborhood of the starting node s is expanded first . this is the first step in the stepwise propagation of a least - cost wave . a bit rate and distortion is calculated for each transition 147 , 148 , 145 , 146 , 149 , and 151 , which encompasses the neighborhood of the starting node s . all distortion values are placed in the heap 5 . the rate is also calculated , and is stored in each node . a pointer from each node to the start is also added . assuming the transition 145 to the node 130 corresponds to the lowest distortion cost that remains under the bit rate ceiling , the node 130 will rise to the top of the heap causing the neighborhood of node 130 to be expanded as shown in fig4 and costs and rates calculated for each of a new set of transitions 173 . further , the “ best path ” parent is also identified . in this figure , we omit the parent arrows for graphical simplicity . this process continues until , as illustrated in fig5 a final optimized path 210 that reaches the end node z is found . again , the process can continue , beginning with the lowest remaining total cost node , to find a more global optimum , unless some time , other constraint prevents it , of it the total cost is not less than that of z . referring to fig6 a device for implementing the processes on a data stream is illustrated . a data source 310 applies a data stream to a processor 300 that is programmed to implement a compression algorithm optimizing quantizers in accord with the invention . the processor then outputs a compressed video data stream 320 . referring to fig7 a flow chart illustrates a process in which a data stream is compressed in an environment that imposes a time limit , or processing resource limit , on the compression process . a new set of data is accepted in step s 10 . for example , a video frame could be accepted for processing in step s 10 . a timer is then initialized in step s 15 ( or a processing resource quantifier ). the timer is then checked for expiration in step s 20 and if there is time ( or processing resources ) remaining , a new optimal path is propagated according to the optimal path algorithm discussed above in step s 25 . flow then returns to input a new set of data at step s 10 . if the timer times out in step s 20 , a best ( least cost ) path among the candidate paths found in each iteration of step s 25 is identified in step s 30 . then , in step s 35 , the data is compressed according to the quantizers identified in step s 30 , the compressed data is output , and the process flows back to step s 10 . it will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments , and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof . the present embodiments are therefore to be considered in all respects as illustrative and not restrictive , the scope of the invention being indicated by the appended claims rather than by the foregoing description , and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein . | 7 |
the preferred embodiment is directed to etching the top working surface of a wafer to form a silicon stylus with a predetermined geometry . here and throughout the descriptions , working surfaces refer to the surfaces of interest that a specified operation is being performed on . for ease of presentation , “ top ” refers to the working surfaces of the wafer that are part of the silicon stylus formed or to be formed , while “ bottom ” refers to working surfaces that are not part of the silicon stylus to be formed or formed . the wafer is typically either a silicon wafer , a p - doped silicon wafer , an n - doped silicon wafer , a p - doped silicon - on - insulator ( soi ) wafer or a n - doped silicon - on - insulator wafer . fig1 a - 1d show steps for making a silicon nitride layer with a protruding silicon stylus . a wafer 50 is provided with a top silicon working surface 52 and a bottom silicon working surface 54 . the wafer 50 is a silicon wafer or a silicon - on - insulator wafer . in the case shown , the wafer is a silicon wafer that is p - doped , n - doped or un - doped silicon . the top working surface 52 , as shown in fig1 a , has been etched , according to known techniques , the details of which are readily available to produce a silicon stylus 60 with a height from 0 . 1 μm to 50 μm , but typically about 10 μm . the silicon stylus 60 is a tapered silicon structure that has an apex 62 and a base 64 , as shown in fig1 a . note that the silicon stylus 60 can be doped at any time during the method described when the silicon stylus or stylus apex is exposed . the preferred method for doping the stylus is by ion implantation , but any known method may be employed . notably , doping is useful for altering the conductivity of the tip itself . there are many reasons to control the conductivity including reducing electrostatic effects during dynamic operation , and having the ability to use the tip as an electrical ohmic point probe or an electric field probe . when using the tip 60 in such electrical applications , a metal element ( not shown ) may be connected from the tip 60 to the die or probe mount ( not shown ) in order to facilitate connection to the instrument . doping may also be changed in order to use the high doping as an etch stop , for example , in order to make a “ shell ” tip . it is well known that silicon highly doped with boron is an effective etch stop in silicon anisotropic etches ( i . e ., koh , edp , tmah ). by intensely boron doping the tip , the body of the tip can be etched away from the back side , leaving only the outside shell of the tip . this is advantageous because it will reduce the mass of the tip without affecting its functionality . operationally , the benefit of a lower mass tip is that it will cause the resonant frequency of the device to increase . higher resonant frequency cantilevers , with similar spring constants , have been shown to provide higher resolutions and faster responses when used as sensors . turning to fig1 b , a silicon dioxide ( sio 2 ) layer 66 , is grown over the wafer including the silicon stylus 60 . this layer is grown in conventional fashion in a manner that will cause the silicon tip to become sharper . an example of this would be an oxidation step using steam at 950 degrees c ., a well known process . the thickness of the resulting oxide layer should be great enough to serve as an etch stop for the subsequent silicon nitride etch . typically , 0 . 25 nm is a preferred thickness for the oxide layer . a silicon nitride layer 68 is then deposited over the silicon dioxide layer 66 . the silicon nitride layer 68 is deposited by one of a group including chemical vapor deposition ( cvd ), low pressure chemical vapor deposition ( lpcvd ), plasma enhanced chemical vapor deposition , chemical deposition , evaporation and sputtering , and is preferably 10 nm to 10 μm thick . as will become apparent , it is the oxide layer 66 that operates not only as an etch stop but as an intermediate “ bonding ” layer between the silicon tip and the silicon nitride cantilever . a protective coating 70 is then deposited on the silicon nitride layer 68 . preferably , coating 70 is a photoresist applied by spin coating , so that the coating thickness is less than the height of the silicon nitride covered silicon stylus 60 . an additional lithography step , which clears any resist from the apex 62 of tip 60 , could be used at this point . more particularly , the height of the tip 60 is known from prior processing . and , the properties of the resist are typically well known by the manufacturer , with the resist typically being provided with a look - up table that contains values for the final resist thickness for different spin speeds and durations . notably , even though the apexes of the tips may be covered by the initial application of the resist , the subsequent spin planarazation will clear them adequately . if this is a concern , a quick resist etch may be applied to clear any residual resist “ scum ” from the apex 62 . this process will leave a very thin coating , to no coating , of resist on the apex of the stylus . turning to fig1 c , a silicon nitride covered silicon stylus 60 is etched to expose the underlying silicon dioxide layer 66 , but not over - etched to the point that the silicon stylus 60 is exposed . the etch control is accomplished by knowing the etch rates of both the film being etched , the etch stop , and the etch mask of the particular etch tool being used . with these numbers , along with knowledge of the thickness of the film being etched , the etch stop , and the etch mask , a process window can be calculated that will give a range of etch times that will clear the stylus without clearing the etch stop or the etch mask . if these calculations do not yield an adequate etch window , the etch process or etch tool must be changed to increase the selectivity of the etch to the etch stop and the etch mask . this protects the apex 62 of the stylus 60 from this etch , and the subsequent cantilever release etch . in many cases , the combination of the etch selectivity between silicon nitride 68 and the resist 70 , and the height of the silicon nitride coated stylus will require multiple coatings of resist 70 to be applied . this would occur if all the resist is etched off the wafer before the silicon nitride on the silicon stylus is completely removed . the old resist can optionally be stripped off and new resist applied , and the etch continued . notably , during the clearing of the apex it is often convenient to pattern the shape of the cantilever . this is done by standard photolithography either during the stylus clearing or in a subsequent lithography step . it should be noted that photoresist need only be used if lithography is employed . otherwise polyimides , epoxies , waxes , etc . can be used for the tip definition . also , consumption of resist by the etch can be used , in conjunction with the total resist thickness , to tailor the amount of the stylus 60 that will be exposed . after the stylus has been exposed by the etch , the remaining resist is removed from the top silicon working surface of the wafer in conventional fashion . turning to fig1 d , a device is now released by etching away the back side silicon . this etch is stopped when the silicon is removed from under the silicon nitride layer 68 ( i . e ., cantilever ), but before the silicon stylus 60 is removed . in the case of an soi wafer , the middle oxide is used as an etch stop . the silicon dioxide layer 66 may then be removed . the protective oxide layer is preferably removed in an etch that is highly selective to silicon nitride and silicon , such as 6 : 1 buffered oxide etch , so that the characteristics of the tip ( for example , sharpness ) are not compromised . as a result , the silicon dioxide is removed without unbonding the silicon tip 60 from the silicon nitride cantilever . in sum , an oxide layer 66 is inserted so that the tip 1 ) is protected to the end of the process ( i . e ., the oxide operates as a passivating layer ), and 2 ) is coupled to the silicon nitride , albeit via the oxide . in the completed device , the tip 60 is cleared of oxide on its apex , but again not in the region that affixes the tip 60 to the silicon nitride 68 . therefore , the method removes the silicon nitride from the tip 60 while at the same time preserves the designed characteristics of the tip . notably , because the oxide passivation layer protects the tip throughout the entire process , including the exposing of the apex , but also through the release of the cantilever structure , the step of releasing the cantilever 68 via the backside silicon wafer etch does not ruin the tip 60 . a reflective coating 72 may then be deposited on a back side 74 of the cantilever 68 . again , this coating 72 may serve multiple purposes including , for example , a surface for reflecting a laser beam toward a photodetector in an optical beam - bounce measurement apparatus . the reflective coating can optionally be applied , in process , on the front side of the cantilever . this is advantageous because the reflective coating can be patterned into a specific shape . an example of a useful shape would be a reflective coating near the free end of the cantilever but not on the base of the cantilever . this configuration also would minimize the residual bending of the cantilever due to stress in the applied reflective film , and bending from thermal effects . fig2 a - 2d illustrate steps for making a silicon nitride layer with a protruding silicon stylus and a front side reflective coating . the process is the same as with respect to fig1 a - 1d , only now a reflective film 80 is deposited over the silicon nitride 68 . this film 80 may or may not be patterned separately from patterning the cantilever structure . the film is patterned separately when the desired shape of the reflector is different from the desired shape of the cantilever . this may be done to optimize cantilever parameters such as stress or reflectivity . if patterned separately , it is removed from the stylus stack before the silicon nitride stylus clearing etch . if a separate lithography is not used , this reflective coating can be cleared in the same manner as the silicon nitride 68 , only with a suitable etch . an additional lithography , which clears the resist 70 from the apex 62 of the tip 60 , could be used at this point . notably , the process illustrated in fig2 a - 2d is contrary to conventional practice in , for example , producing probes for surface analysis tools such as an atomic force microscope . again , in conventional production , the metal reflector is disposed on the back side of the cantilever in the final step of production because the laser used in the measurement apparatus ( e . g ., using an optical beam - bounce technique ) is typically reflected off the back side of the cantilever . and , in conventional production , the last step is the first time the back side of the cantilever is revealed so it cannot be deposited earlier in the process . the result of the process illustrated in fig2 d is a reflector on the front side of the cantilever , disposed in process prior to the back side being revealed . because the cantilever is transparent , a suitable reflector results , much how the metalization on a household mirror is disposed on the far side of the glass . this technique has significant advantages including the fact that the metal reflector can be shaped , and thus can be kept separate from critical elements . moreover , it is easier to process and more robust , and stress can be better controlled because the substrate is more stable . and , the process yields less worry about residual coating of the tip 60 because the reflective film 80 is actively etched away . moreover , this technique is particularly useful when producing thin cantilevers that need reflectors . the afm industry , for one , seems to be moving towards thinner levers , and therefore thinners reflectors . this process of producing a front side reflector can offer improvements over bulk back side coating because , as noted above , by patterning the reflector just where you need it , you can eliminate stress problems and thermal drift problems . fig3 a - 3d illustrate the fundamental steps for making a silicon nitride layer with a protruding metal stylus 90 . the same process is used as in forming the silicon stylus ( fig1 a - 1d ), only the etch is not stopped when the field silicon is clear , but when all the silicon is consumed , as shown in fig3 c . if an soi wafer is used , an extra oxide etch must be inserted , as appreciated by those skilled in the art . a metal film 90 is then deposited from the back side of the cantilever until the hole or aperture 92 formed by the removed silicon stylus is filled with metal and metal protrudes beyond silicon nitride cantilever to define stylus or tip 90 . the result of the deposition will be the formation of a metal tip 90 with electrical contact to the base of the cantilever . notably , the metal tip will be self - sharpening to a degree . as the aperture closes the apex will come to a point . however , it typically is not nearly as sharp as the silicon tip . this is acceptable as “ metal tip ” applications usually do not require a tip as sharp as applications that require a silicon tip . fig4 a and 4b illustrate the fundamental steps for making a silicon nitride layer with a protruding thermally sensitive stylus . the structure of fig3 a to 3d is formed and therefore the previous steps will not be repeated . thereafter , a dissimilar metal 100 is then deposited on the front or top surface 102 of the cantilever . the junction of the two metals 90 , 100 , which only occurs substantially at the apex 110 of tip 108 , forms a thermocouple . as previously noted , it is well known that dissimilar metals in contact will produce a voltage that is proportional to temperature . electrical contact is made to the thermocouple from contacting the respective metals 90 , 100 on the mounting section area 104 , 106 , respectively . turning to fig5 , a method 110 of producing a silicon nitride cantilever having a silicon tip is shown . initially , in block 112 , a substrate , such as a silicon wafer or a silicon - on - insulator wafer , is provided . then , one or more tips or styluses are formed on the working surface of the substrate in block 114 . at this point , an optional doping step may be performed to alter the make - up of the silicon stylus ( es ) in block 116 , as described previously . again , this doping step may be performed to alter electrical properties of the tip , or to form a “ shell ” tip , etc . next , in block 118 , an oxide layer is deposited on the top working surface of the substrate . preferably , this oxide layer acts as a sharpening step that results in a silicon dioxide layer residing on the silicon substrate including the silicon tips . then , a cantilever material layer ( preferably , silicon nitride ) is deposited on the silicon dioxide layer in block 120 . once the silicon nitride layer is formed so as to provide a cantilever having a selected thickness , a protective coating is deposited on the top working surface in block 122 . preferably , this is a spin coated resist that is deposited in conventional fashion . in block 124 , the apex of the tip is cleared of the silicon nitride . this is accomplished by using an appropriate etch . notably , the shape of the cantilever can be patterned in an optional operation as part of block 124 . importantly , upon completion of clearing the apex in block 124 , the protective silicon dioxide layer remains on the tip . in block 126 , the cantilever is released by etching away the silicon from the back side of the wafer . notably , the integrity of the characteristics of the tip are maintained in this step due to the fact that the silicon dioxide layer remains on the tip . once the cantilever is released in block 126 , the silicon dioxide on the tip ( and back side of substrate ) is removed using an appropriate etch so as to not compromise the integrity ( e . g ., sharpness ) of the tip in block 128 . then , in block 130 , a reflective coating is deposited on the cantilever of the probe from the back side working surface . of course , as highlighted above in discussing fig2 a - 2d , this reflective coating may be deposited on the front side working surface of the wafer during formation of the cantilever , after deposition of the silicon nitride layer in block 120 . method 110 is terminated in block 132 , to produce a scanning probe device suitable for use in , for example , an atomic force microscope . although the best mode contemplated by the inventors of carrying out the present invention is disclosed above , practice of the present invention is not limited thereto . it will be manifest that various additions , modifications and rearrangements of the features of the present invention may be made without deviating from the spirit and scope of the underlying inventive concept . the scope of still other changes to the described embodiments that fall within the present invention but that are not specifically discussed above will become apparent from the appended claims . | 8 |
fig1 schematically shows the components of a vehicle with two - axle steering , to the extent that they are needed to comprehend the invention . the vehicle , not shown in further detail , has a front axle 1 and a rear axle 3 , each of which is embodied as steerable . to that end , each axle has a translationally movable steering gear 5 , which is movable by means of a hydraulic cylinder 7 . the hydraulic cylinder 7 of the front axle 1 communicates via hydraulic lines 9 , 11 with connections a , b of a 6 / 4 - steering mode selection valve 13 . other connections c , d of the steering mode selection valve 13 communicate with the hydraulic cylinder 7 of the rear axle 3 via hydraulic lines 16 , 17 . if one of the hydraulic cylinders 7 is acted upon by the hydraulic medium on one side , then the applicable steering gear 5 of the respective axle 1 , 3 moves in the direction determined by the pressure force and induces a corresponding steering operation . the swiveling motion of the applicable wheel is attained by means of one schematically shown steering suspension each . for instance , if the hydraulic cylinder 7 of the front axle is acted upon with the pressure medium via the line 9 , then the steering gear 5 moves to the right , creating the steering motion of the wheels of the front axle 1 toward the left . correspondingly , by action on the hydraulic cylinders 7 , the desired steering motions of the axles 1 , 3 can be brought about . the steering mode selection valve 13 has two further connections l , r , which are connected via hydraulic lines 9 , 21 to a steering controller 23 of the vehicle . the steering controller 23 includes a unit 25 whose outputs are connected to the hydraulic lines 19 , 21 . the unit 25 is coupled to a steering wheel 27 of the vehicle . when the steering wheel 27 is turned to the left , the unit 25 brings about an inflow of hydraulic medium into the line 19 . correspondingly , when the steering wheel is turned to the right the unit 25 brings about an inflow of hydraulic medium into the hydraulic line 21 in the direction of the steering mode selection valve 13 . the quantity of hydraulic medium delivered into the respective line 19 , 21 depends on the rotational angle of the steering wheel 27 . in the embodiment shown in fig1 the steering mode selection valve 13 has four switching positions , marked i , ii , ii , iv . switching position i defines exclusive control of the vehicle by means of the front axle ( front - axle steering ), while switching position iii defines exclusive control of the vehicle by means of the rear axle 3 ( rear - axle steering ). switching position ii brings about two - axle steering , in which the front axle 1 and rear axle 3 are each triggered in the same direction . in other words , at the same time , a steering motion of both the front and rear axle to the right or left is generated at the same time . the switching position iv brings about so - called crab steering of the vehicle , in which the front axle 1 and the rear axle 3 are each triggered in opposite directions . in other words , if at the front axle 1 a steering motion to the left is brought about , then at the rear axle 3 a steering motion to the right is generated , and vice versa . to select the steering modes in switching positions i - iv , the steering mode selection valve 13 has an actuating arrangement 29 . the actuating arrangement includes at least one or more mechanical actuators for actuating the valve positions , and the selection of valve positions can be done by means of electrical triggering ( not shown ) of the actuating arrangement . fig2 a shows the schematic layout of the steering mode selection valve 13 of the invention ; switching position iii is shown , that is , rear - axle steering of the vehicle . as can be seen from fig2 a , the 6 / 4 - way valve 13 is formed by a total of seven 2 / 2 - way valves 31 , 33 , 35 , 37 , 39 , 41 , 43 , which communicate via hydraulic lines in such a way that the switching positions i - iv of the steering mode selection valve 13 can be realized by means of corresponding switching positions of the 2 / 2 - way valves 31 - 43 . the 2 / 2 - way valves are embodied as seat valves , each of which has one open position and one blocked position . embodying them as seat valves offers the advantage that in the blocked state , no leakage whatever occurs . each of the 2 / 2 - way valves are actuated by means of resilient elements 31a - 43a in such a way that if the actuating motion is absent they are transferred to the blocked state . for actuating the position - seat valves 31 - 43 , these valves each have a respective tappet 31b - 43b . the actuating arrangement 29 of the exemplary embodiment shown in fig2 a - 2d includes a shaft 45 , on which cam disks 47 , 49 , 51 , 53 , 55 , 57 , 59 are provided . the cam disks 47 - 59 are solidly joined to the shaft 45 , so that upon a rotation of the shaft 45 , the tappets 31b - 43b of the position - seat valves 31 - 43 are actuated in the desired way by the cam disks . to that end , it is understood that the contours and phase relationships of the cam disks be selected in a suitable way . in the rear axle steering shown in fig2 a , only the cam disks 53 and 61 act upon the valves 33 and 39 , so that in each case a connection of the input l to the output d and a connection of the input r to the output c of the steering mode selection valve 13 is made . all the other position - seat valves are in the blocked state . fig2 b , conversely , shows switching position i of the steering mode selection valve 13 , i . e ., front - axle steering , in which the input l is connected to the output a , and the input r is connected to the output b . to that end , as can be seen in fig2 b , only the position - seat valves 35 and 43 are in the open position and to that end are acted upon in a suitable way by the cam disks 57 and 59 , respectively . all the other position - seat valves are again in the blocked state . fig2 c shows two - axle steering of the vehicle , in which the input l of the steering , mode selection valve 13 is connected to the output a and the input r is connected to the output c , and furthermore the outputs b and d are connected to one another . thus when pressure is exerted by the line 19 , for instance , the front axle 1 undergoes a steering motion to the left ( pressure imposition by the line 9 ) and by pressure imposition through line 17 as a consequence of the communication with the &# 34 ; return line &# 34 ; 11 , a steering motion to the left is also brought about at the rear axle 3 . as can be seen in fig2 c , to that end the position - seat valves 31 , 35 and 39 are controlled to the open state . this is done by a corresponding rotation of the shaft 45 via the cam disks 49 , 51 and 57 associated with the respective seat valves . finally , fig2 d shows the switching positions of the position - seat valves 31 - 43 for the switching position iv of the steering mode selection valve 13 , that is , for so - called crab steering . a s can be seen from fig1 to this end the input l may be connected to the output a , and the input r must be connected to the output d , and the output b must also be connected to the output c of the valve . to achieve this , the seat valves 35 , 37 , 41 must be directed to the closed state ( see fig2 d ). all the other seat valves are in the blocked state . in this switching position , when pressure is exerted through the line 19 , for instance , the front axle 1 is steered to the left , while the rear axle 3 , because of the communication of the &# 34 ; return line &# 34 ; 11 with the line 15 , is steered to the right . in order upon a rotation of the shaft 45 to direct only the appropriate seat valves into the open state , the cam disks must have the form and angular position relative to one another that can be seen in fig2 a - 2d . these depend naturally on the orientation of the tappets 31b through 43b of the seat valves 31 - 43 . in this respect , the embodiment of the cam disks in fig2 a - 2d should be considered merely a schematic example . as can be seen in fig2 a , the actuating arrangement 29 can have an actuating gear or detent locking gear 61 . the actuating gear comprises a toothed wheel 63 , which is solidly connected to the shaft 45 and is acted upon by an actuating element 65 in the form of a displaceable tappet . the tappet 65 is retained in an outset position by a spring 67 and can be deflected vertically downward , in the exemplary embodiment shown in fig2 a , by means of an electromagnet 69 . this causes a rotation of the toothed wheel 63 and thus of the shaft 45 . the deflection of the actuating element 65 by the electromagnet 69 should be dimensioned such that upon each displacement motion of the actuating element 65 , the toothed wheel 63 is rotated onward by an angular amount corresponding to one tooth each time . after each displacement motion of the actuating element 65 , this element is moved back again to the outset position by the spring 67 , so that upon another activation of the electromagnet 69 , another indexing onward of the actuating gear by one tooth of the toothed wheel 63 takes place . to prevent reverse rotation of the toothed wheel 63 , a locking latch 71 , embodied as a spring - impinged displaceable tappet , engages the teeth of the toothed wheel 63 . it is understood that any arbitrary other actuating gear may be used , instead of the embodiment shown in fig2 a - 2d . in principle , an electric motor rotary drive is also suitable for moving the shaft 45 . however , using an actuating gear has the advantage that at least in the switching positions , detent positions exist . to that end , naturally the actuating gear may also be embodied such that on each shifting operation of the actuating gear ( by one tooth ), a transition occurs from one switching position i - iv of the steering mode selection valve 13 to the respective next switching position . moreover , the use of an actuating gear makes it possible in a relatively simple way to achieve manual emergency actuation of the gear , in case the electromagnetic actuation of the actuating element 65 fails . fig3 shows concrete embodiment for the actuating gear 61 , in section . the toothed wheel 63 , which is solidly joined to the shaft 45 ( not shown in fig3 ) is surrounded by an annular element 73 , which together with a driving element or pin 75 guided substantially radially displaceably in the annular element 73 forms the actuating element 65 . the annular element 73 is surrounded on its outside by a curved resilient element 76 , which with its resilient leg acts upon the outside of the pin 75 , while a bent - over region of the other end of the spring 76 , for the sake of connection with the annular element 73 , engages a slit in the annular element 73 . the entire actuating gear 61 is disposed in a housing 77 of the steering mode selection valve 13 . also disposed in this housing 77 is the locking latch 71 , which has a pin that acts upon the teeth of the toothed wheel 63 . the pin is held displaceably and under spring action in a part that is screwed into the housing 77 . am o ring 79 for sealing purposes is disposed between the housing 77 and the retaining part of the locking latch 71 . the annular element 73 , with a portion of its circumference , engages the inside of a fork 81 and is connected to the ends of the fork by means of a pivot pin 63 . upon a substantially vertical motion of the fork 81 , accordingly , this substantially translational motion is converted into a rotary motion of the annular element 73 . an end of the tappet 85 that is provided with a thread is screwed into the upper region of the fork 81 . the tappet engages the inside of a power region of a magnet tube 87 of the electromagnet 89 . the magnet tube has a male thread on its lower end , with which it is screwed into a bore with a female thread in the housing 77 . for sealing off from the housing 77 , an o ring 89 is again provided between a shoulder of the magnet tube 87 and the housing 77 . above the tappet 85 in the magnet tube 87 , a stationary element 91 of a ferromagnetic material , preferably steel , is provided . the element 91 has a central bore which is engaged by an upper region of the tappet 85 . below this upper region , the tappet 85 has a flange 85a , which is acted upon by a spring 93 that is supported by its lower end on the top of a nut 95 that is screwed from below into the magnet tube 87 . thus in the inactive state of the electromagnet 69 , the tappet 85 is moved with its flange 85a against the underside of the element 91 , and in this way an outset position of the tappet 85 or of the annular element 73 is defined . the nut 95 has a bore 95 a , which has a diameter slightly larger than the outer diameter of the tappet 85 . as a result , adequate play for the tappet 85 is made possible , so that upon a vertical motion the tappet can execute a slight tilting motion , which is necessary in order to create a rotary motion of the annular element 73 . on the other hand , the diameter of the bore 95a is selected to be small enough that adequate guidance of the tappet 85 is assured . inside the central bore of the element 91 , the tappet 85 is acted upon from above by a pin 97 , which is solidly joined to a main tappet 99 . the main tappet 99 is guided displaceably substantially in the upper half of the magnet tube 87 , that is , in a space above the element 91 . the magnet tube is encompassed by a winding 101 , whose terminals are extended outward into a plug element 103 . the plug element 103 can thus be coupled with a cable , not shown in further detail , so that in this way the winding 101 can be acted upon by current . when current is exerted on the winding 101 , the winding generates a magnetic flux in a magnetic circuit , which is formed by the armature parts of ferromagnetic material 105 , 107 , by the upper portion of the magnet tube 87 and by the main tappet 99 , as well as by the element 91 and the lower portion of the magnet tube 87 . to avoid a magnetic short circuit , the magnet tube 87 , in a middle region , has an insulating region 109 of a magnetically insulating material . in this way it is assured that when current is imposed on the winding 101 , the main tappet 99 together with the pin 97 is moved vertically downward . in this process the pin 97 acts upon the tappet 85 , thus generating a rotary motion of the annular element 73 , so that a shifting operation of the actuating gear is performed . for the sake of completeness , it will be noted that the winding 101 is naturally shielded from the armature part 105 by an insulating layer 111 . the armature parts 107 ( which may be embodied as disks ) and the armature part 105 are also surrounded by a further insulating layer 113 , to protect them against environmental factors and mechanical damage . on its upper end , the magnet tube 97 has a central bore , in which a manually actuatable emergency actuation pin is retained in displaceable fashion . this pin , on its lower end , has a region of widening diameter , so that together with an inner shoulder of the magnet tube 87 a stop is formed for the emergency actuation pin 115 . with its underside , the emergency actuation pin 115 acts upon the main tappet 99 , so that even if the electromechanical actuation by an imposition of current on the winding 101 fails , manual actuation of the actuating gear is still possible . to that end , the upper end of the emergency actuation pin 115 , which protrudes past the magnet tube 87 or is at least accessible at the upper end thereof , can be manually actuated . | 5 |
the present invention as shown in fig1 is a locking key ring 10 comprising a quarter turn lock cylinder assembly 12 including a cam lock 14 and a housing 16 , and a shackle 18 in the form of a key ring for supporting one or more keys k . the housing 16 preferably carries identifying and instructional data in the form of indicia i . the identifying information could include a company or an individual &# 39 ; s name , an address , and a phone number . the instructional information would inform a locksmith to notify an authority prior to duplicating the key or keys k . fig2 shows the locking key ring 10 further comprising an irregular shaped ninety degree turn stop 20 , a cylindrical bushing 22 , and a circular locking cam 24 . the cam lock 14 , as shown in fig1 has a key hole 26 disposed at a proximal end thereof and a tail shaft 28 ( in the form of a double - d shaft ) extending from a distal end . the tail shaft 28 carries the ninety degree turn stop 20 , the bushing 22 , and the locking cam 24 . the turn stop 20 and the locking cam 24 are each provided with an aperture which matingly engages the tail shaft 28 . without the presence of the turn stop 20 , the operating key ( not shown ) could rotate the tail shaft 28 indefinitely . the turn stop 20 functions in cooperation with a protrusion 30 extending from a lower rear portion of the cam lock 14 . it is this cooperative relationship which limits the rotational travel of the tail shaft 28 to ninety degrees or one quarter turn . the bushing 22 disposed between the turn stop 20 and the locking cam 24 provides a desired spatial separation between the turn stop 20 and the locking cam 24 . the locking cam 24 includes two semi - circular notches 32 disposed 180 degrees apart about the outer periphery thereof . the housing 16 contains the cam lock 14 , the turn stop 20 , the bushing 22 and the locking cam 24 . a pin 34 is engagable with a hole 36 in the housing 16 and a hole 38 in the cam lock 14 which coaligns with a hole 36 in the housing 16 . the pin 34 maintains the cam lock 14 in a position relative to the housing 16 retaining the cam lock 14 , the turn stop 20 , the bushing 22 and the locking cam 24 therein . two openings 40 are located at the rear of the housing 16 which are purposed to receive end portions of the shackle 18 . the shackle 18 is substantially u - shaped and the end portions thereof each include a reduced diameter end portion 42 and an intermediate shoulder 44 . referring now to fig2 and 3 , and more specifically to fig3 showing the relationship between the shackle 18 and the locking cam 24 . interiorly of the rear end of the housing is 16 disposed a blind hole 46 to accommodate the distal end of the tail shaft 28 . the space provided between the rear interior surface of the housing 16 and the rear surface of the cam lock 14 provides a loose fit for the turn stop 20 , the bushing 22 and the locking cam 24 disposed therebetween . the locking key ring 10 is shown in a locked position with the ninety degree turn stop 20 rotated fully clockwise and the locking cam 24 engaging the reduced diameter end portion 42 of the shackle or key ring 18 . the washer 22 maintains the locking cam 24 in a spaced apart relation relative to the ninety degree turn stop 20 . in this position , the shackle 18 is not removable from the rear of the housing 16 . the housing 16 is fixed relative to the cam lock 24 preventing the shackle 18 and the housing 16 alike from being rotated to release the shackle 18 . by turning the cam lock 14 counter clockwise ninety degrees rotating the tail shaft 28 and , in turn , the ninety degree turn stop 20 and locking cam 24 , the semi - circular openings 32 are aligned with the end portions of the shackle 18 permitting the shackle 18 to be released from the rear of the housing 16 . fig4 and 5 show an alternative locking key ring 110 comprising a lock assembly 112 including a cam lock 114 , a housing 116 and a rear housing plug 118 , and a shackle or a key ring 120 . the tail shaft 122 extending from the rear of the cam lock 114 is provided with a male thread which is threadably engagable with a female threaded aperture 124 centrally located in a forward portion of the rear housing plug 118 . elongated concave slots 126 are provided within the inner peripheral walls of the housing 116 and are spaced one hundred and eighty degrees apart . the rear housing plug 118 has a reduced diameter surface 128 and a head 130 . similar to the housing 116 , the reduced diameter surface 128 also has elongated concave slots 132 spaced one hundred and eighty degrees apart and which mutually align with respective elongated slots 126 located interiorly of the housing 116 . these slots 126 , 132 mutually align to form an elongated circular opening . the shackle 120 is substantially u - shaped and has substantially circular end portions 134 which are each engagable with a respective circular opening form by respective concave slots 126 , 132 . each end portion 134 of the shackle 120 further includes an offset segment 136 . notches 138 are provided in the rear shoulder 140 of the housing 116 adjacent the rear extremity of the elongated slot 126 . according to this embodiment , with an operating key ( not shown ), the tail shaft 122 may be rotated clockwise or counter clockwise indefinitely . to lock the shackle 120 in the locked position shown in fig5 the circular end portions 134 of the shackle 120 are inserted into the housing 116 and so as to engage the concave slots 126 therein . the aperture 124 in the plug 118 is aligned with the threaded tail shaft 122 while at the same time , the concave slots 132 associated with the plug 118 are aligned with both the circular end portions 134 and the concave slots 126 disposed interiorly of the housing 116 alike . as the tail shaft 122 is rotated clockwise , the plug 118 is drawn into the housing 116 until the shoulder 142 of the head 130 contacts the shoulder 140 of the housing 116 . with the tail shaft 122 fully engaging the aperture 124 in the plug 118 , the shackle 120 is intact . the circular end portions 134 occupy the circular openings defined by the mutually corresponding concave slots and the offset segments 136 each extend through the notches 138 . with the circular end portions 134 occupying the circular openings , the plug 118 remains fixed relative to the housing 116 and similar to the first embodiment , the housing 116 remains fixed relative to the cam lock 114 by a pin 144 mutually engagable with the housing 116 and the cam lock 114 . to disengage the shackle 120 , simply rotate the operating key counter clockwise which , in turn , rotates the tail shaft 122 counter clockwise causing the tail shaft 122 to disengage the aperture 124 further causing the plug 118 to egress from the housing 116 . it should be noted that the principle of the underlying invention remains irregardless of the materials and the particular configurations shown . the material used in fabricating the locking key rings 10 , 110 is not limited to a particular material and the configuration may be arranged in any suitable manner to produced the instant invention as claimed . the present invention is not limited to the embodiments described above , but encompasses any and all embodiments within the scope of the following claims . | 4 |
hereinafter , an explanation is given of a method for manufacturing a semiconductor memory according to embodiment 1 of the present invention with reference to the drawings . fig1 a to 1c , 2 a to 2 c and 3 are sectional views illustrating the steps of manufacturing a dram of a cub structure according to embodiment 1 of the present invention . according to the method of the present embodiment , in the step shown in fig1 a , an sti 1 is formed first to surround part of a silicon substrate 20 where a transistor will be formed . then , a gate insulating film 2 a of 6 nm in thickness is formed on the silicon substrate 20 . further , polysilicon ( not shown ) is deposited on the gate insulating film 2 a and then dry - etched using a mask ( not shown ) formed on the polysilicon , thereby forming a gate electrode 2 b of 150 nm in thickness which functions as a word line . then , ion implantation is carried out using the gate electrode 2 b as a mask to form an impurity diffusion layer 3 of 100 nm in thickness in part of the silicon substrate 20 located at each side of the gate electrode 2 b . then , a first interlayer insulating film 4 made of bpsg ( boron phospho - silicate glass ) is deposited on the silicon substrate 20 to cover the gate electrode 2 b . the first interlayer insulating film 4 is then planarized by cmp so that it has a uniform thickness of about 500 nm . then , in the step shown in fig1 b , a mask ( not shown ) is formed on the first interlayer insulating film 4 and etching is carried out to form a bit line contact hole ( not shown ) and a capacitor contact hole ( not shown ) which penetrate the first interlayer insulating film 4 to reach a drain region and a source region in the impurity diffusion layer 3 , respectively . then , the surfaces of the bit line contact hole and the capacitor contact hole are covered with barrier metals 5 a and 6 a made of tin of 10 nm in thickness , respectively , and the contact holes are filled with conductive films 5 b and 6 b made of tungsten , respectively . thus , a bit line contact 5 and a capacitor contact 6 are formed . then , an insulating film 7 such as a silicon nitride film of 50 nm in thickness is deposited on the first interlayer insulating film 4 . further , in the step shown in fig1 c , a second interlayer insulating film 8 of 800 nm in thickness made of bpsg is formed on the insulating film 7 . then , a resist mask ( not shown ) having an opening corresponding to a capacitor region is formed on the second interlayer insulating film 8 and dry etching is carried out to remove the second interlayer insulating film 8 and the insulating film 7 in the capacitor region . thus , a storage node hole 9 is formed . when viewed in plan , the top end part h 1 of the storage node hole 9 ( part of the sidewalls of the storage node hole 9 closer to the top surface of the interlayer insulating film 8 ) is in the form of a rectangle having a long side length of 0 . 5 μm and a short side length of 0 . 2 μm . the storage node hole 9 is formed by two - step dry etching . more specifically , first dry etching is carried out using the insulating film 7 as an etch - stop to remove the second interlayer insulating film 8 until the surface of the insulating film 7 is exposed , and then second dry etching is carried out to selectively remove the exposed insulating film 7 . then , in the step shown in fig2 a , a tin film of 30 nm in thickness ( not shown ) is formed over the bottom surface and the sidewalls of the storage node hole 9 and the surface of the second interlayer insulating film 8 outside the storage node hole 9 . then , a resist ( not shown ) is applied to the substrate and light exposure is carried out over the entire surface of the substrate to leave the resist ( not shown ) only in the storage node hole 9 . then , anisotropic etching is carried out to selectively remove the tin film , thereby forming a lower electrode 10 made of tin of 30 nm in thickness on the bottom surface and the sidewalls of the storage node hole 9 . at this time , the anisotropic etching is carried out such that the tin film is removed by about 80 nm in thickness , thereby positioning the upper end of the lower electrode 10 lower than the top surface of the second interlayer insulating film 8 by about 50 nm . that is , the lower electrode 10 is formed on the sidewalls of the storage node hole 9 at a deeper position than the top surface of the second interlayer insulating film 8 by about 50 nm or more . then , in the step shown in fig2 b , a capacitive insulating film 11 made of ta 2 o 5 of 20 nm in thickness is deposited over the lower electrode 10 and the second interlayer insulating film 8 . since the lower electrode 10 is positioned lower than the top surface of the second interlayer insulating film 8 , part of the sidewalls of the storage node hole 9 which is not in contact with the lower electrode 10 , i . e ., the surface of the top end part h 1 of the storage node hole 9 , comes into direct contact with the capacitive insulating film 11 . thereafter , a tin film of about 50 nm in thickness ( not shown ) is formed on the capacitive insulating film 11 to form an upper electrode 12 . then , in the step shown in fig2 c , a mask ( not shown ) having an opening in a bit line contact region is formed on the upper electrode 12 and etching is carried out to form an opening 17 . at this time , the upper electrode 12 is over - etched by about 30 %, i . e ., about 15 nm in terms of the tin film , so as not to leave the upper electrode 12 and the capacitive insulating film 11 in a bit line contact region the memory cell region and the other regions than the memory cell region . fig2 c shows that the opening 17 is misaligned from the desired position and the left end of the opening 17 reaches the capacitor in the storage node hole 9 . the misalignment of the opening 17 is derived from the mask ( not shown ) for forming the opening 17 which is misaligned from the desired position . then , in the step shown in fig3 , a third interlayer insulating film 13 of 600 nm in thickness made of bpsg is deposited on the upper electrode 12 and planarized by cmp such that the thickness thereof on the upper electrode 12 outside the storage node hole 9 is reduced to 200 nm . then , a bit line contact 14 is formed through the third interlayer insulating film 13 and the second interlayer insulating film 8 below the opening 17 to reach the bit line contact 5 . then , a first wiring layer 15 is formed on the third interlayer insulating film 13 to be in contact with the bit line contact 14 . through the above steps , a capacitor of a cub structure is obtained . hereinafter , the effect of the manufacturing method of the present embodiment will be described in comparison with that of the conventional method . in the conventional method , a margin c shown in fig8 b is narrowed as the device is further miniaturized . therefore , as shown in fig8 a , an opening 117 is misaligned and an upper electrode 112 at the top end part h 3 of a storage node hole 116 is removed to expose a capacitive insulating film 111 . on the other hand , in the present embodiment , the lower electrode 10 is positioned lower than the top surface of the second interlayer insulating film 8 as shown in fig2 c . accordingly , at the top end part h 1 of the storage node hole 9 , the upper electrode 12 is formed along the sidewalls of the storage node hole 9 . as a result , part of the upper electrode 12 at the top end part h 1 of the storage node hole 9 is given with a large thickness as compared with that obtained by the conventional technique . therefore , in the step of forming the opening 17 , even if the opening 17 is misaligned to overlap the capacitor and the upper electrode 12 is over - etched in the vertical direction , part of the capacitive insulating film 11 which stores the capacitance of the capacitor will not be exposed . the part of the capacitive insulating film 11 which stores the capacitance of the capacitor mentioned herein is part of the capacitive insulating film 11 sandwiched between the upper and lower electrodes 12 and 10 . for example , the lower electrode 10 does not exist at part of the capacitive insulating film 11 sandwiched between the top end part h 1 of the storage node hole 9 and the upper electrode 12 . therefore , even if the capacitive insulating film 12 is exposed as shown in fig2 c , adverse effect such as the occurrence of leakage current is not caused . as described above , if a capacitor is formed by the method of the present embodiment , the capacitance of the capacitor will not be affected even if the opening 17 is formed to overlap the capacitor . this eliminates the need of providing an alignment margin c between the opening 17 and the capacitor in the storage node hole 9 , though it has been necessary in the conventional method . that is , according to the present embodiment , the storage node hole 9 is enlarged to be in contact with the opening 17 at the top end part h 1 as shown in fig4 , while the memory cell size is not changed . thus , a larger amount of capacitance is stored in the capacitor while device miniaturization is achieved . fig4 is a view illustrating a planar configuration of the semiconductor memory of embodiment 1 of the present invention . next , a comparison as to the total area of the capacitor is made between the capacitor of the present embodiment and a conventional capacitor . the total area of the capacitor mentioned herein is the sum of the area of the capacitor at the bottom of the storage node hole 9 ( bottom area ) and the area of the capacitor at the sidewalls of the storage node hole 9 ( lateral area ). the conventional capacitor shown in fig8 b has a short side length a of 0 . 2 μm , a long side length b of 0 . 45 μm and an alignment margin c of 0 . 05 μm and the storage node hole 9 has a height of 0 . 85 μm ( height of the capacitor region ). under these conditions , the total area of the conventional capacitor is calculated as follows . on the other hand , the present embodiment eliminates the need of the alignment margin . therefore , the long side length of the capacitor increases by 0 . 05 μm in a memory cell having the same area as the conventional memory cell . further , at the top end part of the storage node hole 9 , the lower electrode 10 is formed at a deeper position than the top surface of the second interlayer insulating film 8 by 50 nm or more . therefore , the height of the capacitor becomes smaller by 0 . 05 μm than the conventional capacitor . as a result , the capacitor of the present embodiment has a short side length a of 0 . 2 μm , a long side length b ( including the margin c ) of 0 . 5 μm and the height of 0 . 8 μm . under these conditions , the total area is calculated as follows . from the above results , it is understood that the capacitor of the present embodiment is given with a larger area than the conventional capacitor . hereinafter , with reference to the drawings , an explanation is given of a method for manufacturing a semiconductor memory according to embodiment 2 of the present invention . fig5 a to 5c , 6 a to 6 c and 7 are sectional views illustrating the steps of manufacturing a dram of a cub structure according to embodiment 2 of the present invention . according to the method of the present embodiment , an sti 1 is formed in a silicon substrate 20 , and then a gate insulating film 2 a , a gate electrode 2 b , an impurity diffusion layer 3 and a first interlayer insulating film 4 are formed in the step shown in fig5 a in the same manner as embodiment 1 . then , in the step shown in fig5 b , a bit line contact 5 , a capacitor contact 6 and an insulating film 7 are formed . then , in the step shown in fig5 c , a second interlayer insulating film 21 of 750 nm in thickness is formed on the insulating film 7 and an insulating film 22 of 50 nm in thickness is formed on the second interlayer insulating film 21 . the second interlayer insulating film 21 is made of a material which is wet - etched at a higher rate than the insulating film 22 . for example , the second interlayer insulating film 21 may be made of psg and the insulating film 22 may be made of nsg . as described later , the wet etching mentioned herein is carried out to etch the second interlayer insulating film 21 and the insulating film 22 to form a storage node hole 9 . then , a resist ( not shown ) having an opening corresponding to the capacitor region is formed on the insulating film 22 and dry etching is carried out using the resist as a mask , thereby forming a storage node hole 9 which penetrates the insulating film 22 , the second interlayer insulating film 21 and the insulating film 7 to reach the top surface of the capacitor contact 6 . then , wet etching is carried out using a hydrofluoric acid solution under such conditions that the second interlayer insulating film 21 is etched faster than the insulating film 22 . thus , in the storage node hole 9 , the second interlayer insulating film 21 is removed more than the insulating film 22 . as a result , part of the storage node hole 9 where the second interlayer insulating film 21 forms the sidewalls thereof becomes about 40 nm larger in diameter than part of the storage node hole 9 where the insulating film 22 forms the sidewalls thereof . instead of forming the second interlayer insulating film 21 and the insulating film 22 from different materials , boron may be implanted into the top part of an interlayer insulating film ( not shown ) so that the top part of the interlayer insulating film is given with an etch rate different from that of the other part . for example , the interlayer insulating film is formed to have a thickness of 800 nm and then boron is implanted therein down to a depth of 50 nm from the top surface thereof . since the wet - etch rate decreases with an increase in boron concentration , the top part of the interlayer insulating film becomes lower in etch rate than the other part . then , in the step shown in fig6 a , a tin film of 30 nm in thickness ( not shown ) is formed on the bottom surface and the sidewalls of the storage node hole 9 . thereafter , a resist ( not shown ) is applied to the substrate and light exposure is carried out over the entire surface of the substrate , thereby leaving the resist only in the storage node hole 9 . then , etching is carried out to remove only 130 nm of the tin film to form a lower electrode 23 made of tin . in this etching step , the upper end of the lower electrode 23 which is uncovered with the resist is thinned down to about 10 nm in thickness , while the other part of the lower electrode 23 remains unetched because it is covered with the resist . then , in the step shown in fig6 b , a capacitive insulating film 24 made of ta 2 o 5 of 20 nm in thickness is formed on the lower electrode 23 in the storage node hole 9 and the insulating film 22 outside the storage node hole 9 . then , an upper electrode 25 made of tin of 50 nm in thickness is formed on the capacitive insulating film 24 . then , in the step shown in fig6 c , a mask 26 having an opening corresponding to a bit line contact region is formed on the upper electrode 25 , and then dry etching is carried out using the mask 26 to form an opening 27 . fig6 c shows the opening 27 which is misaligned from the desired position and the left end of the opening 27 reaches the capacitor in the storage node hole 9 . the misalignment of the opening 27 is derived from the mask 26 which is misaligned from the desired position . then , in the step shown in fig7 , a third interlayer insulating film 13 , a bit line contact 14 and a first wiring layer 15 are formed in the same manner as embodiment 1 . through the above - described steps , a capacitor of a cub structure is obtained . in the capacitor of the present embodiment , as shown in fig5 c , the side edge of the insulating film 22 at the top end part h 2 of the storage node hole 9 protrudes toward more inside of the storage node hole 9 than the side edge of the second interlayer insulating film 21 . since the lower electrode 23 is not formed on the protruding side edge of the insulating film 22 at the top end part h 2 of the storage node hole 9 , the capacitive insulating film 24 formed on the insulating film 22 at the top end part h 2 of the storage node hole 9 does not store the capacitance . therefore , no problems arise even if the opening 27 is misaligned to overlap the capacitor as shown in fig6 c , thereby removing parts of the upper electrode 25 and the capacitive insulating film 24 formed at the top end part h 2 of the storage node hole 9 . on the other hand , the capacitance is stored in the lower electrode 23 , capacitive insulating film 24 and upper electrode 25 which are formed at a level lower than the top end part h 2 of the storage node hole 9 . as shown in fig7 , since the insulating film 22 at the top end part h 2 of the storage node hole 9 protrudes toward inside of the storage node hole 9 to generate a dent part below it , the upper electrode 25 is reduced in level difference which is generated at part thereof covering the boundary between the insulating film 22 and the dent part below it . therefore , even if the opening 27 is misaligned to overlap the capacitor , the lower electrode 23 , capacitive insulating film 24 and upper electrode 25 formed in the storage node hole 9 at a level lower than the insulating film 22 are less likely to be removed . as described above , in the capacitor manufactured by the method of the present embodiment , the capacitive insulating film 24 which contributes to the capacitance will not be damaged even if the opening 27 overlaps the capacitor . therefore , unlike the conventional method , there is no need of providing an alignment margin between the opening 27 and the capacitor in the storage node hole 9 . more specifically , in the present embodiment , the capacitor in the storage node hole 9 is enlarged to be in contact with the opening 17 , while the memory cell size is not changed . as a result , a larger amount of capacitance is stored while device miniaturization is achieved . in the present embodiment , the following conditions are preferably satisfied so as to prevent the capacitive insulating film 24 which contributes to the capacitance from damage even when the opening 27 overlaps the capacitor . as a first condition , the side edge of the insulating film 22 is formed to protrude toward more inside of the storage node hole 9 than the side edge of the second interlayer insulating film 21 by the length same as or larger than the thickness of the lower electrode 23 . if the protruding length of the side edge of the insulating film 22 is smaller than the thickness of the lower electrode 23 , as a second condition , the upper electrode 25 is formed to have a thickness larger than the difference between the thickness of the lower electrode 23 and the protruding length of the insulating film 22 ( the thickness of the lower electrode 23 minus the protruding length ). if one of these conditions is satisfied , the capacitive insulating film 24 which contributes to the capacitance will not be damaged by dry etching for forming the opening 27 . the opening 27 is allowed to overlap the capacitor as long as it does not exceed a boundary d shown in fig6 c , i . e ., as long as the capacitive insulating film 24 formed at the bottom of the storage node hole 9 is not exposed . | 7 |
in fig1 a camera 10 is schematically shown . an accessory support member 12 , generally called a tray in the art , is fastened to the bottom of camera 10 with a screw 14 using a standard mounting position . for descriptive purposes , three arm segments 16 are shown in fig1 clamped to each other in a desired configuration by side clamps 18 . the lower arm segment 16 is connected to tray 12 by any suitable means and is not described here . a strobe light 20 is mounted on the upper arm segment 16 with a saddle clamp 22 which is described later with respect to fig8 . side clamps 18 are depicted in fig2 . fig2 shows that the arm segments 16 are provided with spherical ball ends 24 . side clamp 18 has a pair of clamping plates 26 . each plate 26 has two spherical indentations 28 therein , sized to accept balls 24 in intimate and extensive contact . indentations 28 , if desired , may comprise holes that extend through plates 28 with beveled edges to engage balls 24 . a threaded bolt 30 passes through both plates 28 and into the deeply threaded hub 32 of an adjustment knob 34 . since the hub 32 is threaded , a large number of threads are available to engage bolt 30 , thus , allowing a wide range in adjustment of the pressure of plates 26 on balls 24 . with knob 34 slightly loosened , each segment 16 can be angled through an arc of nearly 270 degrees , because of the narrow necks 36 , and also rotated about its own axis , so that virtually any relative position may be achieved . the knob 34 is then retightened to lock the segments in place . referring simultaneously to fig3 - 5 , it may be seen that arm segments 16 comprise cylindrical rods with a central longitudinal axis 38 , and four longitudinal channels 40 formed along the sides of the segment . channels 40 are sized to leave four strips or ribs of material 42 at the maximum diameter of segment 16 so as to maintain the strength and rigidity of arm segment 16 . this configuration also gives segment 16 a generally square cross section that is easy to grip in an underwater environment . channels 40 and ribs 42 are easiest to visualize in the cross sectional view of fig4 . returning to fig3 a series of transverse holes 44 are visible that extend from one channel 40 through to the opposite channel 40 . there is also a series of orthogonal transverse holes that intersect holes 44 . if segment 16 is rotated 90 degrees about its central axis 38 in fig3 it would appear exactly the same as fig3 except that the orthogonal holes 44 would now be visible . the diameter of holes 44 should be as large as possible without cutting through ribs 42 . as can be seen in the sectional view of fig5 the diameter of holes 44 are about 40 to 50 percent the diameter of segment 16 . the separation of holes 44 along the longitudinal axis is also kept to a minimum without eliminating the wall of material 46 that spaces ribs , as most easily seen in fig4 and 7 . as shown in fig7 the thickness t of wall 46 is less than half the diameter of holes 44 , preferably , about or even less than 15 percent of the diameter of holes 44 . with the holes 44 this proximate to each other , water can easily flow not only through the individual holes , but also in one hole and easily out the orthogonal intersecting hole as illustrated by the arrows 50 in fig5 . thus , underwater movement of the camera and strobe arms is much easier because water resistance is very much lower as the water flows with minimum turbulence and direction change . fig6 further demonstrates the transparency of the arm segments to water flow . in fig6 the portion of segment 16 shown in fig3 is shown rotated 45 degrees about longitudinal axis 38 . this view direction is that indicated by arrows 48 in fig4 and 5 . as can be seen in fig4 - 6 , water can flow through the openings in numerous ways so as to minimize resistance . however , the segment 16 remains very rigid due to the preservation of longitudinal ribs 42 transversely located by walls 46 . strobe lights and other accessories may be attached to the articulated collection of arm segments with a segment that is designed to connect to the accessory , as necessary , and also designed with a ball end 26 , so that side clamps 18 may be employed to locate it . alternatively , fig8 shows a saddle clamp 22 that is similar to side clamp 18 with clamping plates 52 , a knob 54 , and a bolt 56 . however , plates 52 have projections 58 that rest in channels 40 . with this arrangement , the saddle clamp 22 can be slid along the length of segment 16 to any desired position , and locked in place by tightening knob 54 on bolt 56 . plates 53 then clamp a ball end 60 which is connected by a neck 62 to the desired accessory mount . saddle clamp 22 also allows a new branch of connected arm segments to be started . it is evident that any collection of strobes and accessories , in any position , may be quickly and easily assembled from the novel segments and clamps of the present invention . the resulting collection is light , rigid , and low in water resistance . we intend to be limited not to the specific arrangements shown in the drawings , but only by the appended claims and their equivalents . | 6 |
where r and r 2 are as defined above for the formula ( i ) compound is reacted with the desired amine r 1 h as defined for the r 1 group , to give the intermediate enamine ( ib ) where r 1 is as defined above for the formula ( i ) compound , which is subsequently transformed into the final compound ( i ). the transformation from compound ( ia ) to ( ib ) is accomplished with known techniques , but it has been seen that the reaction is conveniently achieved by treating compound ( ia ) with the amine r 1 h in the presence of lewis acids , for example triflates , such as trimethylsilyltrifluoromethane sulphonate , or protic acids , such as sulphonic acids , e . g . p - toluenesulphonic acid . the reaction is carried out in a solvent which is inert to the reagents and the reaction products , or , in a preferred embodiment , the amine r 1 h can be used in relation to compound ( ia ) in an excess such as to constitute the reaction medium . the reaction parameters are not critical and can be determined by a technician with average experience in the field on the basis of his or her own general knowledge of the subject . for example , the molar ratios of compound ( ia ) to amine r 1 h may range from 1 : 1 to an excess of amine in the sense referred to above . the reaction temperature will be selected also in relation to the type of reagents used , their molar ratios , and the optional presence of a solvent , in which case it may even be as high as the boiling temperature of the solvent , providing this does not lead to decomposition of the reagents themselves . the reaction times are selected on the basis of the parameters outlined above and will be such as to complete the reaction . attempts to optimise the reaction do not constitute an additional experimental burden and are part of the normal techniques used in chemical synthesis . the transformation of the enamine into the formula ( i ) compound is achieved by means of the reduction of the double enamine bond and falls within the sphere of the normal expertise of the average technician . suitable reducing agents can be retrieved in the relevant literature manuals and do not require any particular specialist knowledge . for example , one suitable reducing agent is sodium borohydride . for this second step , too , the considerations outlined above regarding the reaction parameters and solvents hold good . the isolation and purification of the formula ( i ) compound are accomplished with normal known procedures ; in particular , the separation of the enantiomorphs can be done , amongst other things , as described in the above - mentioned patent application . the process according to the invention described herein can be used to prepare benzothiazepines in general and , on proceeding with the reduction of the enamine , dihydrobenzothiazepines . in a first preferred embodiment of the invention , the formula ( ia ) compound is reacted with amine r 1 h , using the latter as a reaction medium , when its physicochemical characteristics so permit . the triflate preferred is trimethylsilyltrifluoromethane sulphonate . the reaction temperature is approximately 120 ° c . and the reaction time approximately 3 hours . in a second preferred embodiment of the invention , the formula ( ia ) compound is reacted with amine r 1 , using the latter as the reaction medium , when its physicochemical characteristics so permit . the preferred sulphonic acid is p - toluenesulphonic acid . the reaction temperature is approximately 180 ° c . and the reaction time approximately 1 - 2 hours . the isolation and purification of the formula ( i ) compound are achieved with normal known procedures ; in particular , the separation of the enantiomorphs can be accomplished , amongst other things , as described in the above - mentioned patent application , or , according to one embodiment of the invention described herein , by fractionated crystallisation . examples are provided for the preparation of (±)- 7 - chloro - 9 -( 4 - methylpiperazin - 1 - yl )- 9 , 10 - dihydropyrrolo [ 2 , 1 - b ][ 1 , 3 ] benzothiazepine ( st1455 ), one of the preferred compounds described in patent application wo 00 / 06579 . it is perfectly obvious that the examples provided here apply to all formula ( i ) compounds , with suitable modifications which can be implemented by the average technician in the field . to a mixture of ketone [ 9b ] ( 4 . 5 g ; 18 mmol ) and n - methylpiperazine ( 15 ml ) was added drop - wise trimethylsilyl - trifluoromethane sulphonate ( 5 . 7 ml ; 31 . 5 mmol ) in 5 minutes . the reaction temperature was brought up to 120 ° c . the reaction , monitored via tlc , was completed in 3 hours . the reaction mixture was left to cool at ambient temperature and the resulting solid mass was dissolved in methylene chloride ( 50 ml ) and washed with water ( 2 × 30 ml ). the organic phase was anhydrified on sodium sulphate and filtered . evaporation of the solvent at reduced pressure enabled a crude reaction product to be recovered , which , when chromatographed on silica gel ( n - hexane / ethyl acetate 50 : 50 ) finally yielded 4 . 7 g of the title compound . yield : 78 % tlc ( acoet ) rf = 0 . 25 ; mp : 127 ÷ 128 ° c . 1 h - nmr ( 300 mhz , cdcl 3 ) δ 7 . 6 ( d , 1h , j = 2 . 1 hz ); 7 . 4 ( d , 1h , j = 8 . 5 hz ); 7 . 2 ( dd , 1h , j 1 = 8 . 4 hz , j 2 = 2 . 0 hz ); 6 . 7 ( m , 1h ); 6 . 6 ( m , 1h ); 6 . 2 ( m , 1h ); 6 . 1 ( m , 1h ); 2 . 9 ( m , 4h ); 2 . 6 ( m , 4h ); 2 . 3 ( s , 3h ). 13 c - nmr ( 300 mhz cdcl 3 ) δ 143 . 8 ; 140 . 5 ; 137 . 9 ; 134 . 8 ; 133 . 2 ; 129 . 8 ; 129 . 6 ; 127 . 9 ; 123 . 2 ; 112 . 7 ; 111 . 6 ; 111 . 2 ; 55 . 2 ; 50 . 1 ; 46 . 2 . elemental analysis : ( c 17 h 18 cln 3 s ): compliant a mixture of ketone [ 9b ] ( 0 . 15 g ; 0 . 6 mmol ), n - methylpiperazine ( 0 . 18 g ; 1 . 8 mmol ) and p - toluenesulphonic acid ( 0 . 296 g ; 1 . 56 mmol ) was heated to 180 ° c . the reaction , which rapidly took on a dark colouring , was completed in 1 . 5 hours ; the mixture was left to cool at ambient temperature and the resulting - solid mass was dissolved in methylene chloride ( 10 ml ) and washed with water ( 2 × 10 ml ). the is organic phase was anhydrified on sodium sulphate and filtered . evaporation of the solvent at reduced pressure yielded a crude reaction product which was chromatographed on silica gel ( n - hexane / ethyl acetate 50 : 50 ) giving the title compound . the compound [ 10b ] ( 2 . 97 g ; 8 . 97 mmol ) was dissolved in acetic acid ( 25 ml ); the solution was brought down to a temperature of 0 ° c . and nabh 4 ( 400 mg ) was added cautiously . the reaction was completed in 2 hours the mixture was evaporated at reduced pressure . methylene chloride was added , and three washings with water and bicarbonate were done . the organic phase was anhydrified on sodium sulphate , filtered and evaporated at reduced pressure . 2 . 75 g of product were obtained with 95 % purity , as calculated at hplc . the tables given here below show the values of the individual process steps according to the invention described herein ( table 1 ) as compared to the process described in patent , application wo 00 / 06579 ; see in particular pp . 29 - 30 and example 2 of the patent application cited ( table 2 ). the racemic mixture obtained was separated into the two optically active isomers by means of fractionated crystallisation of the diastereoisomeric salts obtained by salification with tartaric acid , according to the procedure outlined here below . 2 . 5 g of st1455 ( 7 . 5 mmol ) were dissolved hot in ethanol and added with 1 . 12 g of d (−) tartaric acid ( 7 . 5 mmol ). the solution was held overnight at ambient temperature . the tartrate crystals thus obtained were filtered and recrystallised by a 3 : 1 ethanol / methanol mixture . the solution was held overnight - at ambient temperature . after filtration , 1 . 1 g of tartrate of the (+) enantiomorph were obtained , which at hplc presented an optical purity of 97 . 3 . column : chiralpack - ad ( 5 m ), 4 . 6 × 250 mm ; t = 23 ° c . ; mobile phase : n - hexane - ethanol , tea ( 95 / 5 / 0 . 1 v / v ); flow : 1 ml / min ; rt = 5 . 6 min the tartrate was then converted to a free base by treatment with nahco3 and extraction by acoet . similarly , st1455 was treated with l (+) tartaric acid to yield the corresponding tartrate of the (−) enantiomorph . the method of separating the racemic mixture by fractionated crystallisation is particularly advantageous compared to that obtained by separation on a semipreparative chiral column , whenever the amounts of product required are considerably greater than those normally deriving from a laboratory synthesis process . | 2 |
an understanding of the present invention will be had by taking into consideration the following description in connection with the drawings . referring first to fig1 a drive motor b1 is positioned on a suitable mounting plate or base with the drive shaft mounted below the base as may be seen by reference to fig2 . located on the upper surface of the base are guide posts g1 , g2 , g3 , g4 and g5 respectively on which tape tp1 is positioned . as may be noted , tp1 includes a 180 ° twist or turn as may be noted between guides g1 and g2 . a recording playback head pu1 is positioned so that the tape surface of tape tp1 rides across its surface in a conventional manner . drive for the tape is provided by either capstan c1 or c2 which are kept in contact with the tape by means of pressure rollers pr1 or pr2 respectively which in turn are actuated by electromagnets m1 or m2 respectively which may be seen by referring to fig2 . one or the other of these pressure rollers maintain a constant pressure against the tape , placing it in contact with its associated driving capstan , which in turn is rotated from below the base by a pulley combination which may be seen by reference to fig2 . a constant pressure is also placed upon the tape tp1 by a guide tag projecting upward from tension arm ta which is located below the base and projects upward through a slot in the base . also included on the base as may be noted in fig1 is a light source mounting ls in which is mounted a light source ls1 . also positioned in such a manner so that a reflective surface on the tape will reflect light from light source ls1 onto its surface , is a photosensitive device lr1 which is mounted in photosensitive device mounting lr . by reference to fig2 it will be noted that motor b1 &# 39 ; s drive shaft has mounted thereon two drive pulleys pu1 and pu2 connected by means of drive belts db1 and db2 to pulleys pu3 and pu4 respectively which are directly connected to capstans c1 and c2 . pulley pu3 is fastened to the lower end of capstan c1 and pulley pu4 to capstan c2 , which project through the base to drive the tape as noted in fig1 . as noted previously , a tension arm guide as seen in fig1 projects through a slot in the base but is connected to the tension arm ta . tension arm ta is pivoted at point pv and maintained under tension by coil spring s . from the above it would be obvious that motor b1 drives capstan c1 and c2 , and that the combination of either pressure roller pr1 and capstan c1 or pressure roller pr2 and capstan c2 may be employed to advance the tape . the tension arm ta is biased by coil spring s to keep the tape at a constant pressure on the tape head . also mounted on the bottom of the base are magnets m1 and m2 which are associated with pressure rollers pr1 and pr2 respectively . it is actuation of these magnets that causes the selected pressure roller to be employed to cause drive at the appropriate speed . pressure roller pr1 actuated by magnet m1 causes the advance of the tape at normal speed while operation of magnet m2 operates pressure roller pr2 to drive the tape at the fast forward speed . as may be noted by referring to the schematic diagram of fig4 light sensitive device lr1 has been shown as a photosensitive diode while the associated light source ls1 has been shown as an incadescent lamp . it would be obvious to those skilled in the art that other forms of light source may be employed as well as other types of photosensitive devices . referring now to the partial schematic circuit diagram of the present invention shown in fig4 light source ls1 , as will be noted , provides light when a reflective surface on the tape is properly located to cause operation of light sensitive diode lr1 whose output will be amplified to provide an operating signal to relay k1 . also shown is relay k2 which operates to break the operating path from magnet m1 and actuates magnet m2 in response to an amplified signal from magnetic pickup pu1 . referring to the above drawings now in combination , a description of the operation of the present invention is as follows : assume that tape tp1 is positioned on the device and that its reflective surface located on the tape ( as may be seen in reference to fig3 ), will cause an output at light sensitive device lr1 which will cause operation of relay k1 . since relay k1 is operated at its contacts k1a , the normal operating path from motor b1 is open and the device is at rest . assume now that switch s1 ( which may be operated in any conventional manner ) is operated , power will be supplied from a dc power source to motor b1 causing it to operate and advance the tape tp1 . as the reflective segment of the tape advances so that light is no longer reflected on light sensitive diode lr1 , relay k1 will restore and at contacts k1a an operating path will be maintained for motor b1 even though switch s1 may have been restored . as it will be observed , magnet m1 is also actuated and will cause pressure roller pr1 to engage the tape and force it against capstan c1 . the tape now in response to drive from capstan c1 will make one complete revolution but becuase of the 180 ° twist occurring in the tape the light reflective surface will now be positioned on the opposite side of the tape and unless other means are provided will continue on to make a second complete revolution returning the reflective segment on the tape again to its homing position wherein light would be reflected from light source ls1 onto light sensitive diode lr1 to cause the reoperation of relay k1 which at its contacts k1a will break the operating power for motor b1 . assuming however that the entire tape length has not been utilized for recording information , it is desirable to rapidly return the tape to its homing position after completion of the message . to accomplish this a tone signal is prerecorded on the tape at the completion of the information . this tone signal is picked up by magnetic pickup pu1 , amplified and utilized to drive tone sensitive relay k2 . on operation relay k2 transfers operating potential from magnet m1 to magnet m2 . in this manner in a response to the release of the magnet m1 , pressure roller pr1 is withdrawn from contact with the tape and pressure roller pr2 is placed in contact with the tape , causing the tape to be advanced by capstan c2 instead of capstan c1 . because of the different pulley and capstan diameters employed , pressure roller pr2 will advance the tape at a much higher speed than that caused by capstan c1 . in one practical embodiment of the present invention the reduction provided in the slow speed ratio by the combination of pulley pu1 the flywheel diameter of flywheel f1 and the capstan diameter of capstan c1 will provide a tape speed of approximately 0 . 5 inches per second . the speed provided by pulleys pu2 and pu4 and capstan c2 was approximately 30 inches per second . this arrangement gave a ratio of approximately 60 to 1 over the slow speed . in other words a 30 second message after being delivered would take approximately 1 / 2 second to reset by fast forwarding the tape to the homing position . inasmuch as magnets m1 and m2 are both operated from make break contacts k2a of relay k2 , the system is electrically interlocked so that both drives cannot operate simultaneously . when magnet m2 is operated , the tape advances at the fast speed until the reflective surface again appears and the motor b1 is rendered inoperative in the manner previously described , returning the system to rest . in addition to its simplicity the present system has the advantages of long tape life , becuase there is no layer - to - layer friction causing wear of tape such as is present in tape cartridges . the system also incorporates economic advantages since the cost of a simple magnetic tape loop is substantially less than that of cartridges or cassettes . it will be obvious to those skilled in the art that numerous modifications of the present invention may be made without departing from the spirit and scope of the present invention which shall be limited only by the scope of the claims appended hereto . | 6 |
hereinafter , examples of the present invention will be described , and molecular weights , fourier transform infrared ( ft - ir ) spectroscopy results , and x - ray diffraction ( xrd ) results were measured by the following methods . number - average molecular weight ( mn ), weight - average molecular weight ( mw ) and molecular weight distribution ( mw / mn ) when converted into polystyrene were measured by gel permeation chromatography ( gpc ). sample preparation method : 1 mg of a polymer obtained from the final polymerization reaction was dissolved in 1 ml of tetrahydrofuran ( thf ), and then 100 μl of the resulting solution was injected . solvent : the molecular weights were measured by injecting thf at a rate of 1 ml / min . other environmental conditions : a gpc column was made by connecting two zorbax mixed - b columns , and then used at 40 ° c . detection method : a refraction index ( ri ) was detected by a refractometer . sample preparation method : 3 mg of a sample was well mixed with 1 g of completely - dried kbr in a mortar , and then a pellet was made for use in a diameter of 10 mm by applying a pressure of 10 gpa . sample preparation method : a sample was sintered at 1200 ° c . for 4 hours , and then scanned at a rate of 0 . 500 °/ min to obtain xrd data . 2 l of a toluene solvent was first placed in a 4 - neck round flask , and 320 g of metal sodium cut into a size of 8 cm 3 was then mixed with the solvent and stirred in a nitrogen atmosphere . the mixture was heated to 110 ° c . to disperse the metal sodium in the toluene organic solvent . an allylmethyldichlorosilane monomer was mixed with a phenylmethyldichlorosilane monomer in a molar ratio of 9 : 1 , and 800 ml of the mixed monomer solution was injected into the solution in which the metal sodium was dispersed at a rate of 100 ml / hr using a funnel for 12 - hour reaction at 110 ° c . when a purple precipitate formed after the reaction , the resulting product was cooled to room temperature , treated with methanol to remove remaining sodium , and washed with distilled water and alcohol after filtering , thereby obtaining white polyallylphenylsilane powder . the white polyallylphenylsilane powder was dried in vacuum , and transferred to an autoclave , in which a first conversion reaction was performed under 10 atm at 350 ° c . for 6 hours , and then a second conversion reaction was performed at 450 ° c . for 6 hours , resulting in the synthesis of polyallylphenylcarbosilanes having various molecular weights . the entire experiment was performed in a nitrogen atmosphere , and during the reaction , the reactants were stirred by a stirrer . after the final reaction , the reactant was dissolved in hexane and filtered to remove polyallylphenylcarbosilane that was not dissolved in hexane . after distilling hexane , polyallylphenylcarbosilane was obtained . a yield of the polyallylphenylcarbosilane was about 65 %, the weight - average molecular weight ( mw ) when converted into polystyrene measured by gpc was 2180 . according to the ft - ir measurement results shown in fig1 , a strong peak of — si — ch 2 — si was shown at 1035 cm − 1 . from these data , it can be confirmed that polyallylphenylcarbosilane includes a structural unit of formula 3 containing allyl and phenyl groups . in addition , the polyallylphenylcarbosilane was treated with heat at 1200 ° c . in an argon atmosphere , and analyzed by xrd . the result , as shown in fig2 , was matched with that of β - sic , and thus it can be confirmed that the polyllaylphenylcarbosilane is a suitable material for a sic precursor . the polyallylphenylcarbosilane yielded in example 1 of the present invention was dissolved in hexane to a concentration of 30 wt % and thus could be used as a precursor for sic coating . 2 l of toluene solvent was first placed in a 4 - neck round flask , and 320 g of metal sodium cut into a size of 8 cm 3 was then mixed with the solvent in a nitrogen atmosphere . the mixture was heated to 110 ° c . and stirred to disperse the metal sodium in the toluene organic solvent . an allylmethyldichlorosilane was mixed with a phenylmethyldichlorosilane monomer in a molar ratio of 5 : 5 , and 800 ml of the mixed monomer solution was injected into the solution in which the metal sodium was dispersed at a rate of 100 ml / hr using a funnel for 12 - hour reaction at 110 ° c . when a purple precipitate formed after the reaction , the resulting product was cooled to room temperature , treated with methanol to remove remaining sodium , and washed with distilled water and alcohol after filtering , thereby obtaining white polyallylphenylsilane powder . the white polyallylphenylsilane powder was dried in vacuum , and transferred to an autoclave , in which a first conversion reaction was performed under 10 atm at 350 ° c . for 6 hours , and a second conversion reaction was then performed at 450 ° c . for 6 hours , resulting in the synthesis of polyallylphenylcarbosilane . the entire experiment was performed in a nitrogen atmosphere , and during the reaction , the reactants were stirred by a stirrer . after the final reaction , the reaction product was dissolved in hexane and filtered to remove polyallylphenylsilane that was not dissolved in hexane . in the case of mixing the allylmethyldichlorosilane monomer with the phenylmethyldichlorosilane monomer in the molar ratio of 5 : 5 , a large quantity of high molecular - weight polyallylphenylcarbosilane ( mw = 6000 or more ) that was not dissolved in hexane was produced . after distilling hexane , polyallylphenylcarbosilane having a low molecular weight that was dissolved in hexane was recovered . a yield of the polyallylphenylcarbosilane was about 40 %, and a weight - average molecular weight ( mw ) when converted into polystyrene measured by gpc was 3140 . according to the ft - ir measurement results shown in fig3 , a strong peak of — si — ch 2 — si was shown at 1035 cm − 1 , and thus it can be confirmed that polyallylphenylcarbosilane has a structural unit of formula 4 including allyl and phenyl groups . the polyallylphenylcarbosilane yielded in example 2 of the present invention was dissolved in hexane to a concentration of 30 wt %, and thus could be used as a precursor for sic coating . 2 l of toluene solvent was first placed in a 4 - neck round flask , and 320 g of metal sodium cut into a size of 5 cm 3 was then mixed with the solvent in a nitrogen atmosphere . the mixture was heated to 110 ° c . and stirred to disperse the metal sodium in the toluene organic solvent . 340 ml of allylmethyldichlorosilane and 460 ml of phenylmethyldichlorosilane were individually prepared in a molar ratio of 5 : 5 , and then both monomers were simultaneously injected into both sides of the round flask at a rate of 100 ml / hr for 12 - hour reaction at 110 ° c . while a purple precipitate formed after the reaction , the resulting product was separated into two layers , in which one layer floated over the toluene solvent and the other layer was precipitated to the bottom . that is , the allylmethyldichlorosilane monomer was separated from the phenylmethyldichlorosilane monomer , and thus polyallylphenylcarbosilane was not synthesized . after that , the resulting product was cooled to room temperature , treated with methanol to remove remaining sodium , and washed with distilled water and alcohol after filtering , thereby obtaining white powder . the powder was dried in vacuum , and transferred to an autoclave , in which a first conversion reaction was performed under 10 atm at 350 ° c . for 6 hours , and a second conversion reaction was performed at 450 ° c . for 6 hours . however , no change occurred , that is , no polyallylphenylcarbosilane was produced . although a few embodiments of the present invention have been shown and described , it will be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention , the scope of which is defined in the claims and their equivalents . | 2 |
the invention relates to multipulse converter arrangements of the 12 - pulse and 18 - pulse types using a special fork connected auto transformer with appropriate phase shift and conduction angle which eliminates the need for interphase transformers and provides a symmetry such that step up or step down voltages can be obtained without causing unbalance effects . this arrangement when combined with appropriate ac line reactances , or with appropriately designed transformer leakage reactance , leads to reduction of harmonic currents such that equipments can easily meet prevailing harmonic distortion specifications . the decision to use 12 - pulse or 18 - pulse is a matter of system and equipment design trade - offs . the final approach rests upon the observation that higher order harmonic frequencies have frequency of ( kq ± 1 ) with amplitudes of 1 /( kq ± 1 ) where q is the pulse number , and k is any integer . a similar transformer with fork winding construction is used for 12 - pulse and 18 - pulse cases , but with different turns ratios and winding sections . u . s . pat . no . 5 , 124 , 904 achieves similar excellent harmonic reduction results , but due to an inherent increase of about 10 . 3 % in the dc output voltage it has the disadvantage in most cases of requiring an additional winding rated at full current to step down the voltage to be within 5 % of the dc voltage corresponding to a three - phase bridge converter . the new fork transformer overcomes this disadvantage and inherently provides a converter dc output within 4 . 2 % of a three - phase bridge converter . in common with u . s . pat . no . 5 , 124 , 904 there is no need for an interphase transformer and for providing a neutral reference point between the converter bridges , also the transformer rating is less than that of the load . referring to fig2 a basic three - phase rectifier bridge is shown in which 6 diodes are connected to a three - phase supply and a dc circuit incorporating a load and dc filter components . the open circuit dc output voltage from this circuit is given by : the line current harmonics of this circuit under load are at harmonic frequencies of the form ( 6k ± 1 ) and with amplitude 1 /( 6k ± 1 ), where k is any integer . fig3 a and 3b show a basic arrangement of a 12 - pulse symmetrical fork transformer arrangement and computer calculated results for the ac line currents of the form i h where h is the harmonic number . referring to fig3 a and 3b , a three - phase power source is applied to terminals a , b , and c . this generates 12 ac outputs , numbered 1 through 12 , suitable for powering a 12 - pulse converter . the transformer windings are shown as blocks . each phase of the transformer comprises a main winding n m , two auxiliary windings n x , two extender windings n y , and one delta winding n d . the delta winding can have any convenient number of turns . the object of the invention is to establish unique ratios between n m , n s , and n y to give the desired characteristics . outputs such as v 1 - n , v 2 - n , etc . are all equal in amplitude . ( n . sub . x + n . sub . y )/ sin 45 °= n . sub . m / sin 75 ° thus n . sub . y = 0 . 464 n . sub . m ( 2 ) using the desirable ratios , given in equations ( 1 ) and ( 2 ) the output voltages such as v 1 are given by : the converter open circuit dc output voltage , v do , is given by : v . sub . do = 2 √ 2 v . sub . o ( 3 / π ) ∫ cos wt dwt over the range (- π / 6 ) to ( π / 6 ) in a straight - through three - phase bridge converter connection without transformer , such as used in the ubiquitous variable frequency drive , and shown in fig2 the open circuit dc output voltage is given by : thus the proposed 12 - pulse arrangement has a dc voltage which is only 3 . 4 % greater than a straight through connection . this is easily tolerated in most practical designs . further , it allows for the inclusion of additional ac line reactance to filter and reduce the residual harmonic currents . typical ac line current waveforms are shown in fig3 a and 3b . fig4 shows idealized theoretical waveshapes of current in the 12 - pulse version of the new fork transformer . fig5 shows application of the new 12 - pulse transformer with a symmetrical overwind coil n r to supply power for a regeneration converter . for reliable regeneration performance , i . e ., dc to ac power flow , it is essential to ensure satisfactory commutation of the thyristors under inverting conditions . to achieve this it is known to use a step - up transformer to raise the voltage applied to by appropriately sizing the extra winding n r on the fork the inverting bridge by about 15 %. this is very readily achieved transformer . a complete scheme for regeneration is shown in fig5 . in this figure the inverting bridge is shown in a 6 - pulse arrangement . the extra harmonic currents associated with 6 - pulse conversion should not be a concern for loads with intermittent regeneration requirements , however , where the regeneration feature is a large part of the duty cycle an option is known to obtain 12 - pulse regeneration by using a method which reverses the dc link voltage . in this case the extra coil n r is not required . fig6 shows the symmetrical fork transformer connected to produce a nine phase supply suitable for powering an 18 - pulse converter . the three - phase input is connected to terminals a , b , and c , and the nine outputs which are at a slightly lower voltage are numbered 1 through 9 . in this figure the windings on the symmetrical fork transformer are given a different terminology to those on the 12 - pulse arrangement for the purposes of discussion . solving for the geometry of the voltage vectors in fig6 it is determined that for an 18 - pulse converter the open circuit dc output voltage is given by : where v l - n is the line to neutral voltage of the three - phase power source applied to terminals a , b , and c . thus the dc output is only 4 . 2 % greater than that provided by a straight - through three - phase bridge connection . fig7 a and 7b show complete idealized waveforms of current in the 18 - pulse connection . practical transformer turns must be integer values . some practical turns for equipments up to 480 - v , 500 - kw rating are shown in table 1 for 12 - pulse converters and table 2 for 18 - pulse converters . table 1______________________________________practical examples of turns for the 12 - pulseauto fork transformer . n . sub . m n . sub . y n . sub . xmain extender auxiliary______________________________________26 12 741 19 1156 26 15______________________________________ table 2______________________________________practical examples of turns for 18 - pulse fork transformer . ______________________________________zig winding 16 22 60 97teaser winding 3 4 11 18long winding 22 29 80 131amplitude error - 0 . 3 % - 0 . 35 % + 0 . 16 % -. 012 % phase error - 0 . 8 ° + 0 . 893 ° + 0 . 425 ° - 0 . 11 ° ______________________________________ it will be apparent to those skilled in the art that the same winding topology shown in fig1 and 2 can be used if the power source is applied to the delta windings . by these means the same optimum features are retained but the dc isolation associated with double - wound transformers is provided . in this case there is no inherent restriction on the range of output voltage available . | 7 |
according to the present invention , a bag is provided for encasing an item , such as a corsage . broadly , the bag is constructed from a sheet of material having a bonding material disposed on isolated and individualized sections of the sheet of material . once the bonding material is on the sheet of material , it is articulated into a bag having fin and / or lap seams at the point of sealing . in one embodiment , the bonding material may be a heat sealable lacquer which is applied to isolated and individualized sections of the sheet of material . referring now to the drawings , and more particularly to fig1 shown therein and designated by reference numeral 5 is a sheet of material . the sheet of material 5 is articulated into a bag 10 as shown in fig2 . the term “ sheet of material ” when used herein means at least one flexible sheet of material . the thickness of the sheet of material may vary , but generally the sheet of material will have a thickness in a range from about 0 . 0002 mil to about 30 mil , and more desirably from about 0 . 01 mil to about 20 mil . the sheet of material may be any material capable of being articulated into a bag configuration , such as polymeric film , foil , paper , tissue , laminations and combinations thereof . the sheet of material may have a substantially textured surface . the term “ paper ” as used herein , means treated or untreated paper , corrugated paper or cardboard or any other form of paper material . the term “ polymeric film ” means a synthetic polymer such as polypropylene or a naturally occurring polymer such as cellophane . a polymeric film is relatively strong and not as subject to tearing as might be the case with paper or foil . when the sheet of material is a polymeric film , a flexible sheet of liquified thermoplastic film can be extruded from an extruder in a conventional and well known manner . the flexible sheet of liquified thermoplastic film can be passed through a cooler which cools the liquified thermoplastic film into a sheet of solidified thermoplastic film , i . e . the sheet of material . the sheet of material may also be formed of two or more sheets of material which have been laminated or adhesively connected to one another . the sheet of material may also vary in color . further , the sheet of material may be provided with designs or decorative patterns which are printed , etched , and / or embossed therein using inks or other printing materials . when printed and embossed , the design or decorative patterns may be in register , may be out of register , or may be partially in register and partially out of register . an example of an ink which may be applied to the surface of the sheet of material is described in u . s . pat . no . 5 , 147 , 706 entitled “ water based ink on foil and / or synthetic organic polymer ” issued to kingman on sep . 15 , 1992 and which is hereby incorporated herein by reference . additionally , the sheet of material may have various colorings , flocking and / or metallic finishes , or other decorative surface ornamentation applied separately or simultaneously or may be characterized totally or partially by pearlescent , translucent , transparent , iridescent or the like qualities . each of the above named characteristics may occur alone or in combination . the sheet of material may also be opaque , translucent , partially clear , and / or tinted yet having some transparency . as shown in fig1 the sheet of material 5 has a first surface 30 , the first surface 30 having a first edge portion 40 , a second edge portion 50 , and a third edge portion 55 . a bonding material 58 is disposed on a portion of the first surface 30 such that the bonding material 58 extends along the first edge portion 40 , the second edge portion 50 , and the third edge portion 55 substantially as shown in fig1 . thus , the first , second , and third edge portions 40 , 50 , and 55 of the first surface 30 define areas of adhesion 57 . the remaining portion of the sheet of material 5 , which is free of adhesive , defines a substantially open area 59 which does not have the bonding material 58 thereon . the bonding material 58 may be disposed in a continuous manner across the entirety of the first edge portion 40 , the second edge portion 50 , and the third edge portion 55 of the first surface 30 . in an alternative embodiment , the bonding material 58 may be selectively applied in such a manner as to not completely cover the first edge portion 40 , the second edge portion 50 , and the third edge portion 55 . in this embodiment , the bonding material 58 may be applied as a plurality of dots , strips , or dabs of the bonding material 58 which are applied to alternating areas of the first edge portion 40 , the second edge portion 50 , and the third edge portion 55 . furthermore , the bonding material 58 can be applied in any geometric form and in any pattern . in any event , it is to be appreciated that the bonding material 58 is not applied to the entirety of the sheet of material 5 , but rather to selective parts of the sheet of material 5 to leave the open area 59 on the first surface 30 of the sheet of material 5 . the bonding material 58 may be applied to the sheet of material 5 in any manner which allows for the timely and economical placement of the bonding material 58 onto the sheet of material 5 . for example , the bonding material 58 may be printed onto the sheet of material 5 by brushes , rollers , wires , sponges , and / or other mechanical and / or automated processes . furthermore , the bonding material 58 may be printed onto the sheet of material with a jet printer , such as an ink jet printing apparatus . in any event , any mechanical or automated process which allows for the correct placement of the bonding material 58 onto the sheet of material 5 is contemplated for use . the term “ bonding material ” may be any material capable of bondingly holding at least two surfaces in a substantially adjacent position . the bonding material may be a hot stamped adhesive , a pressure adhesive , a hot melt adhesive , a water - proof adhesive , a cohesive , a heat sealable lacquer and combinations thereof . the term “ heat sealable lacquer ” as used herein means a coating substance consisting of resinous materials , such as cellulose esters , cellulose ethers , shellac , gum , alkyd resins and the like , which are dissolved in a solvent that evaporates rapidly on application such as ethyl alcohol , thereby leaving a tough , adherent film . lacquers which are useful in the present invention maybe mixtures , such as lacquers produced by mixing styrene - acrylic emulsions , such as lucidene 603 and lucidene 395 ( morton international , inc ., 100 north riverside plaza , chicago , ill . 60606 ) with a non - ionic surfactant , such as sufynol 465 ( air products and chemicals , inc ., 751 hamilton boulevard , allentown , pa . 18195 - 1501 ) and ammonia ( g . s . robbins and company , 126 chateau avenue , st . louis , mo . 63102 ). the lacquer produced as described above may also contain a wax emulsion in water , such as liquitron 440 ( carrol scientific , inc ., 5401 s . dansher road , countryside , ill . 60525 ). as stated above , the bonding material 58 may be an adhesive , such as a pressure sensitive adhesive , or a cohesive . where the bonding material 58 is a cohesive , a similar cohesive material must be placed on both surfaces which are to be bonded together . as stated above , the bonding material 58 may be heat sealable and in this instance , the adjacent portions of the materials must be brought into contact and then heat must be applied to affect the seal . the lacquers described above are but one type of the bonding material 58 which is heat sealable . the bonding material 58 may also be a material which is sonic sealable and vibratory sealable . in the case of one type of heat sealable lacquer , the heat sealable lacquer may be applied to a sheet of material 5 and then heat , sound waves , or vibrations are then applied to effect the sealing . the term “ bonding material ” also includes any heat or chemically shrinkable material , static , electrical or other electrical , magnetic , mechanical or barb - type fastening or clamps , curl - type characteristics of the film and the materials in a sheet of material which cause the sheet of material to take on certain shapes , and any type of welding method which may weld the sheet of material into an articulated bag . the sheet of material 5 may further include at least one scent , the bonding material 58 may also include a scent , or both the sheet of material 5 and the bonding material 58 may include a scent . the scent may be incorporated into the structure of the sheet of material 5 during the fabrication of the sheet of material 5 or may be applied to the sheet of material 5 after it has been manufactured and before the sheet of material 5 is articulated into the bag of the present invention , such as bag 10 ( fig2 ). the scent may also be applied to the bag 10 of the present invention after it has been articulated from the sheet of material 5 . examples of scents utilized herein include floral scents ( flower blossoms or other portions of plants ), food scents ( chocolate , sugar , fruits ), herb or spice scents ( cinnamon ), and the like . additional examples of scents include flowers ( i . e . roses , daisies , lilacs ), plants ( i . e . fruits , vegetables , grasses , and trees ), foods ( i . e . candies , cookies , cake ), food condiments ( i . e . honey , sugar , salt ), herbs , spices , woods , roots , and the like , or any combinations of the foregoing . such scents are known in the art and commercially available . the scent may be applied to the sheet of material 5 by spraying the scent thereon , painting the scent thereon , brushing the scent thereon , lacquering the scent thereon , immersing sheet of material the 5 in a scent - containing liquid , exposing the sheet of material 5 to the scent containing gas or any combination thereof . the scent may also be incorporated onto the sheet of material 5 during the manufacture , extrusion , and / or lamination of the sheet of material 5 . when articulated , the sheet of material 5 forms a generally tubular sheath , indicated by reference numeral 60 shown in fig2 . the tubular sheath 60 is provided with an interior surface 70 , an exterior surface 80 , a end top 90 , and a bottom end 100 . the tubular sheath 60 is articulated from the sheet of material 5 by folding the sheet of material 5 over and onto itself such that the first edge portion 40 of the sheet of material 5 is substantially adjacent the second edge portion 50 thereof . as shown in fig2 where the first edge portion 40 is adjacent the second edge portion 50 , a first area of engagement 120 is defined . when the sheet of material 5 is folded over and onto itself , the third edge portion 55 folds over and onto itself as well , thereby defining a second area of engagement 130 . the first area of engagement 120 is exaggerated in size in fig2 for purpose of description and it should be appreciated that the first area of engagement 120 , in practice , may be substantially smaller and less noticeable . the first area of engagement 120 is generally shaped and sized as a fin seal — i . e ., the first edge portion 40 is directly adjacent and in alignment with the second edge portion 50 . the first area of engagement 120 also has an amount of the bonding material 58 disposed between the first edge portion 40 and the second edge portion 50 of the sheet of material 5 for affecting a seal therebetween . when sealed in this manner , the sheet of material 5 is articulated into the tubular sheath 60 having a fin seal seam , defined generally by the first area of engagement 120 . as stated above , the second area of engagement 130 is created by the third edge portion 55 being folded over onto itself . through the creation of the second area of engagement 130 , the bottom end 100 of the tubular sheath 60 is generally flattened . an amount of the bonding material 58 , which is disposed on the third edge portion 55 , is thus operably interspersed in the second area of engagement 130 such that the bottom end 100 is substantially closed . in the embodiment shown in fig2 the bottom end 100 is sealed in a fin seal manner generally along the second area of engagement 130 . thus , as shown in fig2 when the first and second areas of engagement 120 , 130 have been articulated and bondingly sealed , the bag 10 is formed . the bag 10 defines an interior retaining space 140 which is suitable for holding and retaining an item , such as a floral grouping or a corsage . thus , the top end 90 of the bag 10 is in a substantially open and unobstructed configuration prior to an item being placed in the interior retaining space 140 of the bag 10 and the top end 90 coordinates with the interior retaining space 140 to provide egress to the interior retaining space 140 . after an item is placed in the interior retaining space 140 , the top end 90 may be crimped , folded , stapled , glued and / or mechanically closed in any manner whatsoever which allows for the retention of the item within the interior retaining space 140 of the bag 10 . in an alternative embodiment of the invention , shown in fig3 and 4 , a bag 10 a ( fig4 ) is formed from a sheet of material 5 a ( fig3 ) having a first surface 30 a and a second surface 150 . the first surface 30 a includes a first edge portion 40 a and a second edge portion 50 a . the second surface 150 includes a third edge portion 55 a . the third edge portion 55 a does not extend the entire length of an outside edge 160 located on the second surface 150 of the sheet of material 5 a : rather , the third edge portion 55 a extends generally to a midpoint 165 of the sheet of material 5 a , with the midpoint 165 being indicated generally by a dashed line shown in fig3 . a bonding material 58 a is disposed on at least a portion of the first , second , and third edge portions 40 a , 50 a , and 55 a , respectively . thus , the first , second , and third edge portions 40 a , 50 a , and 55 a , respectively , define areas of adhesion 57 a . the remaining portion of the sheet of material 5 a which is free of adhesive defines a substantially open area 59 a which does not have the bonding material 58 a thereon . still referring to fig4 when articulated , the sheet of material 5 a forms a generally tubular sheath 60 a , having an interior surface 70 a , an exterior surface 80 a , a top end 90 a , and a bottom end 100 a . the tubular sheath 60 a is articulated from the sheet of material 5 a by folding the sheet of material 5 a over and onto itself such that the first edge portion 40 a is substantially adjacent the second edge portion 50 a . the sheet of material 5 a is folded generally along the midpoint 165 when forming the tubular sheath 60 a . as shown in fig4 when the bag 10 a is articulated , i . e . where the first edge portion 40 a is adjacent the second edge portion 50 a , a first area of engagement 120 a is generally defined . also , when the bag 10 a is articulated , the third edge portion 55 a is folded up toward the top end 90 a such that the third edge portion 55 a bondingly engages the exterior surface 80 a of the tubular sheath 60 a , and thereby defines a second area of engagement 130 a . in the embodiment shown in fig3 and 4 , the first area of engagement 120 a is generally sized and shaped as a fin seal — i . e . the first edge portion 40 a is adjacent the second edge portion 50 a . the bonding material 58 a is located between the first edge portion 40 a and the second edge portion 50 a of the sheet of material 5 a such that first and second edge portions 40 a and 50 a are bondingly connected to one another so as to form the fin seal where the fin seal is generally defined by the first area of engagement 120 a . the second area of engagement 130 a is generally characterized as being defined by a lap seal , i . e ., the third edge portion 55 a is folded up toward the top end 90 a such that the third edge portion 55 a bondingly engages the exterior surface 80 a of the tubular sheath 60 a . by creating this lap seal at the second area of engagement 130 a , the bottom end 100 a is substantially flattened and closed , thereby providing the tubular sheath 60 a having two sealed areas of engagement 120 a , 130 a , respectively , and the substantially open top end 90 a . thus , as shown in fig4 when the first and second areas of engagement 120 a , 130 a have been articulated and bondingly sealed the bag 10 a is formed . the bag 10 a has an interior retaining space 140 a which is suitable for holding and retaining an item , such as a floral grouping or a corsage . the top end 90 a is in a substantially open and unobstructed configuration prior to an item being placed within the interior retaining space 140 a . after an item is placed in the interior retaining space 140 a , the top end 90 a may be crimped , folded , stapled , and / or mechanically closed in any manner whatsoever which allows for the retention of the item in the interior retaining space 140 a . in another embodiment of the present invention , shown in fig5 and 6 , a bag 10 b ( fig6 ) is formed from a sheet of material 5 b . the sheet of material 5 b has a first surface 30 b and a second surface 150 b . the first surface 30 b includes a first edge portion 40 b and a second edge portion 50 b . the second surface 150 b includes a third edge portion 55 b . a bonding material 58 b is disposed on at least a portion of the first edge portion 40 b , the second edge portion 50 b , as well as on the third edge portion 55 b . thus , the first , second and third edge portions 40 b , 50 b , 55 b , respectively , define areas of adhesion 57 b . the remaining portion of the sheet of material 5 b which is free of adhesive defines a substantially open area 59 b which does not have the bonding material 58 b thereon . when articulated , the sheet of material 5 b forms a generally tubular sheath 60 b . the tubular sheath 60 b further includes an interior surface 70 b , an exterior surface 80 b , a top end 90 b , and a bottom end 100 b . the tubular sheath 60 b is articulated from the sheet of material 5 b by folding the sheet of material 5 b over and onto itself such that the second edge portion 50 b overlaps and is substantially adjacent the third edge portion 55 b . as shown in fig6 where the second edge portion 50 b overlaps the third edge portion 55 b , a first area of engagement 120 b is defined . when the sheet of material 5 b is folded , the first edge portion 40 b is folded onto itself and defines a second area of engagement 130 b . the first area of engagement 120 b is generally sized and shaped as a lap seal , i . e ., the third edge portion 55 b is adjacent the second edge portion 50 b . the first area of engagement 120 b also has an amount of the bonding material 58 b disposed between the third edge portion 55 b and the second edge portion 50 b . the bonding material 58 b holds and seals the second edge portion 50 b adjacent the third edge portion 55 b . when folded and sealed in this manner , the sheet of material 5 b is articulated into the tubular sheath 60 b having a lap - seal seam . this lap seal is defined generally by the first area of engagement 120 b . as stated above , the second area of engagement 130 b is created by the first edge portion 40 b being folded over and onto itself . through the articulation of the second area of engagement 130 b , the bottom end 100 b of the tubular sheath 60 b is generally flattened . the bonding material 58 b , which is disposed on the first edge portion 40 b , is thus operably interspersed within the second area of engagement 130 b such that the flattened bottom end 100 b of the tubular sheath 60 b is held and sealed by the bonding material 58 b . in the embodiment shown in fig6 the bottom end 100 b of the tubular sheath 60 b is sealed in a fin seal manner generally along the second area of engagement 130 b . thus , as shown in fig6 when the first and second areas of engagement 120 b and 130 b have been articulated and bondingly sealed , the bag 10 b is formed . the bag 100 b has an interior retaining space 140 b which is suitable for holding and retaining an item , such as a floral grouping or a corsage . the top end 90 b is in a substantially open and unobstructed configuration prior to an item being placed in the interior retaining space 140 b . after an item is placed in the interior retaining space 140 b , the top end 90 b may be crimped , folded , stapled , curved , and / or mechanically closed in any manner whatsoever which allows for the retention of the item within the interior retaining space 140 b . in an additional embodiment of the present invention , shown in fig7 and 8 , a bag 10 c is formed from a sheet of material 5 c . the sheet of material 5 c has a first surface 30 c and a second surface 150 c . the first surface 30 c includes a first edge portion 40 c . the second surface 150 c includes a second edge portion 50 c and a third edge portion 55 c . the third edge portion 55 c does not extend along the entire length of an outside edge 160 c of the second surface 150 c ; rather , the third edge portion 55 c extends generally to a midpoint 165 c of the sheet of material 5 c , with the midpoint 165 c being indicated generally by a dashed line in fig7 . a bonding material 58 c is applied to at least a portion of the first , second , and third edge portions 40 c , 50 c , and 55 c , respectively . thus , the first , second and third edge portions 40 c , 50 c , and 55 c , respectively , define areas of adhesion 57 c . the remaining portion of the sheet of material 5 c which is free of adhesive defines a substantially open area 59 c which does not have the bonding material 58 c thereon . when articulated , the sheet of material 5 c forms a generally tubular sheath 60 c , having an interior surface 70 c , an exterior surface 80 c , a top end 90 c , and a bottom end 100 c . the tubular sheath 60 c is articulated from the sheet of material 5 c by folding the sheet of material 5 c over and onto itself such that the first edge portion 40 c overlaps and is substantially adjacent to the second edge portion 50 c . as shown in fig8 where the first edge portion 40 c overlaps the second edge portion 50 c , a first area of engagement 120 c is defined . during folding , the third edge portion 55 c is folded over and onto itself defining a second area of engagement 130 c . the first area of engagement 120 c is generally sized and shaped as a lap seal , i . e ., the first edge portion 40 c is adjacent the second edge portion 50 c . the first area of engagement 120 c also has an amount of the bonding material 58 c disposed between the first edge portion 40 c and the second edge portion 50 c . the bonding material 58 c holds and seals the first edge portion 40 c adjacent the second edge portion 50 c . when folded and sealed in this manner , the sheet of material 5 c is articulated into the tubular sheath 60 c having a lap seal seam . this lap seal seam is defined generally by the first area of engagement 120 c . the second area of engagement 130 c is generally formed into a lap seal , i . e ., the third edge portion 55 c is folded up and bonded to the top end 90 c of the tubular sheath 60 c such that the third edge portion 55 c bondingly engages the exterior surface 80 c of the tubular sheath 60 c . by creating this lap seal at the second area of engagement 130 c , the bottom end 100 c of the tubular sheath 60 c is substantially flattened , closed , and sealed by the bonding material 58 c disposed on the third edge portion 55 c . the tubular sheath 60 c is thereby provided having the two sealed first and second areas of engagement 120 c , 130 c and the substantially open top end 90 c . thus , as shown in fig8 when the first and second areas of engagement 120 c , 130 c have been articulated and bonded , the bag 10 c is formed . the bag 10 c has an interior retaining space 140 c which is suitable for holding and retaining an item , such as a floral grouping or a corsage . the top end 90 c is in a substantially open and unobstructed configuration prior to an item being placed in the interior retaining space 140 c . after an item is placed in the interior retaining space 140 c , the top end 90 c may be crimped , folded , stapled , and / or mechanically closed in any manner whatsoever which allows for the retention of the item in the interior retaining space 140 c . thus it should be apparent that there has been provided in accordance with the present invention a bag that fully satisfies the objectives and advantages set forth above . although the invention has been described in conjunction with specific embodiments thereof , it is evident that many alternatives , modifications , and variations will be apparent to those skilled in the art . accordingly , it is intended to embrace all such alternatives , modifications and variations that fall within the spirit and broad scope of the appended claims . | 1 |
the paper punching mechanism of the invention may desirably take the form illustrated in prior u . s . pat . no . 3 , 227 , 023 . as there shown , an oscillating punch drive shaft successively and sequentially operates a plurality of punch pins by a pair of spaced radially extending actuator elements that are angularly offset with respect to each other to effect operation of the punched pin pressure bar from one end toward the other . in the schematic illustration of fig1 the punch comprises a pierced die member 10 having a plurality of apertures 11 through which punch pins 12 are driven by a pressure bar 13 which is driven downwardly , and then upwardly , by actuating elements 14 and 15 carried by the punch drive shaft 16 . the punch drive shaft 16 is driven by a reduction gear transmission 17 driven by a motor 20 which is of a conventional split phase capacitor run type such as , for example , marketed by von weise . the output shaft 21 of the motor 20 carries a brake 22 which will , as described below , be engaged prior to reverse actuation of the motor in either normal or jam type operation . functionally , the system can be understood from a consideration of fig2 . as there shown , both normal and jam cycles are shown for comparison . in the normal cycle the motor 20 operates in the clockwise ( cw ) mode in the direction for driving the punches downwardly to punch the paper . counterclockwise rotation operates , conversely , to positively withdraw the punches from the paper . accordingly , upon the application of a trigger pulse , which occurs upon a manual switch application , the motor is , in a normal cycle , driven clockwise during a time time period t1 to t2 through a distance sufficient to drive the pins completely through the lift of paper , which distance is shown as x in fig2 . upon passage of the pins through the lift , the motor is deenergized and a brake momentarily applied during the period t2 through t3 . at this time the motor is reversed and driven counterclockwise during the period from t3 through t6 to the at - rest condition , at which it remains until again supplied with a manual trigger pulse . as shown in the lower portion of fig2 a jam cycle provides a somewhat different sequence of operation . as there shown , upon the application of the trigger pulse , the motor rotates in the clockwise direction , but achieves only a distance y , insufficient to penetrate the complete lift of paper , even though the time extends beyond t2 . in the jam situation , after completion of t4 , even without completion of the punching of the lift , the motor is deenergized and the brake actuated during the time period t4 to t5 . following this point in the operation , the motor is energized in the reverse , or counterclockwise direction at t5 and returns the system to the at - rest condition upon the completion of the time t7 . from the at - rest condition , the punch may be reenergized by a new trigger pulse , in which case , the motor tries to complete the piercing operation in a recycling manner . the manual trigger may be pulsed as many times as desired in an effort to complete the punch . however , in practice , it is preferred that having recognized a jam condition , by virtue of the fact that the lift has not been completely pierced , the operator will divide the lift into two parts which may be recycled separately . upon using the punch for a very short period of time , the usual operator has no difficulty in sensing the proper lift size to allow non - jamming , normal , cycling , even though that lift size is substantially less than the lift opening provided in the punch . control of the motor and the brake is accomplished by way of an electrical controller indicated at 25 in fig1 . the controller 25 , which is shown in schematic detail in fig3 provides , as there shown , a power source , typically 15 volt alternating current at p1 , p2 . photon coupled interrupter mechanisms , such as for example , general electric part no . h2 2 b3 , are provided for detecting the position of the punch drive shaft 16 . as shown in fig1 the shaft 16 drives a flag element 26 between an upper position in which the punch has completed punching of the lift , and the at - home position , in which the punches have moved upwardly to their maximum , at - rest condition in which the lift opening of the punch is open for insertion of a new lift of paper to be punched . in the drawing the photon coupled interrupter mechanisms include a light - emitting diode q2a which energizes the switch q2b to disconnect operation of the motor reversing circuit upon achievement of the at - rest , home , condition . similarly , the photon coupled interrupter combination q3a and q3b operate to terminate operation of the forward motor energization when the flag 26 reaches the punch complete position , as shown in fig1 . in the circuit shown in fig3 q14 comprises a light - emitting diode providing illumination for the switch s1 which may be pulsed by momentary closure to trigger a timer element which may , for example , comprise an r . c . a . part no . ca 555 - ce . the timer q4 starts , with current flowing through q3b energizing the diode actuated triac q8 energizing the forward direction motor windings via triac q11 . the optical coupled triacs q8 , q9 , and q10 may comprise optron part nos . opi 3022 and the triacs q11 and q13 may comprise teccor part nos . q601025 . similarly , the triac q12 may comprise a teccor part no . q600424 . upon the initial operation of the switch s1 , above described , current is supplied via q3b to the optical coupled triac q8 and the optical coupled triac q9 which , when thus energized , energizes a brake release mechanism removing brake force from the shaft 21 to permit rotation of the shaft while the motor is energized in the forward direction . at this time , current flowing through r8 is diverted to a momentary ground at terminal 7 of the second timer q6 , so that the optical coupled triac q10 is not energized . when the photon coupled interrupter q3b is interrupted by movement of the flag 26 , following completion of the punching stroke , the circuit is interrupted and q8 and q9 are deenergized , with the result that the brake 22 is applied . interruption of the circuit initiates timer q6 which then , via terminal 3 energizes the optical coupled triacs q9 and q10 , releasing the brake 22 and energizing the motor in the reverse direction , which reverse action is terminated when the photo coupled interrupter q2b is interrupted . in the event of a jam situation , the photon coupled interrupter q3b is not interrupted , since the flag 26 never completely obscures the light emitting diode q3a , in this event , the timer q4 operates to interrupt the circuit powering q8 and q9 by interrupting current flow at time t4 shown in fig2 . this interruption operates , as in a normal cycle , to provide application of the brake and timed operation of the reverse motor optical coupled triac q10 . the circuit shown in fig3 may , of course , be modified and is shown as a satisfactory embodiment only . circuit values as there shown are as follows : r1 , r2 are 100 , 000 ohms each ; r3 is 470 , 000 ohms ; r4 is 22 , 000 ohms ; r5 is 10 , 000 ohms ; r6 is 22 , 000 ohms ; r7 is 1 , 000 ohms ; r8 is 560 ohms ; r9 , r10 , r11 are 100 ohms each and r12 is 220 ohms . capacitances c1 and c2 are 100 microfarads each ; c3 is 0 . 1 microfarad ; c4 is 0 . 01 microfarad ; c5 is 2 . 2 microfarads ; c6 is 2 . 2 microfarads and c7 is 6 . 8 microfarads . the diodes d2 , d3 , d4 , d5 and d6 may comprise part nos . in914 with d1 being for example , part no . in4002 . the npn transistor q5 may comprise part no . 2n4400 and the pnp transistor q7 may , similarly , comprise part no . 2n3905 . it will , of course , be obvious that different timer and motor controller elements may be used , and that depending upon the inertia characteristics of the motor and the transmission , the brake may be modified or eliminated . accordingly , it is our intention that the scope of the present invention be limited by that of the appended claims only . | 8 |
a preferred embodiment of the proposed system for de - icing is illustrated in fig1 . the nozzle 10 for supplying a de - icing liquid is supported by a first pivot support that is attached to an extendable support arm 15 . the first pivot support 12 provides an adjustable orientation of the nozzle 10 by a horizontal pivot axis allowing a pivotal motion in a vertical plane embedding the adjustable support arm 15 , and a normal pivot axis allowing sideways motions with respect to the extendable support arm 15 . the first pivot support 12 is also provided with actuation mechanisms enabling an automated pivotal motion of the nozzle 10 . the nozzle is supplied with de - icing liquid via conduits 14 . the support arm is provided with conduit supports 16 for preventing a slackening of the conduits 14 when the length of the extendable support arm 15 is changed . the support arm 15 is divided into three segments that can slide with respect to one another , thereby enabling a extension of the support arm 15 by a telescopic action . in fig1 the support arm is shown at its maximum extension . the support arm 15 is supported by a second support 17 attached to a boom 21 . the second pivot 17 defines a horizontal pivot axis allowing a pivotal motion in a vertical plane and a vertical pivot axis allowing a pivotal motion in a horizontal plane . a cabin 18 is connected to the vertical pivot axis so that the turning of the cabin 18 is synchronized with the horizontal turning of the support arm 15 . the boom 21 in turn is supported by a third pivot support 22 . the third pivot 22 defines a horizontal pivot axis allowing a pivotal motion in a vertical plane . the boom 21 is provided with a parallel displacement joint 20 which is connected to the third pivot support 22 via the boom 21 itself and a parallel displacement bar 30 to define a parallelogram linkage . thereby , the vertical pivot axis of the second pivot 17 is maintained in a vertical orientation , even though the inclination of the boom 20 is changed . the third pivot support 22 is anchored to the roof 23 of a housing 26 on a truck 29 behind the driver &# 39 ; s cabin 28 . a hand rail 24 traces the edge of the roof 22 , which can be reached from the ground via a ladder 25 at the back of the truck 29 . the housing 26 encloses a tank for storing the de - icing liquid and a pump for supplying the nozzle 10 with pressurized de - icing fluid via the conduits 14 . the housing also encloses a heater that can optionally heat the de - icing fluid . the inside of the housing 26 can be reached via a sliding door 27 . a pair of distal contact sensors 47 , in form of freely extending rods , is mounted in a downward orientation at the distal end of the support arm 15 . if any of these contact sensor sensors come in physical contact with another object , all movements of the support arm 15 and the boom 21 will terminate , which will reduce the risk for collisions with the aircraft while de - icing . a preferred embodiment of the distal end of the support arm of the de - icing system is illustrated in fig2 a . a first pivot support 12 is attached to the distal end of the distal telescopic segment 31 of the extendable support arm 15 . the first pivot support 12 supports a nozzle 10 through which a de - icing liquid can be expelled under pressure . the orientation of the nozzle 10 can be changed by pivoting it around a horizontal pivot axis 32 , allowing a pivotal motion in a vertical plane , and a normal pivot axis 33 allowing sideways motions with respect to the extendable support arm 15 . a distance sensor 11 in the form of an ultrasonic range finder is rigidly mounted onto the nozzle 10 by a fixed attachment 34 . in alternative embodiments the distance sensor 11 can be a laser , radar , or infrared rangefinder . the measurement direction 35 of the distance sensor 11 points in the general direction 36 of the expelled liquid 37 . the position of the distance sensor 11 relative to the nozzle 10 is such that , under normal operation conditions , the distance measurements are through the expelled de - icing liquid . the distance sensor 11 also doubles as a detector for detecting the edges of an aircraft wing 38 by reacting to rapid changes in the distances measured or the loss of a reflexion signal . for example , the distance sensor 11 typically measures a distance in the range of 0 . 5 to 2 meters to the upper surface 39 of the aircraft wing . if the distance sensor instead would point at the ground , the distance measured would at least be larger than 2 . 5 meters . the rapid change from a measured distance in the range of 0 . 5 to 2 meters to a measured distance larger than 2 . 5 meters then correspond to a detection of the leading edge 40 or the trailing edge 41 . an alternative embodiment of the distal end of the support arm of the de - icing system is illustrated in fig2 b . all features that are common to this embodiment and the previously described embodiments have been given the same index numbers . in this alternative embodiment , the sensor 11 is connected to the nozzle 10 via a pivotal support 42 , allowing the sensor 11 to sweep independently from the nozzle , both in a vertical plane and sideways with respect to the nozzle . another alternative embodiment of the distal end of the support arm of the de - icing system is illustrated in fig2 c . all features that are common to this embodiment and to the previously described embodiments have been given the same index numbers . in this alternative embodiment the sensor 11 is connected to the part of the first pivot support 12 that is fixed relative to the distal segment 31 of the telescopic support arm 15 . the connection is achieved via a pendulum sensor support 43 and orients the sensor 11 so that its measurements direction 35 of the sensor 11 is held essentially vertical by the force of gravity . yet another alternative embodiment of the distal end of the support arm of the de - icing system is illustrated in fig3 . all features in common with the previously described embodiments have been given the same index numbers . in this alternative embodiment , the sensor 11 is connected to the nozzle 10 via a fixed attachment 34 , where the distance sensor 11 is a rotating sensor that scans in a vertical plane to detect the surface of the aircraft wing and the distance thereto . by the mounting 49 the rotating sensor 11 is fixed to the fixed pivot support 12 , whereby the rotating sensor 11 follows the support arm 15 . yet another alternative embodiment of the distal end of the support arm of the de - icing system is illustrated in fig4 . all features that are common to this embodiment and the previously described embodiments have been given the same index numbers . in this alternative embodiment , the sensor 11 is connected to the nozzle 10 via a fixed attachment 34 . an additional sensor 44 is connected to the nozzle 10 via an additional fixed attachment 45 . the sensor 11 is oriented so that , at typical operation conditions , its line of measuring does not point towards the expelled de - icing liquid 37 . similarly , the additional sensor 11 is oriented so that , at typical operation conditions , its line of measuring 46 does not cross the expelled de - icing liquid 37 . the placement of the two sensors is such that the two lines - of - measuring are on opposite sides of the expelled de - icing fluid 37 . by this , if the sensors are used to detect the edges of the aircraft wing in a vertical sweep by the nozzle 10 , the projected de - icing liquid will not cross the edge before detection of the same . hence , the amount of de - icing liquid lost outside the upper surface 39 of the wing 38 is significantly reduced . a preferred embodiment of the proposed method for de - icing is illustrated in fig5 as a flow - chart 59 . initially , the extendable support arm is manually controlled so that the distance sensor and the nozzle are positioned directly above an aircraft wing . a preferred vertical distance between the distance sensor and the aircraft wing is defined in the step of defining parameters 60 . the preferred vertical distance in question has the value r 0 . in the step of defining a fluid application path 61 , a horizontal plane having the cartesian coordinates ( x , y ) is first defined , in which the fluid application path is embedded . the fluid application path is defined as changes in the x and y coordinates , where each change in the x coordinate is represented by the incremental step dx i , and each change in the y coordinate is represented by the incremental step dy i . here , the subscript i correspond to the order in which the incremental steps are performed . this way , the polygonal fluid application path in the horizontal plane is non - localised and completely defined by the two sets dx and dy having the same integer number n of elements . the two sets can be written as : dx ={ dx 1 , dx 2 , . . . , dx n - 1 , dx n } and dy ={ dy 1 , dy 2 , . . . , dy n - 1 , dy n }. here , dx i and dy i are real - valued , i . e . they can be positive , zero , or negative . if ( x 0 , y 0 ) are defined as the starting coordinates , the localized fluid application path can then be described by a sequence of the coordinates : in addition to the fluid application path , a vertical line having the coordinate z is defined . naturally , the vertical line is normal to the horizontal surface embedding the fluid application path . further , an incremental step dz is defined along the vertical line , where the step has the absolute value | dz |. a de - icing fluid is applied to the aircraft wing in the step of applying a de - icing fluid 62 . this step 62 is performed continuously during all of the following steps , which is illustrated in fig5 by placing all the following steps inside the step of applying a de - icing fluid 62 . this means that the de - icing fluid is applied continuously to the aircraft wing during operation . in the step of measuring 63 , an integer counter q , which has the initial value of 0 , is first increased by one , whereupon the first distance to the aircraft wing is measured along a vertical measurement direction , giving the measured distance value p q . in the following step of evaluating 64 the preferred distance value r 0 is recalled 75 and subtracted 76 from the measured distance value p q . from the result of the subtraction 76 it is determined whether p q is smaller than r 0 77 , is equal to r 0 78 , or p q is larger than r 0 79 . in the subsequent step of deriving a control signal 65 , the incremental steps dx q and dy q are recalled from dx and dy 83 , respectively , where q correspond to q &# 39 ; th element of the sets . the incremental step dz q is set to +| dz | if p q is smaller than r 0 80 , to 0 if p q is equal to r 0 81 , or to −| dz | if p q is larger than r 0 82 . the combined incremental steps ( dx q , dy q , dz q ) correspond to a single step in three - dimensions , which is subsequently inserted into a function f translating it into machine instructions s 85 . the machine instructions s are sent as a control signal 70 to an automated control system . in the subsequent step of controlling 66 the automated control system carries out the instructions and moves the nozzle according to the combined incremental steps ( dx q , dy q , dz q ). in the subsequent step of repeating 67 , the operation returns 72 to the step of measuring 63 , from which the described process is repeated again , but with the integer counter q increased by one . for the sake of clarity , in fig5 the connection 73 has been indexed to stress that r 0 is defined in the step of defining parameters 60 , while the connection 74 has been indexed to stress that dx q and dy q are defined in the step of defining a fluid application path 61 . in fig6 an aircraft wing 110 having a leading edge 112 and a trailing edge 113 is illustrated . the wing 110 is connected to the fuselage 111 of the aircraft . a fluid application path 121 defining a fixed horizontal distance to the leading edge of an aircraft wing has been outlined . in a preferred embodiment , the fluid application path 121 is achieved by detecting at least two points on the leading edge 112 . these points are used to define a horizontal straight line for the case of two points , or polygon in a horizontal plane for the case of more points . the fluid application path is then defined by parallel transporting the straight line or polygon in a horizontal direction so that all the points shift the same horizontal distance . here , the horizontal shift corresponds to the fixed horizontal distance . in fig7 a fluid application path 122 defining a fixed horizontal distance to the trailing edge 113 of an aircraft wing 110 is illustrated , which instead is achieved by detecting at least two points on the trailing edge 113 . a fluid application path 124 defining a fixed horizontal distance to the bisector 123 of an aircraft wing 110 is illustrated . the bisector 123 is determined by detecting the horizontal position of at least two equidistant points on the leading edge 112 in a first series , and the same number of equidistant points on the trailing edge 113 in a second series . the distance between the points in the first series is the same as between the points in the second series . the points on each edge are ordered according to their distance to the fuselage . points of the same order in the two series are paired together , where each pair define a line . the bisector 123 is then defined as the polygon through the middle points of these lines . the fluid application path 124 is then defined by a parallel transport of the bisector 123 in the preferred horizontal direction . fig9 and fig1 illustrate fluid application paths defining a series of single - loops having smooth turns 126 and sharp turns 127 , respectively . in a preferred embodiment , the fluid application paths are initially non - localized and have no pre - defined orientations with respect to the aircraft wing 110 . the placing and orientation are manually defined by an operator by setting two coordinates corresponding to the start point 128 and end point 129 of the fluid application path . fig1 illustrates a fluid application path 134 defining a zigzag pattern along an aircraft wing 110 . in a preferred embodiment , this is achieved by defining a first line 139 and a second line 140 in a horizontal plane . the lines are non - parallel , initially non - localized , and have no pre - defined orientation with respect to the aircraft wing , but have a fixed orientation with respect to one another . an operator defines the start point 135 and the direction for the first line 139 , while the end point 136 is determined by detecting the first edge , which in this example is the leading edge 112 . the end point 136 is located at a certain distance from the first edge and is subsequently defined as the start point 136 for the second line 140 . the direction of the second line 140 is already determined by its predefined relative orientation with respect to the first line 139 . the end point 137 of the second line 140 is determined by detecting the second edge , which in this example is the trailing edge 113 . the end point 137 is located at a certain distance from the second edge and is subsequently defined as the start point 137 for another line , thereby allowing the fluid application path to be extended in zigzag pattern following a recursive sequence involving the described steps of a detecting edges and defining start and end points . fig1 illustrates a fluid application path 141 defining a zigzag pattern across an aircraft wing 110 . in a preferred embodiment this is achieved by combining the methods described in connection with fig6 and fig7 , i . e . by defining a first line 142 being parallel to the leading edge 112 and a second line 143 being parallel to the trailing edge 113 . the first turn point 144 and the one or more intermediary turn points 145 of the zigzag pattern are predefined by an operator ; while the last turn point 146 is defined by detecting the edge , which in this example is the trailing edge 113 . the last turn point is located at a certain distance from the edge . fig1 illustrates a fluid application path 147 defining a square pattern along an aircraft wing . in a preferred embodiment , this is achieved by defining a first line 148 at a first fixed distance from the edge and a second line 149 at a second fixed distance form the edge . in this example , the edge is the leading edge 112 and the first distance is smaller than the second distance . the fixed distances are obtained by a method similar to that discussed in connection with fig6 . the fluid application path is then defined by connecting the paths at predefined intervals , where the connections 150 are substantially perpendicular to the edge . 121 fluid application path defining a fixed horizontal distance to the leading edge 122 fluid application path defining a fixed horizontal distance to the trailing edge 124 fluid application path defining a fixed horizontal distance to the bisector 126 fluid application path defining a series of single - loops having smooth turns 127 fluid application path defining a series of single - loops having sharp turns 134 fluid application path defining a zigzag pattern along an aircraft wing 141 application path defining a zigzag pattern across an aircraft wing 147 fluid application path defining a square pattern along an aircraft wing | 1 |
the inventors have found purinergic ( p2x ) receptors in extracellular body fluids of individuals having various forms of cancer . this is a surprising finding as all p2x7 receptors to date have been found to be anchored into the cell surface lipid bilayer by one or two transmembrane spanning domains . hence the teaching in the art to date has been that purinergic ( p2x ) receptors are expressed predominantly on the cell membrane . the finding that certain purinergic ( p2x ) receptors are found in the extra - cellular body fluids of individuals having various disease and conditions , or predisposed to same is significant because in certain embodiments individuals may be screened on the basis of an extra - cellular body fluid sample , which is generally much more simple to isolate than a tissue biopsy . the latter has been required to determine cell membrane expression of purinergic p2x receptors to date . in certain embodiments there is provided an isolated purinergic ( p2x ) receptor , p2x monomer or fragment thereof obtainable from an extra - cellular body fluid . typically the receptor is a p2x7 receptor , monomer or fragment thereof . in certain embodiments , a p2x7 receptor includes all receptors including at least one p2x7 monomer sequence , whether or not the p2x7 receptor is functional in the sense of capable of binding to atp and or forming a pore for ingress of cations into a cell leading to programmed cell death . an example of a p2x7 receptor that has impaired atp binding function is a receptor having a cis isomerisation at proline 210 of the sequence shown in seq id no : 1 . the fluid may be selected from the group consisting of blood , plasma , serum , lymph , urine , semen , saliva , sputum , ascites , faeces , uterine and vaginal secretions , bile , amniotic fluid , cerebrospinal fluid and organ and tissue flushings . the extra - cellular body fluid is typically cell - free although in some circumstances it may contain residual cells or fragments thereof . the receptor , monomer or fragment thereof may include an amino acid sequence as shown in table 1 below . the receptor , monomer or fragment thereof may have an amino acid sequence consisting of part of any one of the sequences listed in table 1 . typically a fragment is part of a monomer of at least about 10 amino acid residues length and no more than about 595 amino acids in length . the receptor , monomer or fragment thereof may be linked to a fragment of a cell membrane . the cell membrane fragment may be the result of cell lysis or membrane blebbing . the cell membrane fragment may be provided in the form of a liposome - like or micelle - like structure with purinergic ( p2x ) receptors located thereon . in certain embodiments the receptor is linked to a solid phase , such as an assay plate , bead or tissue culture vessel . these forms of the receptor are particularly useful for preparation of antibodies to the receptor described further below which may be used in the diagnostic and therapeutic applications described further below . in another embodiment there is provided an immune complex formed from the binding of an anti purinergic ( p2x ) receptor antibody or fragment thereof to a purinergic ( p2x ) receptor , monomer or fragment thereof as described above . generally an immune complex otherwise known as an antigen - antibody complex is a product that is formed from the binding of an antibody via an antibody binding site to an epitope on a antigen against which the antibody was raised . the complex may or may not consist of more than one antibody . typically the receptor is a p2x7 receptor and the antibody is an anti p2x7 antibody or fragment thereof . the immune complex is particularly important as detection of this in vitro or in vivo is indicative of presence of , or predisposition to a disease or condition including preneoplasia and neoplasia . these detection methods are described in more detail below . as is generally understood in the art , neoplasia is literally new growth and usually refers to abnormal new growth or proliferation generally persisting in the absence of an original growth stimulus . neoplasia may be benign or malignant . pre - neoplasia is generally a form of cellular growth or transformation preceding neoplasia . it may be characterised by hyperplasia and / or appearance of mitotic figures histologically without marked anaplasia or loss of cell differentiation . pre - neoplastic tissue is sometimes found in regions adjacent to a tumour lesion . the extra - cellular body fluid is typically cell - free although in some circumstances it may contain residual cells or fragments thereof . however , the immune complexes are predominantly formed from antibody binding to receptors , monomers or fragments thereof that are not located on a cell surface of an intact or whole cell , but rather to receptors , monomers or fragments thereof that are suspended or dissolved in the body fluid . the antibody may be a whole antibody of any isoform . the antibody may be one obtained from monoclonal or polyclonal antisera . the antibody may be produced by hybridoma , or by recombinant expression . the antibody may be human or one formed by grafting cdrs onto a xenogeneic or allogeneic framework . where the antibody is an antibody fragment , the antibody fragment is selected from the group consisting of a dab , fab , fd , fv , f ( ab ′) 2 , scfv and cdr . the antibody may bind to an extra - cellular domain of a purinergic ( p2x ) receptor . in one embodiment , the purinergic ( p2x ) receptor is a p2x7 receptor . as discussed herein , there are a number of isoforms of the p2x7 receptor . the antibody may bind to any one of the domains of these isoforms . a full length isoform includes an intra - cellular n - terminal domain , a transmembrane domain , an extra - cellular domain , a further transmembrane domain and a c - terminal intra - cellular domain . examples of epitopes located on an extra - cellular domain of a p2x7 receptor are set forth in table 2 . the antibody or antibody fragment may be attached to a solid phase , such as a bead or a plate , or blotting paper , for example nitrocellulose paper , so that the immune complex is attached to a solid phase when formed . in this embodiment the antibody may function as a “ capture ” antibody . alternatively , a receptor or fragment thereof is attached to a solid phase . the anti p2x7 receptor antibody may be labelled for detection of formation of the immune complex . the immune complex may further include a further antibody or fragment thereof , for example for capture of the immune complex . the further antibody or fragment thereof may be bound to the anti p2x7 receptor antibody . also the further antibody or fragment thereof may be bound to the receptor or fragment thereof . the further antibody or fragment thereof may be bound to a solid phase such as a phase described above . the further antibody or fragment thereof may be labelled for detection of formation of the immune complex . examples of labels include fluorophores , dyes , isotopes etc . as an alternative , a complex may be provided by contacting a purinergic ( p2x ) receptor , such as a p2x7 receptor to a compound capable of binding to the receptor to form a detectable complex . thus in a further embodiment them is provided a complex formed from the binding of a purine or purine related compound to a p2x7 receptor , monomer , or fragment thereof as described above . an example is atp or atp analogue such as benzoyl - benzoyl atp . the atp may be bound or conjugated to a label to facilitate detection of formation of the complex . in still further embodiments there is provided an antibody or fragment thereof for binding to an epitope on an extra - cellular purinergic receptor , monomer or fragment thereof , the epitope not being found on a purinergic receptor , monomer or fragment thereof that is expressed on a cell surface membrane . typically the antibody binds to an epitope on an extra - cellular p2x7 receptor , monomer or fragment thereof . an example of an antibody fragment includes a dab , fab , fd , fv , f ( ab ′) 2 , scfv and cdr . in certain embodiments there is provided a method for determining whether an extra - cellular body fluid contains a purinergic receptor , monomer or fragment thereof including : contacting an extra - cellular body fluid with an anti purinergic receptor antibody or fragment thereof in conditions for forming an immune complex , and detecting whether an immune complex has been formed , wherein the detection of an immune complex indicates that the fluid contains a purinergic receptor , monomer or fragment thereof . typically the antibody is an anti purinergic ( p2x ) receptor antibody such as an anti p2x7 receptor antibody or , fragment thereof . in other embodiments there is provided a use of an anti p2x7 - receptor antibody or fragment thereof in the manufacture of means for determining whether an extra - cellular body fluid contains a p2x7 receptor , monomer or fragment thereof . in other embodiments there is provided a method for determining whether an extra - cellular body fluid contains an antibody against an extra - cellular purinergic receptor , monomer or fragment thereof including : contacting extra - cellular body fluid with a purinergic receptor , monomer or fragment thereof in conditions for forming an immune complex between the purinergic receptor , monomer or fragment thereof and an antibody against an extra - cellular purinergic receptor , and detecting whether an immune complex has been formed ; wherein the detection of an immune complex indicates that the fluid contains an antibody against an extra - cellular purinergic receptor , monomer or fragment thereof . typically the purinergic p2x receptor is a p2x7 receptor , monomer or fragment thereof . in other embodiments there is provided a use of a p2x7 receptor , monomer or fragment thereof obtainable from an extra - cellular body fluid in the manufacture of means for determining whether an extra - cellular body fluid contains an anti - p2x7 receptor antibody . the presence of a given protein , or level of expression of a given protein such as a purinergic ( p2x ) receptor or fragment thereof in an extra - cellular body fluid can be detected by any number of assays . examples include immunoassays , chromatography and mass spectrometry . immunoassays , i . e . assays involving an element of the immune system are particularly preferred . these assays may generally be classified into one of : ( i ) assays in which purified antigen is used to detect an antibody in host serum . for example , purified antigen is bound to solid phase by adsorption or indirectly through another molecule and host serum or other body fluid is applied followed by another antibody for detecting presence or absence of host antibody ; ( ii ) assays in which purified antigen is used to detect immune cells , such as t and b lymphocytes . for example , peripheral white cells are purified from a host and cultured with purified antigen . the presence or absence of one or more factors indicating immunity are then detected . other examples include assays that measure cell proliferation ( lymphocyte proliferation or transformation assays ) following exposure to purified antigen , and assays that measure cell death ( including apoptosis ) following exposure to purified antigen : ( iii ) assays in which purified antibody specific for antigen is used to detect antigen in the host . for example , purified antibody is bound to solid phase , host extra - cellular body fluid is then applied followed by another antibody specific for the antigen to be detected . there are many examples of this approach including elisa , ria and the like ; ( iv ) assays in which a purified anti - idiotypic antibody is used to detect host antibody . for example , anti - idiotypic antibody is adsorbed to solid phase , host serum is added and anti - fc antibody is added to bind to any host antibodies having been bound by the anti - idiotypic antibody . ( v ) assays in which extra - cellular body fluid is separated from a protein component contained within it , the protein component is then fixed onto a solid phase and the probed with an antibody . examples include dot blotting and western blotting . a further assay format which does not require formation of an immune complex is one in which an assay output is the result of catalysis of a substrate and the output is observed for example by measuring a change in optical density . the extra - cellular body fluid to be assessed in the above described embodiments of the invention may be selected from the group consisting of blood , plasma , serum , lymph , urine , semen , saliva , sputum , ascites , faeces , uterine and vaginal secretions , bile , amniotic fluid , cerebrospinal fluid , tear , and organ and tissue flushings . the extra - cellular body fluid is typically cell - free although in some circumstances it may contain residual cells or fragments thereof . it will be appreciated that any disease where a purinergic ( p2x ) receptor is expressed in extra - cellular body fluid can be detected by these methods . the disease is typically a cancer such as carcinoma , sarcoma , lymphoma , leukaemia or other parenchymal cell growth abnormality . carcinomas that may be detected include , but not limited to , prostate , breast , skin , lung , cervix , uterus , stomach , esophagus , bladder , and colon cancers . as generally understood , a cancer or tumour is a neoplastic state and may be benign or malignant . in certain embodiments the cancer is metastatic disease . whilst any body fluid can be used to detect any of these diseases , in certain embodiments , some body fluids may be more appropriate than others to detect certain diseases , for example urine may be more appropriate to detect prostate cancer . blood may be more appropriate for detecting blood cancers such as lymphoma . in another embodiment there is provided a method for determining whether an individual has a cancer including the steps of : collecting a sample of extra - cellular body fluid from the individual and contacting extra - cellular body fluid with an anti purinergic ( p2x ) receptor antibody or fragment thereof in conditions for forming an immune complex as described above , and detecting whether an immune complex has been formed . in a further embodiment there is provided use of anti purinergic ( p2x ) receptor antibody or fragment thereof for determining whether an individual has a cancer . in yet further embodiments there is provided a method for determining whether an individual has cancer , or is predisposed to cancer including the steps of : providing a sample of extra - cellular body fluid obtained from an individual in whom the presence or absence of cancer or predisposition thereto is to be determined ; contacting the sample with an anti purinergic ( p2x ) receptor antibody or fragment thereof in conditions for forming an immune complex ( as described above ) between a purinergic ( p2x ) receptor , monomer or fragment thereof in the extra - cellular body fluid in the sample and the antibody or fragment thereof ; and detecting whether the immune complex has been formed , thereby determining whether the individual has a cancer or predisposition thereto . in one embodiment the method is implemented as a direct , indirect or sandwich elisa , ria or like assay involving the application of a liquid sample to an assay system . the sample may or may not be processed prior to contact with an antibody . in yet further embodiments there is provided a method for determining whether an individual has cancer , or is predisposed to cancer including the steps of : providing a sample in the form of a tissue biopsy including an extra - cellular body fluid , the sample being obtained from an individual in whom the presence or absence of cancer or predisposition thereto is to be determined ; contacting the sample with an anti purinergic ( p2x ) receptor antibody or fragment thereof in conditions for forming an immune complex between a purinergic ( p2x ) receptor , monomer or fragment thereof , in or derived from , the extra - cellular body fluid in the sample and the antibody or fragment thereof ; and detecting whether the immune complex has been formed , to determine whether the individual has or is predisposed to a cancer . in one embodiment the method is implemented in an immuno - histochemical format whereby a tissue section containing extra - cellular body fluid is applied to a slide leading to fixing of protein in the fluid to the slide and staining with an antibody . according to these embodiments , the method includes the step of assessing the sample , for example the tissue section , for the presence or absence of the immune complex in an extra - cellular space . examples of these spaces include those in the form of a lumen of a gland , duct or vessel such as a blood vessel or lymphatic . other extra - cellular spaces include those defined by an impermeable or semi - permeable layer of epithelial cells , one example of the former being the space defined by the blood brain barrier , an example of the latter being a convoluted tubule of a nephron . in yet further embodiments there is provided a method for determining whether an individual has cancer or is predisposed to cancer including the steps of : administering an anti purinergic ( p2x ) receptor antibody or fragment thereof to an individual in whom the presence or absence of cancer or predisposition thereto is to be determined in conditions for forming an immune complex between the antibody or fragment thereof and a purinergic ( p2x ) receptor , monomer or fragment thereof in the extra - cellular body fluid of the individual ; and detecting whether the immune complex has been formed to determine whether the individual has a cancer or predisposition thereto . the method may include the step of obtaining a sample of extra - cellular body fluid from the individual and determining whether the sample contains the immune complex , to detect whether the immune complex has been formed . alternatively , the method may include the step of obtaining a sample in the form of a tissue biopsy including an extra - cellular body fluid from the individual and assessing the sample for the presence or absence of the immune complex in an extra - cellular space of the tissue biopsy , to detect whether the immune complex has been formed . in yet further embodiments there is provided a method for determining whether an individual has cancer or is predisposed to cancer including the steps of : providing a sample of extra - cellular body fluid obtained from an individual in whom the presence or absence of cancer or predisposition thereto is to be determined ; applying the sample to a solid phase in conditions for fixing a purinergic ( p2x ) receptor , monomer or fragment thereof in the extra - cellular body fluid of the individual to the solid phase ; contacting the solid phase with an anti purinergic ( p2x ) receptor antibody or fragment thereof in conditions for forming an immune complex between a purinergic ( p2x ) receptor , monomer or fragment thereof fixed to the solid phase and the antibody or fragment thereof ; and detecting whether the immune complex has been formed , thereby determining whether the individual has cancer or predisposition thereto . in yet further embodiments there is provided a kit or composition for determining whether an extra - cellular body fluid contains a purinergic ( p2x ) receptor , monomer of fragment thereof as described above , or an antibody against an extra - cellular p2x7 receptor or fragment thereof as described above including : an anti purinergic ( p2x ) receptor antibody or fragment thereof ; and / or a p2x7 receptor , monomer or fragment thereof obtainable from extra - cellular body fluid as described above ; and optionally a further antibody for binding to the antibody or fragment thereof or the p2x7 receptor , monomer or fragment thereof ; written instructions for use of the kit in a method described above . the following protocols are provided as non - limiting examples of suitable methods for detecting p2x7r in a sample of extra - cellular fluid for the purpose of illustrating the invention . detection of ( p2x ) purinergic receptors in extra - cellular body fluid by direct elisa . plasma samples ( 1 ml ) obtained from 9 patients with grade iii ovarian adenocarcinoma were diluted 1 : 50 for direct elisa in triplicate . control plasma are the 3 samples at left ( fig1 ). only low volumes of samples were required for reliable detection of shed receptor sourced from cancer cells in the patients &# 39 ; plasma . detection of ( p2x ) purinergic receptors in extra - cellular body fluid by indirect elisa . shed receptor from bladder cancer patients was detected in urine . patients with extant disease and those in remission following treatment could be separated using a competition elisa . urine was diluted 1 : 10 and the spiked p2x7 antibody was used at 2 . 5 ug / ml ( fig1 ). test sample 1 was a patient in remission , close to the control level , while test sample 2 had existing disease manifest by the presence of shed receptor . urine samples ( 1 ml ) were sufficient for detection ( in triplicate ). detection of ( p2x ) purinergic receptors in extra - cellular body fluid by dot blotting . samples of urine from patients with ovarian and bladder cancer were examined using dot blots and a range of antibodies to p2x7 receptors . pvdf sheets were wet in pbs for 15 min then air dried . sheets were then dotted with urine or sera ( neat or diluted ) and dried at 37 c . sheets were then placed at 4 c ( dry ) until ready to test . sheets were wet in tbs before blocking in 3 % bsa / tbs for 1 hr . antibodies were added into bags containing nitrocellulose sheets ( 1 sheet per bag ) at 50 ug / ml in 3 % bsa / tbs and incubated on rocker for 2 hrs . sheets were washed three times in tbs before conjugates were added at 1 / 1k concentration in 3 % bsa / tbs and placed on rocker for 1 . 5 hrs . sheets were washed in tbs for 4 solution changes then developed using chloro - 1 - napthol . staining was neutralized in tap water before air drying and photographing with video camera . fig1 is an example of results obtained with ovarian and bladder cancer patients as well as controls . urine from all cancer positive patients was observed to contain p2x7 while the control urine samples were devoid of detectable levels of receptor . detection of ( p2x ) purinergic receptors in extra - cellular body fluid by immuno histochemistry . in one embodiment of the invention we have detected shed receptor in lymph nodes draining the area of identified tumours . in the absence of metastatic cells , lymph nodes considered sentinel nodes for breast and prostate cancers were removed in the course of surgery , fixed and embedded . sections were stained for the presence of non - functional p2x7 receptor . receptor was detected in the sentinel nodes whereas control nodes were devoid of shed receptor in the medulla . examples , include prostate ( a ) and breast ( b ) where brown stain in the form of dab reveals the presence of receptor , ( fig1 ). detection of prostate cancer by detection of ( p2x ) purinergic receptors in serum and urine . in one embodiment of the invention we have used a direct elisa to detect the presence of p2x7 receptor in urine and serum from a patient with advanced prostate cancer . the microtitre plate - based eia kit consists of 12 strips of 8 wells each , pre - coated with e80 , e140 or e200 antibodies to p2x7 . the assay operates on the basis of competition between the shed receptor in the sample and the receptor - enzyme conjugate for the limited number of specific binding sites on the pre - coated microtitre plate . after overnight incubation , unbound reagents were removed by rinsing wells with pbs . the enzyme conjugate utilised horseradish peroxidase ( hrp ) as a tracer . the amount of p2x7 - hrp bound was measured by adding the chromogen substrate 2 , 2 ′- azino - bis ( 3 - ethylbenzthiazoline - 6 - sulfonic acid ) diammonium salt ( arts ). bound p2x7 - hrp conjugate converted the colourless abts solution to a blue product . the abts reaction was stopped by the addition of the stopping solution , 5 % oxalic acid , which converted the solution to a yellow - coloured product . the colour intensity was measured at 405 nm with reference at 490 nm using a microplate reader . the colour intensity was inversely proportional to the p2x7 epitope concentration in the calibrator or sample . faecal samples from two patients with established adenocarcinomas were collected and shed cells buffer extracted . the samples were run on polyacrylamide gels and major p2x7 protein bands identified in a western blot . the figure shows two major bands at molecular weights of 75 kda and 30 kda respectively using an antibody to seq id no : 2 corresponding with full length receptor and a truncated piece of receptor containing the epitope 200 - 216 . | 6 |
approximating language , as used herein throughout the specification and claims , may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related . accordingly , a value modified by a term or terms , such as “ about ”, is not limited to the precise value specified . in at least some instances , the approximating language may correspond to the precision of an instrument for measuring the value . range limitations may be combined and / or interchanged , and such ranges are identified and include all the sub - ranges stated herein unless context or language indicates otherwise . other than in the operating examples or where otherwise indicated , all numbers or expressions referring to quantities of ingredients , reaction conditions and the like , used in the specification and the claims , are to be understood as modified in all instances by the term “ about ”. “ optional ” or “ optionally ” means that the subsequently described event or circumstance may or may not occur , or that the subsequently identified material may or may not be present , and that the description includes instances where the event or circumstance occurs or where the material is present , and instances where the event or circumstance does not occur or the material is not present . as used herein , the terms “ comprises ”, “ comprising ”, “ includes ”, “ including ”, “ has ”, “ having ”, or any other variation thereof , are intended to cover a non - exclusive inclusion . for example , a process , method , article or apparatus that comprises a list of elements is not necessarily limited to only those elements , but may include other elements not expressly listed or inherent to such process , method , article , or apparatus . the singular forms “ a ”, “ an ”, and “ the ” include plural referents unless the context clearly dictates otherwise . turning to the drawings , fig1 and 1a show rotatable sputter target assembly 10 comprising cylindrical target 20 concentrically mounted over cylindrical backing tube 40 . the target 20 and backing tube 40 are adapted for rotation around a central axis 80 of the assembly . means for imparting the desired rotation can be seen for example in u . s . pat . nos . 5 , 262 , 032 and 5 , 464 , 518 , both of which are herein incorporated by reference . a backing material 60 is located between the inner surface 22 of target 20 and the outer surface 41 of backing tube 40 . in accordance with one embodiment of the invention , target 20 may be comprised of a ceramic or metal oxide material , such as indium tin oxide ( tto ) or aluminum zinc oxide ( azo ). the backing tube 40 may be comprised of al , al alloy , stainless steel , copper , titanium , or any other material deemed suitable by a person having ordinary skill in the art . as shown in the drawings , a backing material 60 occupies the annular space between the target 20 and backing tube 40 . in some embodiments backing material 60 is corrugated sheet metal . in other embodiments , backing material 60 is mesh metal . backing material 60 resiliently connects the target 20 and backing tube 40 along a multitude of support locations on the inner surface 22 of the target 20 . backing material 60 could be connected to the target 20 and backing tube 40 by a mechanical or chemical fastener . alternatively , backing material 60 could be secured to the target 20 and backing tube 40 only by friction , such as through a friction fit . accordingly , in one embodiment , this invention utilizes a backing material 60 that is rolled around backing tube 40 . the cylindrical , rotatable ceramic target 20 is then fitted on top of the backing material 60 . backing material 60 functions like multiple springs so as to provide a resilient , fixed mount of the target 20 to the backing tube 40 . resiliently connecting the target 20 and backing tube 40 along a multitude of support locations prevents the formation of concentrated heat areas in the target 20 . thereby reducing the likelihood of crack and nodule formation in or on target 20 . fig2 shows a cross section taken at 1 a of fig1 of an embodiment of the invention which utilizes corrugated sheet metal 60 rolled around the backing tube 40 . the cylindrical , rotatable ceramic target 20 is fitted on top of the corrugated sheet metal 60 . the outer ridges 61 of corrugated sheet metal 60 contact the inner surface 22 of target 20 , and the inner ridges 62 of corrugated sheet metal 60 contact the outer surface 41 of backing tube 40 . in some embodiments , ridges 61 and 62 run parallel to the central axis 80 of the sputter target assembly 10 . in other embodiments , ridges 61 and 62 run perpendicular to the central axis 80 of the sputter target assembly 10 . in additional embodiments , ridges 61 and 62 run both perpendicular and parallel to the central axis 80 of the sputter target assembly ( e . g ., a crisscross pattern ). in additional embodiments , ridges 61 and 62 run neither parallel nor perpendicular to the central axis 80 of the sputter target assembly . in some embodiments , ridges 61 and 62 run parallel with respect to each other . in other embodiments , ridges 61 and 62 run perpendicular with respect to each other . in additional embodiments , ridges 61 and 62 run both perpendicular and parallel with respect to each other ( e . g ., a crisscross pattern ). in some embodiments , ridges 61 and 62 form an obtuse angle with respect to each other . in other embodiments , ridges 61 and 62 form a reflex angle with respect to each other . in other embodiments , ridges 61 and 62 form an acute angle with respect to each other . the inner ridges 62 and outer ridges 61 of the corrugated metal 60 functions like multiple springs so as to provide a resilient , fixed mount of the target 20 to the backing tube 40 . resiliently connecting the target 20 and backing tube 40 along a multitude of support locations prevents the formation of concentrated heat areas in the target 20 . thereby reducing the likelihood of crack and nodule formation in or on target 20 . fig3 shows a cross section taken at 1 a of fig1 of an embodiment of the invention which utilizes mesh metal 60 rolled around the backing tube 40 . the cylindrical , rotatable ceramic target 20 is fitted on top of the mesh metal 60 . the outer wire 61 of mesh metal 60 contact the inner surface 22 of target 20 and the inner wire 62 of mesh metal 60 contact the outer surface 41 of backing tube 40 . in some embodiments , wires 61 and 62 run perpendicular to the central axis 80 of the sputter target assembly 10 . in additional embodiments , wires 61 and 62 run both perpendicular and parallel to the central axis 80 of the sputter target assembly ( e . g ., a crisscross pattern ). in additional embodiments , wires 61 and 62 run neither parallel nor perpendicular to the central axis 80 of the sputter target assembly . in some embodiments , wires 61 and 62 run perpendicular with respect to each other . in additional embodiments , wires 61 and 62 run both perpendicular and parallel with respect to each other ( e . g ., a crisscross pattern ). in some embodiments , wires 61 and 62 form an obtuse angle with respect to each other . in other embodiments , wires 61 and 62 form a reflex angle with respect to each other . in other embodiments , wires 61 and 62 form an acute angle with respect to each other . the wires 62 and 61 of mesh metal 60 function like multiple springs so as to provide a resilient , fixed mount of the target 20 to the backing tube 40 . resiliently connecting the target 20 and backing tube 40 along a multitude of support locations prevents the formation of concentrated heat areas in the target 20 . thereby reducing the likelihood of crack and nodule formation in or on target 20 . another embodiment of this invention is comprised of a method of fabricating a rotatable sputter target assembly 10 comprising the steps of : providing a cylindrical target 20 , a cylindrical backing tube 40 , and a backing material 60 ; the cylindrical backing 40 tube further comprising an outer surface 41 and the cylindrical target 20 further comprising an inner surface 22 . the method is further comprised of rolling the backing material 60 onto the outer surface 41 of the cylindrical backing tube 40 and fitting the cylindrical target 20 on top of the backing material 60 . when assembled , the cylindrical target 20 and the cylindrical backing tube 40 are concentric . the backing material 60 resiliently connects the cylindrical target 20 and the cylindrical backing tube 40 along a multitude of support locations on the inner surface 22 of the target 20 . in one embodiment , the backing material 60 is corrugated sheet metal . in another embodiment , the backing material 60 is mesh metal . in one embodiment , the cylindrical target 20 is comprised of a ceramic or metal oxide material . in another embodiment , the cylindrical target 20 is comprised of at least one of indium tin oxide ( tto ) or aluminum zinc oxide ( azo ). in some embodiments , the cylindrical backing tube 40 is comprised of at least one of al , al alloy , stainless steel , copper , or titanium . another embodiment of this invention is comprised of another method of fabricating a rotatable sputter target assembly 10 . in this method , a cylindrical target 20 and a cylindrical backing tube 40 are provided . the cylindrical backing tube 40 further comprises an outer surface 41 and the cylindrical target 20 further comprises an inner surface 22 . the cylindrical target 20 and cylindrical backing tube 40 are resiliently connected along a multitude of support locations on the inner surface 22 of the target 20 by a backing material 60 , wherein the cylindrical target 20 and the cylindrical backing tube 40 are concentric . in one embodiment , the backing material 60 is corrugated sheet metal . in another embodiment , the backing material 60 is mesh metal . while this invention has been described in conjunction with the specific embodiments described above , it is evident that many alternatives , combinations , modifications and variations are apparent to those skilled in the art . accordingly , the preferred embodiments of this invention , as set forth above are intended to be illustrative only , and not in a limiting sense . various changes can be made without departing from the spirit and scope of this invention . therefore , the technical scope of the present invention encompasses not only those embodiments described above , but also all that fall within the scope of the appended claims . 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 processes . the patentable scope of the invention is defined by the claims , and may include other examples that occur to those skilled in the art . these other examples are intended to be within the scope of the claims if they have 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 language of the claims . | 7 |
referring to the block diagram of fig1 an audio input signal is applied to the input of a variable gain amplifier 1 and the input of a vibrato circuit 2 . the audio input signal is amplified by the variable gain amplifier 1 and the output of the variable gain amplifier 1 is applied to a reverb tank 3 . the reverb tank 3 adds a reverb effect to the amplified audio input signal producing a reverb effect output signal which is then applied to the input of a tremolo circuit 5 in a modulation circuit 4 . the dwell of the reverb effect is determined by the gain of the variable gain amplifier 1 . a higher amount of gain results in a longer dwell of the reverb effect due to the increased power applied to the reverb tank 3 . the modulation circuit 4 comprises the vibrato circuit 2 , the tremolo circuit 5 , and a mixer circuit 7 . the tremolo circuit 5 and the vibrato circuit 2 share a controllable resistance 6 and a tremolo / vibrato selector switch 7 . the output of the tremolo circuit 5 having a reverb effect and the output of the vibrato circuit 2 are both input to a mixer circuit 8 which mixes the two outputs together to produce the final modulated output of the electron tube preamplifier . the modulation circuit 4 is responsive to an oscillator output signal supplied by an oscillator 9 . the controllable resistance 6 is the element of the modulation circuit 4 that is responsive to the oscillator output signal and in turn induces modulation of the modulated output signal appearing at the output of the mixer circuit 8 via one of the tremolo circuit 5 and the vibrato circuit 2 depending upon the position of the tremolo / vibrato selector switch 7 . the mixer circuit 8 variably combines the outputs of the tremolo circuit 5 and the vibrato circuit 2 and in doing so controls the level of reverb effect in the modulated output because the reverb effect passes through the tremolo circuit and appears in the tremolo circuit output . the configuration in fig1 results in a preamplifier having a reverb effect and a tremolo / vibrato effect wherein the reverb circuitry operates independently of the tremolo and vibrato . in fig2 the oscillator circuit 9 is shown in detail . the oscillator circuit 9 has a frequency adjustment consisting of a variable resistor 10 for varying the frequency of the oscillator output signal and thus the speed of the vibrato or tremolo effect . the oscillator utilizes an electron tube 11 of the twin triode variety as an active element . one triode is used in an oscillator 12 while the other is used in an amplifier circuit 13 to provide the oscillator output signal of such a magnitude so as to drive the modulation circuit 4 , shown in fig1 . a connector 14 is provided so that an external vibrato - tremolo switch may be connected . the vibrato - tremolo switch when closed causes the oscillator to cease oscillating and thus turns off the vibrato and the tremolo effect . the vibrato - tremolo switch provides a remote means for controlling the electron tube preamplifier . referring now to fig3 a detailed schematic of the variable gain amplifier 1 is shown . an audio input signal is applied to the audio input of the variable gain amplifier 1 . a first stage 19 of the variable gain amplifier utilizes one half of a twin triode electron tube 17 and drives a potentiometer 18 with its output . the wiper of potentiometer 18 is connected to the input of a second stage 20 of the variable gain amplifier 1 . the potentiometer 18 serves as a gain adjustment and thus controls the dwell of the reverb effect . the output stage 22 of the variable gain amplifier 1 utilizes transformer tr2 to couple its output to the reverb tank 23 . the reverb tank 23 then adds the reverb effect to the output stage output with a reverb effect output signal appearing at the output of the reverb tank 23 . a jack 24 is connected to the output of the reverb tank 23 so that an external reverb switch 25 may be used remotely to turn off the reverb effect by grounding the output of the reverb tank 23 . fig4 shows a detailed schematic of the modulation circuit . the controllable resistance 6 includes an opto - isolator gas discharge tube 26 and a potentiometer 27 . the oscillator output signal is applied to the input of the controllable resistance and drives the opto - isolator gas discharge tube 26 . the photo - resistive element 28 of the opto - isolator gas discharge tube 26 has a resistance that varies with the photon emissions of the opto - isolator gas discharge tube 26 . the resistance characteristic with respect to time is generally sawtooth in nature , with the period of the sawtooth characteristic coinciding with a firing of the opto - isolator gas discharge tube . one side of this photo - resistive element 28 is connected to ground and at the other side it is connect to the wiper of potentiometer 27 . the potentiometer 27 has a first terminal connected to ground and a second terminal connected to the pole of vibrato / tremolo selector switch 7 . varying the wiper position changes the range of variation of the controllable resistance to ground at the second terminal . the potentiometer 27 thus serves as a resistance range adjustment and thereby controls the depth of the tremolo and vibrato effects . it has been found that the use of a potentiometer with a reverse audio taper as potentiometer 27 lends itself well to the control of the vibrato effect . however , the invention does not limit itself to this type of potentiometer . the vibrato / tremolo selector switch 7 connects the controllable resistance to one of the tremolo circuit 5 and the vibrato circuit 2 thus determining which effect is produced . the vibrato circuit 2 utilizes half of a twin triode electron tube 29 as an active element in a cathode follower amplifier . the controllable resistance 6 is capacitively coupled via c3 to a control grid of the cathode follower amplifier loading the bias circuit and the audio input signal applied to the audio input 16 thus creating a modulated output at the output of the cathode follower amplifier and thus a vibrato effect . the vibrato effect comprises both distortion and clipping of the modulated output thus introducing harmonic frequencies of the input audio signal and thus a fluctuation in the harmonic content of the modulated output so as to introduce what is perceived to be shimmering of upper frequencies of the audio spectrum while introducing a lesser amount of this effect upon lower frequencies of the audio spectrum . the selection of the value of c3 controls the quality of the vibrato effect and may be varied to achieve a desired range of distortion and clipping . generally , a value of 0 . 022 microfarads in conjunction with the associated circuitry , provides an even balance of the vibrato effect across the audio spectrum as a listener perceives the effect . however , while a value of 0 . 022 microfarads provides a balance as stated , values in the range of 0 . 01 - 0 . 1 microfarads may be employed to achieve a desired balance . lower values of capacitance accentuate the effect in the upper frequency range of the audio spectrum . although a range of capacitance has been noted , it is understood that it is the time constants of the bias circuit that are created due to the controllable resistance that are of importance in achieving the desired effect . when modulation is not applied , the cathode follower serves as low output impedance buffer for the audio input signal so that it may then be mixed in the mixer circuit with the reverb effect present at the output of the tremolo circuit 5 . the mixer circuit 8 controls the desired amount of reverb in the modulated output signal appearing at the modulated output 30 by means of mixer potentiometer 31 . mixer potentiometer 31 has a wiper connected to the modulated output 30 , a first terminal connected to the output of the tremolo circuit 5 , an output of the vibrato circuit 2 . the wiper position determines the levels of the output signals of the tremolo circuit 5 , and the vibrato circuit 2 that appear at the modulated output 30 and thus the amount of reverb effect present . the tremolo circuit 5 includes the second half of the twin tetrode electron tube 29 &# 39 ; in an amplifier circuit 32 for amplifying the reverb effect output signal and isolating the reverb tank 23 from the following circuitry . the output of the amplifier circuit 32 is capacitively coupled to a tone control circuit 34 including tone adjustment potentiometer 33 , capacitor c1 , and capacitor c2 . the controllable resistance 6 is selectably coupled via vibrato / tremolo selector switch 7 to a first terminal of the tone adjustment potentiometer 33 where the output of the amplifier circuit is also coupled . a second terminal of the tone potentiometer 33 is coupled to ground via capacitor c1 . a wiper of tone potentiometer 33 is capacitively coupled to the first terminal of mixer potentiometer 31 in the mixer circuit 8 . the values of mixer potentiometer 31 , tone potentiometer 33 , capacitor c1 , and capacitor c2 are such that the position of the wiper of the tone potentiometer 33 primarily determines the amount of attenuation of higher audio frequencies appearing at the modulated output 30 . the value of c2 being chosen so as to have an impedance comparable to the mean impedance of the mixer circuit 8 at a frequency in the mid - range of the audio spectrum . the controllable resistance 6 loads down the output of the amplifier circuit 32 thereby modulating the amplified reverb effect output signal . the controllable resistance 6 also loads the tone potentiometer 33 thereby modulating the attenuation of the tone control circuit 34 . a tremolo effect is thus produced upon the modulated output signal . the tremolo effect produced comprises fluctuation in amplitude of the modulated output signal wherein such fluctuation is perceived to be as substantially even across the audio frequency spectrum . the electron tube preamplifier as shown in fig1 - 4 provides both a reverb effect and a tremolo or vibrato effect . the reverb effect may be used simultaneously with either the tremolo or vibrato effects . each effect may be turned off via the use of remote switches connected to the electron tube preamplifier . the adjustments for the dwell , speed , depth , and mixer are all continuously variable . thus a combination of features is provided that is not existing in the prior art . the electron tube preamplifier along with power supply circuitry is housed in a chassis with dimensions of 183 / 4 &# 34 ;× 8 &# 34 ;× 71 / 8 &# 34 ;. this permits the electron tube amplifier to be more readily transportable than electron tube amplifiers of the prior art having a reverb effect because of their larger dimensions . having described a preferred embodiment of the invention with reference to the accompanying drawings , it is to be understood that the invention is not limited to the precise embodiment disclosed , and that various changes and modifications may be effected therein by one skilled in the art without departing from the scope or spirit of the invention defined in the appended claims . | 7 |
the present invention will now be described in detail with reference to a few preferred embodiments thereof as illustrated in the accompanying drawings . in the following description , numerous specific details are set forth in order 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 some or all of these specific details . in other instances , well known process steps and / or structures have not been described in detail in order to not unnecessarily obscure the present invention . while not wishing to be bound by theory , it is believed by the inventor herein that in a plasma processing system , that faceting and / or corner sputtering ( generically , etch profile ) is strongly influenced by ion energy . ion energy , in turn , is strongly influenced by the rf configuration of the bias rf signal , particularly to the frequency component of the bias rf signal . the ion energy is also influenced by the power component of the bias rf signal . the invention thus addresses the use of bias rf signal configuration in plasma processing systems in order to minimize faceting and / or corner sputtering and / or improves the vertical etch profile in dielectric etches , particularly in dielectric etched through low - k layers . it is believed that plasma is generally comprised of weakly ionized plasma . because the plasma discharge is rf driven and weakly ionized , electrons in the plasma are not in thermal equilibrium with ions . that is , while the heavier ions efficiently exchange energy by collisions with the background gas ( e . g ., argon , etc . ), electrons absorb the thermal energy . because electrons have substantially less mass than that of ions , electron thermal velocity is much greater than the ion thermal velocity . this tends to cause the faster moving electrons to be lost to surfaces within the plasma processing system , subsequently creating positively charged ion sheath between the plasma and the surface . ions that enter the sheath are then accelerated into the surface . lower bias rf frequencies tend to cause plasma ions to cross the sheath in less than one rf cycle . generally speaking , lower bias rf frequencies tend to result in higher ion energy , which leads to faceting and / or corner sputtering if the rf bias signal not optimized . likewise , higher bias rf frequencies tend to cause plasma ions take several rf cycles to cross the sheath . generally speaking , the higher bias rf frequencies tend to result in lower ion energy , which results in inadequate etching or non - anisotropic etching if the rf bias signal is not optimized . it is believed that if the ion energy is not properly optimized , the etch is slowed down to the point where the etch rate becomes unduly slow for efficient production . alternatively and / or additionally , faceting and / or corner sputtering occurs . fig3 shows the situation wherein the ion energy is not optimized during the imd trench etch that is employed to create a second metal layer and etch through a via hole to contact barrier layer 104 , resulting in cornering sputtering / faceting . in comparison to etch profile 118 in fig1 h , etch profile 416 has been substantially corrupted due excessive ion energy ( e . g ., by using a bias rf signal with an unduly low frequency ), causing severe faceting and / or corner sputtering . this corner sputtering can be clearly seen by the excessive material removed from the corner regions in mask layer 102 and imd layer 106 . fig4 shows the situation wherein the ion energy is not optimized during the imd trench etch that is employed to create a second metal layer and etch through a via hole to contact barrier layer 104 , resulting in a taper trench profile and an incomplete via etch . referring now to fig5 , a simplified diagram comparing faceting ( represented by the dashed line and measured against axis 502 ), etch rate through the low - k layer ( represented by the solid line and measured against axis 504 ) as a function of the bias rf frequency ( shown on axis 506 ) at a given power level . faceting may be measured using conventional faceting measurement methodology . fig5 intends to illustrate that as the bias rf frequency is increased , the etch rate increases and the amount of faceting / corner sputtering decreases ( e . g ., from about 2 mhz to about 60 mhz in our example ). in particular , the increase in etch rate is rapid to about 30 mhz , and then increases less rapidly to about 60 mhz where the etch rate essentially flattens out until about 70 mhz . after about 70 mhz , the etch rate begins to slow down dramatically ( e . g ., from about 70 mhz to about 100 mhz ), signifying that the ion energy level is now below what is necessary for an efficient etch . at the bias rf frequency of 60 mhz 512 , it is observed by the inventors that the etch rate is at its maximum while the faceting is near its minimum . however , an advantageous process window exists when the bias rf signal is between about 30 mhz and about 80 mhz , and even an even more advantageous process window exists when the bias rf signal is between about 45 mhz and abut 75 mhz where the etch rate is high and the faceting / corner sputtering is low . generally speaking , increasing the bias rf power at a given bias rf frequency setting will cause an increase in both the etch rate and the amount of faceting / corner sputtering . too much bias rf power will cause an excessive amount of faceting / corner sputtering while too little bias rf power will unduly decrease the etch rate . thus , power setting is another knob for controlling the process to stay within the desired etch rate vs . faceting / corner sputtering parameters . in accordance with one embodiment of the invention , in order to optimize the plasma etch rate while also minimizing faceting in a plasma processing system , a bias rf signal of between about 27 mhz and about 90 mhz in frequency may be employed for a dual damascene trench etch through the low - k dielectric layer . bias frequency is important as it controls the ion energy distribution . at a higher bias frequency , the ion energy distribution is narrow and contributes to the reduction of the corner sputtering / faceting problem . the bias rf signal is preferably selected with an optimal combination of bias rf frequency / bias rf power such that the ion energy is optimized and minimal and / or commercially acceptable faceting and corner sputtering is achieved while maintaining a commercially acceptable vertical profile . as the term is employed herein , commercially acceptability denotes that the result falls within specification for satisfactory operation of the final semiconductor product under fabrication . the optimal bias frequency / bias power combination may be empirically determined for a test substrate and the optimal parameters found may be employed during production . of course the optimal bias frequency / bias power combination varies depending on the chemistry employed and the composition of the layer being etched . for example , at about 27 mhz of bias frequency , the rf power setting may be between about 100 w and about 1500 w , more preferably between about 200 w and 1 , 200 w , and preferably at about 400 w . for example , at about 90 mhz of bias frequency , the rf power setting may be between about 200 w and about 2 , 000 w , more preferably between about 400 w and 1 , 500 w , and preferably at about 1 , 000 w . in accordance with another embodiment of the invention , in order to optimize the plasma etch rate while also minimizing faceting in a dual frequency triode plasma processing system , a bias rf signal of between about 30 mhz and about 80 mhz in frequency may be employed . the bias rf signal is preferably selected with an optimal combination of bias rf frequency / bias rf power such that the ion energy is controlled and minimal and / or commercially acceptable faceting and corner sputtering is achieved while maintaining a commercially acceptable vertical profile . for example , at about 30 mhz of bias frequency , the rf power setting may be between about 100 w and about 1500 w , more preferably between about 200 w and 1 , 200 w , and preferably at about 400 w . for example , at about 80 mhz of bias frequency , the rf power setting may be between about 200 w and about 1 , 800 w , more preferably between about 400 w and 1 , 200 w , and preferably at about 800 w . in accordance with another embodiment of the invention , in order to optimize the plasma etch rate while also minimizing faceting in a dual frequency triode plasma processing system , a bias rf signal of between about 45 mhz and about 75 mhz in frequency may be employed . the bias rf signal is preferably selected with an optimal combination of bias rf frequency / bias rf power such that the ion energy is controlled and minimal and / or commercially acceptable faceting and corner sputtering is achieved while maintaining a commercially acceptable vertical profile . for example , at about 45 mhz of bias frequency , the rf power setting may be between about 100 w and about 1500 w , more preferably between about 200 w and 1 , 200 w , and preferably at about 400 w . for example , at about 75 mhz of bias frequency , the rf power setting may be between about 200 w and about 1 , 800 w , more preferably between about 400 w and 1 , 200 w , and preferably at about 800 w . in accordance with another embodiment of the invention , in order to optimize the plasma etch rate while also minimizing faceting in a dual frequency triode plasma processing system , a bias rf signal of about 60 mhz is found to be particularly suitable . the bias rf signal is preferably selected with an optimal combination of bias rf frequency / bias rf power such that the ion energy is controlled and minimal and / or commercially acceptable faceting and corner sputtering is achieved while maintaining a commercially acceptable vertical profile . for example , at about 60 mhz of bias frequency , the rf power setting may be between about 200 w and about 1 , 500 w , more preferably between about 400 w and 1 , 000 w , and preferably at about 600 w . in conjunction with the guidelines discussed above , a graph similar to fig5 also furnishes a way for a process engineer to tune a particular dielectric etch process to a particular plasma processing chamber configuration . if a set of data for etch rate vs . faceting / corner sputtering is empirically obtained for a range of bias rf frequencies of interest and / or a range of rf power settings of interest , the process engineer can more accurately obtain the desired process window with the bias rf frequency knob and the bias rf power knob for a particular dielectric etch process and / or a particular plasma processing system while still achieving the desired parameters ( i . e ., at particular values or within an acceptable range of values ) with respect to the etch rate and faceting / corner sputtering ( generically , etch profile ). with respect to the discussion above , it is noted that the plasma processing chamber may be of a dual frequency design , i . e ., one having a separate source rf signal and a separate bias rf signal . the source rf signal and the bias rf signal may be provided in a dual - frequency diode configuration ( wherein both the source rf signal and the bias rf signal are applied to the substrate such as in an excelan ™ series machine by lam research corporation of fremont , calif . ), a dual - frequency triode configuration ( wherein only the rf bias signal is applied to the substrate ). additionally , the plasma processing chamber may be of a single frequency design , i . e ., only rf bias signal with no separate source rf signal . since the bias rf signal controls the ion energy , proper control of the bias rf signal results in the desired minimization of faceting and corner sputtering while maintaining a commercially acceptable vertical profile . it has been found that with a single - frequency design , a bias rf frequency signal of between about 45 mhz and about 75 mhz is particularly useful for minimizing faceting and / or corner sputtering while maintaining the aforementioned commercially acceptable vertical etch profile . in particular , it has been found that the single frequency design , when operated at a bias rf signal of about 60 mhz is particularly well - suited to for minimizing faceting and / or corner sputtering while maintaining the aforementioned commercially acceptable vertical etch profile for a dual - damascene trench etch . furthermore , it is not necessary that the plasma processing chamber be of a capacitively coupled plasma design . for example , the top rf source may be an inductive coil ( such as those in tcp ™ plasma etchers available from lam research corporation of fremont , calif . ), and the bias rf signal may still be provided to the substrate and controlled during etching . likewise , the top rf source may be an ecr ( electron cyclotron resonance ) source , and the bias rf signal may still be provided to the substrate and controlled during etching . in fact , it is contemplated that the source rf signal may be furnished using any rf signal generation arrangement since the invention deals with controlling the bias rf frequency and / or bias rf power to achieve the desired etch rate and low faceting / corner sputtering parameters . while this invention has been described in terms of several preferred embodiments , there are alterations , permutations , and equivalents which fall within the scope of this invention . for example , although the present invention has been described in connection with lam research plasma processing systems ( e . g ., exelan ™, exelan hp ™, exelan hpt ™, exelan 2300 ™, etc . ), other plasma processing systems may be used . it should also be noted that there are many alternative ways of implementing the methods of the present invention . advantages of the invention include the optimization of rf configurations in a plasma processing system , in which an optimum set of frequencies and an optimum set of power settings are employed to substantially control faceting . additional advantages include optimizing rf configurations in dual damascene plasma processing applications in order to substantially control faceting . having disclosed exemplary embodiments and the best mode , modifications and variations may be made to the disclosed embodiments while remaining within the subject and spirit of the invention as defined by the following claims . | 7 |
in the description which follows , like parts are marked throughout the specification and drawings with the same numerals , respectively . the drawing fig3 b through 3d are intended to be viewed end to end as indicated by the arrangement of the brackets 3b through 3d in fig2 . in the description which follows , the terms &# 34 ; upward &# 34 ; and &# 34 ; downward &# 34 ; are used for convenience in describing the relative positions of the components of the apparatus when viewing the drawings and in the normal attitude of the apparatus in most applications . however , those skilled in the art will appreciate that the apparatus may be inverted or used in a generally horizontal or other directional attitude . referring to fig1 briefly , the apparatus of the present invention comprises a device known in the art as a drilling jar which is adapted to deliver impact blows in an upward or downward direction to dislodge a drill stem which may be stuck in a well bore or to dislodge a component which is to be retrieved from a well bore or the like . fig1 illustrates the drilling jar of the present invention disposed in a generally vertical well bore 10 , and generally designated by the numeral 12 . the drilling jar 12 is provided with an upper end portion having a threaded box provided with internal threads for connection to the lower end of a drill stem 16 . the drill stem 16 normally extends upward to connection with a component for rotating the stem such as a kelly or the like , not shown , engaged with suitable rotary driving apparatus mounted on a drilling rig , also not shown . the drill stem 16 would also be adapted for vertical movement under the control of hoisting apparatus such as a drawworks or the like comprising part of the drilling rig . the lower end of the jar 12 includes a threaded pin portion adapted to be connected to suitable drill collars 20 when the jar is interposed in a conventional drill string , as shown . it will be understood that the jar 12 may be used in various arrangements and the arrangement illustrated in fig1 is exemplary of a particular location and specific application of the jar . as with most drilling operations , a cutting evacuation fluid is pumped down through a central bore in the drill stem and in the jar 12 , through orifices in a drill bit 21 and up through the annulus formed between the drill stem and the well bore . referring now to fig2 the drilling jar 12 is illustrated in the totally collapsed or telescoped condition and is characterized by an elongated cylindrical body member , generally designated by the numeral 22 , which is made up of an upper sub part 24 , a main body member 26 , a floater body 28 and a lower sub 18 . the upper sub 24 is connected to the main body 26 through a conventional cooperating threaded portion 30 , fig3 a , with appropriate sealing members 32 interposed between the upper end of the main body member 26 and a reduced diameter portion of the upper sub . the upper sub 24 also includes an upwardly facing annular impact surface 34 which is adapted to be impacted by a removable cylindrical anvil member or knocker 36 having a downwardly facing anvil surface 37 . the knocker 36 is suitably removably connected to the upper end portion 14 of an elongated mandrel , generally designated by the numeral 42 , by cooperating threads 38 . referring to fig3 d , the lower end of the main body member 26 is threadedly connected to an upper end of the floater body 28 and the floater body is threadedly connected at its lower end to the upper end of the lower sub 18 . the lower sub 18 and the floater body 28 are both provided with suitable annular seals 40 to prevent leakage of fluid in the well bore into the interior of the jar body at the respective threaded connections . in the preferred embodiment of the jar 12 , the upper sub 14 is integrally formed with the elongated cylindrical mandrel member 42 which is disposed in telescoping sleeved relationship within the body 22 . referring to fig3 a through 3c , the mandrel 42 includes an elongated first part 41 having a threaded portion 43 at its lower end which is adapted to be engaged with a member 44 comprising a continuation of the mandrel and commonly referred to as a wash pipe . the wash pipe 44 extends downwardly through the body member 26 , the floater body 28 and into an interior bore 19 of the sub 18 . the mandrel 42 , including part 41 and the wash pipe 44 , is operable to move axially relative to the body 22 and is journaled for relative axial sliding movement by spaced apart sleeve bearings 46 disposed in the sub 24 , bearings 48 disposed in the floater body 28 , and additional bearings 50 disposed in the upper end of the lower sub 18 . the bearings 46 , 48 and 50 may be formed of suitable bearing material such as a carbon filled plastic or the like . referring to fig3 a , an annular wiper seal ring 52 is disposed in a suitable recess in the sub 24 and engageable with a cylindrical surface or seal diameter 54 of the mandrel part 41 . the wiper 52 is provided with a bronze backing member 56 . additional o - ring or quad ring type seals 58 may be provided in the sub 24 and sealingly engaged with the surface 54 . the knocker 36 is provided with a plurality of radial passages 37 to permit drilling fluid to flow freely in and out of the annular chamber 60 formed between the knocker member and the mandrel 42 . the downward facing annular end face 61 of the sub 24 faces an elongated interior chamber formed between the cylindrical surface 54 and the body member 26 , which chamber is designated by the numeral 62 . referring to fig3 c , the chamber 62 is also delimited by a reduced diameter or restricted bore portion 64 of the body member 26 . a second annular chamber 66 is formed between the wash pipe 44 , the upper end of the floater body 28 , and a cylindrical interior wall 69 of the body member 26 . the restricted bore portion 64 on the body member 26 is delimited by upper and lower control edges 70 and 71 , the function of which will be described in further detail herein . the mandrel 42 is provided with an improved removable sleeve member generally designated by the numeral 72 in fig3 b . the mandrel sleeve 72 includes an upper transverse anvil surface 74 which is coactable with the anvil surface 61 on the sub 24 to deliver an impact blow to the body 22 and the drill stem connected thereto in response to rapid movement of the mandrel upwardly with respect to the body . the mandrel sleeve 72 is removable from the mandrel part 41 and is nonrotatably secured thereto by two opposed elongated keys 73 interfitted in suitable slots formed in the sleeve and the mandrel part 41 , as shown also in fig4 . the mandrel sleeve 72 is retained on the mandrel part 41 by the wash pipe 44 , as shown . in the secured and locked position of the wash pipe 44 on the mandrel 42 , a small end clearance on the order of 0 . 020 - 0 . 030 inches is permitted between the lower end of the mandrel sleeve and the upper end face 45 of the wash pipe . the wash pipe 44 is also provided with one or more radially disposed locking screws 47 which are seated in a cooperating annular groove 49 in the lower end of the mandrel part 41 to prevent unwanted disengagement of the wash pipe from the remaining part of the mandrel . the mandrel sleeve 72 is prevented from axial displacement upward with respect to the mandrel part 41 by cooperating undercut shoulder portions designated by the numeral 80 in fig3 b . as shown in fig4 the mandrel sleeve 72 is provided with a plurality of circumferentially spaced axially extending splines 75 which are interfitted in cooperating grooves 77 in the body member 26 so that rotary driving torque may be transmitted from the mandrel to the body or vice versa . however , the interfitting splines between the mandrel sleeve 72 and the body part 26 permit relative axial movement of the mandrel 42 with respect to the body 22 . the mandrel sleeve 72 transmits all of the rotary driving torque between the mandrel 42 and the body 22 , provides an anvil surface for delivering impact blows to the body 22 when jarring in the up direction , and may be easily replaced , if damaged or worn , without requiring replacement of the entire mandrel part 41 . moreover , the sleeve 72 is easily removed from the mandrel part 41 by releasing the screws 47 and unthreading the wash pipe 44 from the lower end of the mandrel part whereby the sleeve 72 may be axially removed from the lower end of the mandrel . referring now to fig3 c , and briefly to fig5 the upper portion of the wash pipe 44 is provided with a plurality of circumferentially spaced , axially extending grooves 82 formed in the outer cylindrical surface 68 of the wash pipe and which extend axially downward to a cylindrical portion 84 having a circumferential seal ring groove 86 formed therein . a second set of axial grooves 88 corresponding substantially to the grooves 82 extend between the cylindrical portion 84 and a second axially spaced cylindrical portion 90 having a circumferential seal ring groove 92 formed therein . downward from the seal ring groove 92 , the outer diameter of the wash pipe is defined by a cylindrical surface 94 which is of a diameter less than the cylindrical surface portion 68 . referring still further to fig3 c , respective positive mechanical seal assemblies 96 and 98 are disposed in the grooves 86 and 92 . the seal assemblies 96 and 98 will be described in further detail herein . the seal assemblies 96 and 98 are adapted to be in sealing engagement with the wall of the restricted bore 64 to substantially seal the chamber 66 from the chamber 62 whereby fluid transferring from one chamber to the other , must pass through a control orifice formed in one of two plugs 100 , depending on the position of the wash pipe with respect to the restricted bore 64 . referring briefly to fig8 the plug 100 is characterized as a round head screw having an orifice 102 extending therethrough and formed of a predetermined diameter . the plugs 100 are interposed in respective passages 101 and 103 which interconnect the grooves 82 with one of the grooves 88 , and the one groove with the portion of the chamber 66 below the cylindrical part 90 of the wash pipe , respectively , as shown . relatively unrestricted flow of fluid between the chambers 62 and 66 is also provided around the respective seal assemblies 96 and 98 by back - to - back check valves 104 and 106 interposed in suitable passages 108 and 110 , respectively . the passages 108 and 110 are arranged to interconnect one or more of the grooves 82 with another one of the grooves 88 and with the portion of the chamber 66 below the enlarged diameter portion 90 of the wash pipe as shown in fig3 c . the check valves 104 and 106 provide for fluid flow to effectively bypass the respective seal assemblies 96 and 98 when the seals are passing through the restricted bore 64 depending on the direction of movement of the mandrel 42 with respect to the body 22 . the outer diameter of the wash pipe 44 between the cylindrical diameter portions 84 and 90 is sufficiently less than the restricted bore 64 to permit relatively unrestricted flow of fluid between respective ones of the grooves 88 . the grooves 88 could be replaced by an annular recess but the lands formed between the grooves are provided to assist in guiding the wash pipe in the bore 64 . the chambers 62 and 66 are adapted to be filled with hydraulic fluid , preferably a fluid having a reduced viscosity variation with temperature , but having suitable lubricity to minimize wear on the cooperating sliding surfaces of the mandrel and the bearings as well as the splines 75 , and the seal assemblies 96 and 98 with respect to the restricted bore 64 . even though the cooperating parts of the jar 12 are designed for minimal wear , the upper end of the floater body 28 is adapted to provide a reservoir portion 29 which , in the normal attitude of the jar 12 , will collect loose wear material which settles out of the chambers 62 and 66 . referring to fig3 d , hydraulic fluid may be introduced into the entire interior cavity formed between the mandrel and body portions of the jar , including the chambers 62 and 66 , through a reservoir chamber 110 formed between the lower end of the wash pipe 44 and the inner bore wall 112 of the floater body 28 . a removable reservoir fill plug 114 is suitably disposed in a cooperating threaded passage in the floater body 28 , as illustrated , for filling the aforementioned chambers . the floater body 28 is provided with elongated passages 116 which interconnect the chamber 110 and the chamber 66 . the minimum working pressure of the fluid within the chambers 110 , 62 and 66 is preferably maintained at a level corresponding to the pressure of the drill cuttings evacuation fluid which is delivered to the bit through an elongated central passage 83 formed by suitable bores in the mandrel part 41 , the wash pipe 44 and a passage 85 in the bottom sub 18 , fig2 . referring further to fig2 and fig3 d , fluid in the passage 83 flows into the annular space between the circumferential surface 94 of the wash pipe and the bore wall 19 of the sub 18 into a passage 120 to a chamber formed between the upper end face 121 of the sub 18 and an annular floater piston 122 . the piston 122 also defines the lower end of the chamber 110 . pressure exerted on the piston 122 by fluid introduced through the passages 120 will cause the pressure in the chambers 62 , 66 and 110 to be nominally equal to the pressure in the passage 83 , which pressure normally exceeds the fluid pressure in the wall annulus . accordingly , any leakage of fluid with respect to the chambers 62 , 66 and 110 will tend to flow out into the well annulus to reduce any tendency to contaminate the interior fluid chambers of the jar 12 . pressurizing the chambers 62 , 66 and 110 to a minimum nominal pressure corresponding to the drilling fluid pressure eliminates any pressure differential across the seals between the passage 83 and these chambers which would tend to cause leakage of the drill cuttings evacuation fluid into the chambers from the passage 83 . moreover , the provision of the floater piston 122 and the reservoir 110 reduces or substantially eliminates any adverse effects resulting from fluid compressibility entrained gases in the hydraulic fluid and thermal expansion of the fluid . the jar 12 may be operated in either the totally telescoped or collapsed condition as illustrated in the drawing figures , in a partially extended condition of the mandrel 42 with respect to the body 22 , and in a totally extended condition of the mandrel with respect to the body wherein the cooperating anvil surfaces 61 and 74 are in engagement . an operation to provide an upward jarring action on the body 22 and the drill stem portion connected to the sub 18 will now be described assuming the jar is initially in the operating condition illustrated in the drawing figures or at least in a condition wherein the seal assembly 98 is below the control edge 71 , viewing fig3 c . if an upward jar is required , the rig operator hoists the drill stem to begin pulling up on the mandrel 42 . as the mandrel and wash pipe assembly move upward relative to the body 22 , and the seal assembly 96 passes the control edge 71 thereby moving into sealing engagement with the wall of the restricted bore 64 , the movement of the mandrel is not retarded thanks to the provision of the passage 108 and the check valve 104 which permits free flow of fluid from the chamber 62 into the chamber 66 . fluid is displaced from the chamber 62 during upward movement of the mandrel 42 due to the fact that the diameter of the portion of the wash pipe 44 delimited by the cylindrical surface 68 is greater than the diameter of the cylindrical surface 54 which is in sealing engagement with the upper sub 24 . accordingly , as the wash pipe 44 moves further into the chamber 62 , the volume of this chamber is decreased and fluid must be displaced into the chamber 66 , which is permitted because the volume of chamber 66 is increasing due to the difference between the diameters of the cylindrical surfaces 68 and 94 . as the seal assembly 96 passes upwardly through the restricted bore 64 , fluid is permitted to flow freely into the chamber 66 until the seal assembly 98 passes the control edge 71 and moves into sealing engagement with the wall of bore 64 . at this point , as the mandrel 42 is pulled upward by the drill stem , fluid displaced from the chamber 62 must flow through the orifice 102 in the lower plug 100 . the retarding effect of the orifice will result in an increased tension in the drill stem above the jar 12 and the stem will be elastically elongated to become , in effect , a tension spring . as the mandrel 42 moves upward with respect to the body 22 at the controlled retarded rate , the tension in the drill stem is maintained until the seal assembly 98 moves upwardly past the upper control edge 70 . at this point , fluid in the chamber 62 may flow freely into the chamber 66 to release the mandrel for sudden relatively free upward movement . since the drill stem , being of substantial length and having undergone substantial elongation , is now permitted to relax somewhat , the mandrel is moved upward rapidly until the anvil surface 74 engages the surface 61 with a substantial impact or jarring below . in normal drilling operations , the jar 12 would be extended , that is , the mandrel 42 would be extended from the upper end of the body 22 to its limit position with the surfaces 61 and 73 engaged . accordingly , when the rig operator sensed the need for applying an upward jarring movement to , for example , loosen a stuck portion of the drill stem below the sub 18 , the operator would slack off hoist tension on the drill stem until the hoist load weight indicator displayed a marked decrease in tension on the drill stem . the weight loss would indicate that the mandrel 42 had moved axially downward with respect to the body 22 until the seal assembly 96 passed the control edge 70 into the restricted bore 64 . the operator could then mark the position of a portion of the drill stem or kelly at the rig floor with respect to a reference point ( such as the kelly bushing ). in the position wherein the seal assembly 96 has passed downward past the control edge 70 the seal assembly 98 is in the restricted bore 64 or has passed below the control edge 71 , depending on the axial spacing of the grooves 86 and 92 and the spacing of the control edges 70 and 71 . the operator could then apply a predetermined upward pull on the drill stem in excess of the drill stem weight to impose an axial load on the mandrel , for example , 50 , 000 lbs ., and set the brake on the drawworks . the action of the jar would then be a retarded upward movement of the mandrel 42 until the seal assembly 98 cleared the control edge 70 and the mandrel would be free to permit rapid elastic contraction of the drill stem to draw the mandrel rapidly upwardly until the anvil surfaces 74 and 61 impacted each other . the operator , upon sensing the tripping of the jar , could then repeat the cycle of cocking or resetting the jar by slacking off less weight on the drill stem with each repeated cycle in order to not let the seal assembly 98 move quite as deep into the restricted bore 64 between the control edges 70 and 71 , thereby taking less time to pull the jar through the tensioning and tripping portion of the cycle . by viewing the position of the mark placed on the drill stem after each jarring action is completed , the operator may recognize any upward movement or loosening of the stuck portion of the stem . the aforedescribed procedure is exemplary but is indicative of a preferred method of using the inventive jar 12 . in order to perform a jarring action in the downward direction , and assuming that the jar in in the extended condition initially , the mandrel 42 is lowered into the body 22 . as the seal assembly 98 passes the control edge 70 and into the restricted bore 64 pressure fluid is allowed to flow freely around the seal assembly through the passage 103 and check valve 106 , from chamber 66 to chamber 62 , until the seal assembly 96 passes the control edge 70 and into the restricted bore 64 . at this point , movement of fluid from the chamber 66 to the chamber 62 may take place substantially only by flow through the orifice 102 in the plug 100 adjacent to the seal assembly 96 . as the seal assembly 96 enters the restricted bore 64 , the drill stem above the jar 12 may undergo some compressive deflection under its own weight as may that portion of the drill stem below the jar . moreover , the weight of the drill stem itself may be sufficient to deliver a substantial blow by engagement of the cooperating anvil surfaces on the sub 24 and the knocker 36 . this action will take place as the seal assembly 96 moves downward past the control edge 71 whereby fluid may rapidly flow out of the chamber 66 into the chamber 62 to permit rapid collapsing of the mandrel into the body and the deliverance of an impact blow to the anvil surface 34 . repeated downwardly directed impact blows may be obtained by pulling upward on the mandrel 42 until the seal assembly 96 moves past the control edge 71 and at least somewhat into the restricted bore 64 , followed by slacking off of the hoisting effect on the mandrel sufficiently to permit the weight of the drill stem to force the mandrel back toward the collapsed condition . the operator may be assured that the seal assembly 96 has moved upward past the control edge 71 by observing an increased reading on the hoist load or weight indicator caused by movement of the seal assembly 98 into the restricted bore 64 . thanks to the provision of the separate upper and lower orifice plugs 100 the orifice size may be selectively varied in one or both plugs to vary the maximum jarring action in one or both directions and to compensate for various types of fluid as well as operating temperature effects on fluid viscosity . although only one orifice plug is shown for controlling the flow around the respective seal assemblies , multiple passages and orifices could be provided to bypass each seal 96 and 98 . those skilled in the art will recognize from the foregoing description that an improved hydraulic bidirectional drilling jar is provided by the apparatus 12 . moreover , the jar 12 may also be used as a suspension tool to control weight on the drill bit . for example , during drilling operations , the rig operator may observe the hoist weight indicator to sense an increase in the suspended weight of the drill stem and then lowering the drill stem a predetermined length , but not enough to place the seal assemblies 96 or 98 downward past the control edge 70 , followed by setting the drawworks brake until the weight indicator again indicates an increase in the suspended weight of the stem . this procedure can be repeated and as long as the mandrel is not fully extended from the body 22 , the weight on the bit will remain substantially constant . accordingly , the jar 12 may be utilized to control weight on the drill stem and bit below the point in the stem where the jar is located . the development of the improved hydraulic drilling jar 12 includes the provision of the improved seal assemblies 96 and 98 . the operating pressures experienced in the cavities 62 and 66 may result in a pressure differential across the seal assemblies 96 and / or 98 of as much as 40 , 000 to 50 , 000 psi . these operating pressures cannot be withstood by conventional seal elements such as o - rings , quad rings , chevron packings and other conventional elastomeric sealing elements . furthermore , in many instances the operating temperatures experienced by downhole tools , and particularly a tool such as the jar 12 , cannot be withstood by the aforementioned types of seals . although a conventional split cylindrical piston ring type seal may be capable of withstanding the aforementioned pressure differentials and the temperature conditions , this type of seal provides a leakage path at the gap where the ring itself is split . this gap becomes another factor in the overall liquid flow area which controls the dashpot action of the drilling jar . moreover , conventional piston ring type seals have a tendency to fail when required to move from a radially free position to a constrained position and vice versa such as is experienced by a seal entering and leaving the restricted bore 64 . in accordance with the present invention , an improved seal assembly is provided by a somewhat spiral type seal ring which is disposed around the periphery of an axial split cylindrical piston ring seal member . referring now to fig6 and 7 , the elements making up the seal assemblies 96 and 98 are illustrated in detail , particularly in fig6 . each of the seal assemblies 96 and 98 includes a spiral seal ring generally designated by the numeral 130 . the seal ring 130 comprises a spring tempered metal band of rectangular cross - section and forming aa plurality of convolutions 131 , 132 and 133 . the convolutions 131 , 132 and 133 are configured so as to provide a ring having flat and parallel opposed sides 134 and 136 . the transition between the convolution 131 and 132 is provided by a relatively short axially aligned portion 137 and the transition between the convolution 132 and 133 is provided by a second angled portion 139 . the distal end of the convolution 131 is tapered at 140 and the opposing distal end of the convolution 133 is tapered at 142 so that the ring 130 assumes the shape of a substantially cylindrical annular member with flat parallel sides or end faces 134 and 136 . the tapered ends 140 and 142 are feathered to essentially a sharp edge to provide a smooth surface of the faces 134 and 136 , respectively , thereby minimizing any possible leakage space formed along the respective radially extending end edges of the ring . the convolutions 131 , 132 and 133 are adapted to lie contiguous with each other to minimize or eliminate any leakage flow path between the axial facing surfaces of the convolutions . alternatively , the convolutions of the ring 130 could follow a continuous helix and the parallel surfaces 134 and 136 could be formed by grinding the outer end faces of the convolutions 131 and 133 . the seal assemblies 96 and 98 also include , respectively , an annular piston ring type seal member 146 provided with an axial gap 148 . the ring 146 is proportioned to be capable of elastic radial contraction to fit within the inside diameter or bore of the spiral seal ring 130 and thereby urge the ring 130 to expand radially to the extent that the outside circumferential surface of the ring 130 will be in fluid sealing engagement with the wall surface of the bore 64 . in the assembled relationship of the rings 130 and 146 , the gap 148 is preferably rotatively positioned opposite the tapered end portions of the convolutions 131 and 133 . referring to fig7 the seal assembly 98 is shown , by way of example , disposed in the groove 92 . the scale of drawing fig7 is exaggerated somewhat to show the small clearances that will be developed as a result of pressure fluid acting against the seal assembly in , for example , the operating condition wherein the mandrel 42 is being pulled out of the body 22 and a pressure differential has developed across the restricted bore 64 between the control edges 70 and 71 . the pressure of the fluid trapped in the chamber 62 thus acts against the face 134 forcing the seal ring 130 against sidewall 93 of groove 92 . the small clearance developed between the surface 134 and the groove opposite sidewall 95 will allow fluid to flow into the groove and also act in a radial outward direction against the inner diameter 150 of the seal ring 146 . accordingly , pressure fluid entering the groove 92 from either end of the restriction formed by the bore 64 will aid in forcing the seal ring members 130 and 146 into engagement with each other and radially outward into sealing engagement with the wall surface of bore 64 , as illustrated in fig7 . however , the seal assembly 98 is required to perform a sealing function in only one direction and the seal assembly 96 is operable , in its groove 86 , to perform a sealing function in the opposite direction . the provision of the composite seal assembly formed by the seal rings 130 and 146 eliminates the leakage path formed by the axial gap in conventional piston rings and also provides for radial expansion and contraction of the seal assembly for insertion and removal of the seal assemblies with respect to the grooves 90 and 92 and to provide for positive engagement of the seal assemblies with the wall of the restricted bore 64 . moreover , the contiguous flat sides of the convolutions of the spiral seal ring 130 and the tapered free end minimizes the fluid leakage flow path area which , in fact , is nil with the configuration of the member illustrated and described . the tapered ends 140 and 142 may be eliminated in the arrangement illustrated using the piston ring seal 146 as long as the piston ring is of a width at least as great as the spiral ring whereby fluid cannot flow radially inward or outward due to the seal barrier formed by the piston ring seal itself . the seal ring 130 may be formed of a suitable material such as beryllium copper or phosphor bronze of spring temper grade . the piston ring type seal member 146 may be formed of a suitable piston ring material such as steel or cast iron . the arrangement of the seal assemblies 96 and 98 is also advantageous in that as they move into and out of engagement with the wall of the restricted bore 64 , radial compression of the seal ring 130 , which is required as the seal assembly engages the control edges 70 or 71 , is obtained without a tendency to break the seal rings 130 or 146 , or the control edges 70 and 71 . the control edges 70 and 71 are defined by respective bevel surfaces intersecting the bore 64 as illustrated . those skilled in the art will appreciate that the jar apparatus 12 is provided with a number of improved features which coact to improve the performance of hydraulic drilling jars and the like and , particularly , those types adapted for use in delivering impact blows in opposite directions . various modifications and substitutions may be made to the specific arrangement disclosed herein without departing from the scope and spirit of the invention as recited in the appended claims . | 4 |
fig1 and the following discussion are intended to provide a brief , general description of a suitable computing environment in which the present invention may be implemented . although not required , the invention will be described in the general context of computer - executable instructions , such as program modules , being executed by a personal computer . generally , program modules include routines , programs , characters , components , data structures , etc ., that perform particular tasks or implement particular abstract data types . as those skilled in the art will appreciate , the invention may be practiced with other computer system configurations , including hand - held devices , multiprocessor systems , microprocessor - based or programmable consumer electronics , network pcs , minicomputers , mainframe computers , and the like . the invention may also be practiced in distributed computing environments where tasks are performed by remote processing devices that are linked through a communications network . in a distributed computing environment , program modules may be located in both local and remote memory storage devices . with reference to fig1 an exemplary system for implementing the invention includes a general purpose computing device in the form of a conventional personal computer 20 , including a processing unit 21 , system memory 22 , and a system bus 23 that couples various system components including the system memory 22 to the processing unit 21 . the system bus 23 may be any of several types of bus structures including a memory bus or memory controller , a peripheral bus , and a local bus using any of a variety of bus architectures . the system memory includes read - only memory ( rom ) 24 and random access memory ( ram ) 25 . a basic input / output system ( bios ) 26 , containing the basic routines that help to transfer information between elements within the personal computer 20 , such as during start - up , is stored in rom 24 . the personal computer 20 further includes a hard disk drive 27 for reading from and writing to a hard disk 39 , a magnetic disk drive 28 for reading from or writing to a removable magnetic disk 29 , and an optical disk drive 30 for reading from or writing to a removable optical disk 31 , such as a cd - rom or other optical media . the hard disk drive 27 , magnetic disk drive 28 , and optical disk drive 30 are connected to the system bus 23 by a hard disk drive interface 32 , a magnetic disk drive interface 33 , and an optical drive interface 34 , respectively . the drives and their associated computer - readable media provide non - volatile storage of computer - readable instructions , data structures , program modules , and other data for the personal computer 20 . although the exemplary environment described herein employs a hard disk 39 , a removable magnetic disk 29 , and a removable optical disk 31 , it should be appreciated by those skilled in the art that other types of computer - readable media that can store data that is accessible by a computer , such as magnetic cassettes , flash memory cards , digital video disks , bernoulli cartridges , random access memories ( rams ), read - only memories ( roms ), and the like , may also be used in the exemplary operating environment . a number of program modules may be stored on the hard disk 39 , magnetic disk 29 , optical disk 31 , rom 24 or ram 25 , including an operating system 35 , one or more application programs 36 , other program modules 37 and program data 38 . a user may enter commands and information into the personal computer 20 through input devices such as a keyboard 40 and pointing device 42 . other input devices ( not shown ) may include a microphone , joystick , game pad , satellite dish , scanner , or the like . these and other input devices are often connected to the processing unit 21 through a serial port interface 46 that is coupled to the system bus 23 , but may also be connected by other interfaces , such as a parallel port , game port or a universal serial bus ( usb ). a display in the form of a monitor 47 is also connected to the system bus 23 via an interface , such as a video card or adapter 48 . one or more speakers 57 may also be connected to the system bus 23 via an interface , such as an audio adapter 56 . in addition to the display and speakers , personal computers typically include other peripheral output devices ( not shown ), such as printers . the personal computer 20 may operate in a networked environment using logical connections to one or more personal computers , such as a remote computer 49 . the remote computer 49 may be another personal computer , a server , a router , a network pc , a peer device or other common network node , and typically includes many or all of the elements described above relative to the personal computer 20 . the logical connections depicted in fig1 include a local area network ( lan ) 51 and a wide area network ( wan ) 52 . such networking environments are commonplace in offices , enterprise - wide computer networks , intranets , and the internet . when used in a lan networking environment , the personal computer 20 is connected to the local area network 51 through a network interface or adapter 53 . when used in a wan networking environment , the personal computer 20 typically includes a modem 54 or other means for establishing communications over the wide area network 52 , such as the internet . the modem 54 , which may be internal or external , is connected to the system bus 23 via the serial port interface 46 . in a networked environment , program modules depicted relative to the personal computer 20 or portions thereof may be stored in the remote memory storage device . it will be appreciated that the network connections shown are exemplary , and other means of establishing a communications link between the computers may be used . the present invention is embodied in the system memory 22 of the computing environment of fig1 . fig2 a and 2b are an architecture diagram illustrating the key components of an exemplary system for implementing the invention on a computer system such as the one illustrated in fig1 . fig2 a and 2b illustrate a management system that includes multiple management applications 62 executing in a user mode 60 . the management system may be any cim schema compliant management system , such as the wmi management system . although embodiments of the present invention may be described here in cooperation with the wmi management system , the present invention is equally applicable to other management systems . reference here to the wmi management system is for illustrative purposes only , and does not limit the applicability of the invention . interfacing with the management applications 62 is a wmi agent 64 . the wmi agent 64 maintains and provides access to a wmi store 65 , which is a database containing management information exposed by the management system . the management information contained in the wmi store 65 comes from multiple providers , such as components 66 and 68 . when the wmi agent 64 receives a request from a management application 62 , for information that is not available in the wmi store 65 , or for notification of events that the wmi agent does not support , the wmi agent forwards the request to an appropriate provider . the provider then supplies the information or event notification requested . one such provider is the wmi extensions to windows driver model ( xwdm ) provider ( the “ wmi provider ”) 70 . the wmi provider 70 includes two parts : a user mode portion of the wdm provider 72 and a kernel mode portion of the wdm provider 74 . the user mode driver 72 communicates with the kernel mode driver 74 in order to pass messages between user mode 60 and kernel mode 76 . thus , the wmi provider 70 allows devices to make management information available to management applications 62 by providing a pipeline between user mode 60 and kernel mode 76 . kernel mode 76 , as shown in fig2 b , includes several hardware devices . the hardware devices shown in fig2 b are hardware storage devices , including : smart disk drives 60 , which includes smart scsi and smart ata / atapi disk drives ; standard , non - smart disk drives , which includes scsi and ata / atapi disk drives 61 ; proprietary disk drives 62 ; other standard storage devices 64 , for example , tape storage devices , dvd roms , cd - roms , etc . ; and non - standard storage hardware , such as a ram disk or a raid controller 65 . each hardware device has an associated device driver . smart hardware devices 60 communicate with a smart aware port driver 70 . for example , a smart scsi device communicates with a scsi port driver , and a smart ata / atapi device communicates with an ata / atapi port driver . although the current implementation of the smart specification only supports scsi and ata / atapi devices , if other devices are implemented as smart devices in the future , the invention shown and described can accommodate additional smart devices in the same manner as the currently supported smart devices . standard , non - smart disk drives 61 communicate with a port driver 71 . proprietary disk drives 62 communicate with a proprietary failure prediction enabled port driver 72 . other standard storage devices 64 , such as tape storage devices , cd - roms , and dvd roms , communicate with a storage device port driver 74 . similarly , non - standard , or proprietary , storage devices , such as a raid controller or a ram disk 65 communicate with a failure prediction enabled storage device driver 75 or a proprietary port driver 72 . a device driver may have an associated failure prediction filter driver . smart hardware devices 60 , e . g ., smart scsi drives and smart ata / atapi drives , do not require a failure prediction filter driver , however , a failure prediction filter driver 80 may optionally be included . standard , non - smart hardware devices 61 , such as a non - smart scsi drive or a non - smart ata / atapi drive , require a failure prediction filter driver 81 . non - standard , proprietary , disk drives 62 may optionally communicate with a failure prediction filter driver 82 . standard devices other than scsi and ata / atapi devices , such as tape drives , dvds , and cd - roms may optionally include a failure prediction filter driver 84 . failure prediction filter drivers are described in greater detail in the discussion accompanying fig4 below . the device drivers for smart devices generally interface with a storage management driver 86 , e . g ., disk . sys . device drivers for smart devices , such as smart scsi and smart ata / atapi devices , can perform the functions generally performed by the storage management driver , e . g ., disk . sys . the device driver of a smart device or a proprietary device can communicate directly with the storage management driver 86 or via a failure prediction filter driver 80 , 82 , respectively . the device drivers associated with standard , non - smart devices communicate with the storage management driver 86 via a failure prediction filter driver 81 . other devices , i . e ., devices that do not adhere to the smart standard , such as tape storage devices , dvd roms and cd - roms , can also interface with a storage management driver 88 . these devices may communicate with the storage management driver 88 via a failure prediction filter driver 84 . other proprietary storage devices 65 , such as a ram disk , may or may not interface with a storage management driver 89 . if a proprietary storage device does interface with a storage management driver 85 then the proprietary storage device can have a failure prediction filter driver that reports the failure predictions to the storage management driver . a failure prediction filter driver can be used to send a proprietary request to the hardware for a hardware device that does not conform to the smart specification , for example , a raid controller . alternatively the proprietary device can have a failure prediction enabled port driver that interfaces directly with the wmi provider . a third possibility is a device driver that does not communicate with a storage management driver 89 and must perform the responsibilities that would otherwise be performed by the storage management driver , including : file system access , polling at a specified time interval , and exposing wmi classes for failure prediction . this driver can also communicate directly with the wmi provider . another embodiment of the invention includes a failure prediction agent 69 in user mode 60 . this agent is used in lieu of the wdm provider 70 described above . this agent could perform all of the work in user mode , for example by accessing device information using public or private apis . the implementation of the invention extends existing smart functionality . this embodiment of the invention makes use of the following new global universal identifications ( guids ) which are associated with wmi classes in the windows wmi schema : ( 1 ) read failure predict status ; ( 2 ) read failure predict data ; ( 3 ) failure predict event ; and ( 4 ) perform failure predict function . the perform failure predict function guid has the following five methods associated with it : ( 1 ) enable / disable hardware failure prediction ; ( 2 ) enable / disable failure prediction polling ; ( 3 ) enable / disable performance degradation for better prediction ; ( 4 ) get failure prediction mechanism ( e . g ., smart ioctl , scsi smart , and ioctl for filter drivers ); and ( 5 ) enabling off - line diagnostics ( ata / atapi only ). fig3 a - 6 are flow diagrams illustrating one embodiment of a process for carrying out the invention . fig3 a - 3b are a flow diagram illustrating the overall logic of this embodiment . the logic of the flow diagrams classifies devices into three categories : smart scsi devices , smart ata / atapi deices and non - smart devices . since the invention extends smart functionality , as described above , the rationale for describing the invention based on these categories is based on the fact that smart scsi and smart ata / atapi devices are currently the only supported smart devices . the embodiment described herein is implemented using the wdm provider 70 . the logic of fig3 a moves from a start block to block 100 where registration with the wmi component is performed . preferably , this is through an api call . next , initialization for each storage device is performed beginning at block 102 . for each storage device , a “ query ” is performed to determine if the device supports failure prediction . see block 104 . this can be accomplished by examining the device type to determine whether the device type is scsi . if so , a hardware command is sent to the disk to try to enable informational exceptions reporting . if this succeeds , the device is a smart scsi device . if the device type is ata / atapi , the ata / atapi identify information contains a flag indicating whether the device supports smart . if the device type is neither scsi nor ata / atapi , a failure prediction ioctl is sent to the device . a successful completion indicates that the device stack includes a failure prediction filter driver . the logic then moves to decision block 106 where a test is made to determine if the device supports failure prediction . if so , the logic moves from decision block 106 to decision block 108 where a test is made to determine if the device is a smart scsi device . if so , the logic moves to block 110 where a read is sent to the smart scsi device , and the resultant sense codes are interpreted to determine if a failure is being predicted , as illustrated in detail in fig4 and described later . if the device is not a smart scsi device , the logic moves from decision block 108 to decision block 112 where a test is made to determine if the device is a smart ata / atapi device . if so , the logic moves to block 114 where the smart ata / atapi device is queried for status , as illustrated in detail in fig5 and described later . if the device is neither a smart scsi device nor a smart ata / atapi device , the device may be a device with a failure prediction filter driver , and the logic moves from decision block 112 to block 116 where the failure prediction filter driver is “ queried ” for status , as illustrated in detail in fig6 and described later . after sending a read to the smart scsi device and interpreting the resultant sense code for failure prediction status 110 , querying the smart ata / atapi device for status 114 , “ querying ” the failure prediction filter driver for status 116 , or if the device does not support failure prediction ( no in decision block 106 ), the logic returns to block 102 where the processing of blocks 102 - 116 is repeated for the next device . when all of the devices have been processed , the logic moves to decision block 120 ( fig3 b ) where a test is made to determine if it is time to exit . for example , an exit signal may be received if the computer is being shut down . it will be appreciated that the logic shown allows for continuous monitoring for the prediction of storage device failures . if it is not time to exit , the logic moves to decision block 122 where a test is made to determine if it is time to check for storage device failures . checking for storage device failures can be performed on a timed bases , e . g ., every hour , or on a request basis , such as at boot or by user request . preferably , an interrupt is used to signal that it is time to check for storage device failures . if it is time to check for storage device failures , the logic moves to decision block 124 where a test is made to determine if the device to be checked is a smart scsi device . if so , the logic moves to block 126 where a read is sent to the smart scsi device so that the resultant sense code can be interpreted to obtain a failure prediction status , as illustrated in fig4 and described later . if not , the logic moves to decision block 128 where a test is made to determine if the device to be checked is a smart ata / atapi device . if so , the logic moves to block 130 where the smart ata / atapi device is queried for status , as illustrated in fig5 and described later . if it is time to check for a storage device failure on a device that is neither a smart scsi device nor a smart ata / atapi device , the logic moves to block 132 where a failure prediction filter driver is “ queried ” for status , as illustrated in fig6 and described later . if it is not time to check for storage device failure (“ no ” in decision block 122 ) or after a smart scsi device has been sent a read so that the resultant sense code can be interpreted for status 126 , a smart ata / atapi device has been queried for status 130 , or a failure prediction filter driver has been queried for status 132 , the logic returns to decision block 120 where the test is repeated to determine if it is time to exit . the processing of blocks 120 - 132 is repeated until it is time to exit , at which point the logic of fig3 a and 3b ends . fig4 illustrates in detail the logic of reading a smart scsi device for status . the logic of fig4 moves from a start block to block 150 where a read request is sent to the scsi device . the disk storage management driver 86 , disk . sys , is capable of communicating directly with a scsi device . scsi devices typically do not have a query smart status command , therefore , a read may be performed in order to obtain a sense code which can be interpreted to determine the failure prediction status . a read can be sent specifically for this purpose . alternatively , any time the scsi device performs i / o for any purpose , the resultant sense code can be interpreted in order to determine if there is a potential storage device failure that should be reported . next failure prediction filter driver functions can optionally be performed . see block 152 . these functions are performed by the optional failure prediction filter driver 80 . for example , statistical analysis can be performed by a failure prediction filter driver 80 . statistical analysis can alter the determination of whether a storage device failure should be reported . for example , if the number of retries is increasing linearly , a failure may be reported . another example of using a failure prediction filter driver is that failures should be reported much sooner for a critical system , such as that used by an airline , than for a non - critical system , such as a home computer system . a failure prediction filter driver can also be used to report failures for devices that do not provide status information . for example , a disk may not provide status information , however the type of disk in question may historically experience storage device errors after a certain amount of use , for example after 5 , 000 hours of use . a failure prediction filter driver can track the amount of usage and report potential storage errors after 5 , 000 hours . next , the logic moves to block 154 where the sense code is interpreted . it will be appreciated that some failure prediction filter driver functions 152 can be performed after interpreting the sense code in addition to , or instead of performing failure prediction filter driver functions 152 before interpreting the sense code 154 . the logic then moves to decision block 156 where a test is made to determinate if a storage device failure should be reported . if so , failure event data is propagated to the management application 62 . preferably , this is done through the use of an api call . if there is not a storage device failure event to propagate , or after the event is propagated , the logic moves to block 160 where the read interval is reset . for example , if the device is read once an hour to check for storage device failures , the interval is reset for the next hour . this allows for continued monitoring of the storage device for potential storage errors that should be reported . this interval is used in order to determine whether it is time to check for storage device failures in block 122 of fig3 b . the logic of fig4 then ends and processing returns to fig3 a or fig3 b . fig5 illustrates in detail the logic of querying a smart ata / atapi storage device for status . the logic of fig5 moves from a start block to block 170 where a read smart status command is sent to the smart ata / atapi storage device . unlike scsi devices , the storage management driver 86 disk . sys can not communicate directly with the ata / atapi device . the logic for obtaining status from an ata / atapi device is divided between the disk storage management device 86 , e . g ., disk . sys , and the ata / atapi port driver 80 or 81 . the logic then moves to block 172 where failure prediction filter driver functions may be performed by a failure prediction filter driver 81 . next , in block 174 , the status response is read . it will be appreciated that some failure prediction filter driver functions 172 can be performed after reading the status response in addition to , or instead of performing failure prediction filter driver functions 172 before reading the status response 174 . the logic then moves to decision block 176 where a determination is made whether there is a smart ata / atapi storage device failure that should be reported . if so , failure event data is propagated to the management application 62 in block 178 . if there was not a failure to report , or after the event is propagated , the logic moves to block 180 where the query interval is reset . the logic of fig5 then ends , and processing returns to fig3 a or fig3 b . fig6 illustrates the logic of “ querying ” a non - smart device that has a failure prediction filter driver . the logic moves from a start block to block 190 where a failure prediction filter driver device is “ queried ” for status . the method for determining if failure is predicted for the device is dependent upon the type of device . for example , the device may be queried similar to a smart ata / atapi device , or a read may be required , similar to a smart scsi device , or any other acceptable method as defined by the manufacturer of the device . examples of these storage devices include ram disks , cd - roms , dvd roms , and tape storage devices . it will be appreciated that the foregoing examples are illustrative , and other types of devices may be included . the logic then moves to block 192 where information may be obtained from the device hardware . based upon this information or other information maintained by the failure prediction filter driver , a determination of the failure prediction status is made . a storage management driver 88 may query the filter driver in order to obtain failure prediction information that is maintained within the failure prediction driver 84 . the failure prediction driver can employ various mechanisms , for example , statistical analysis , in order to determine the failure prediction information . the storage management driver 88 may also query the failure prediction filter driver so that the failure prediction filter driver can perform a hardware request to a storage device 64 . the failure prediction filter driver 84 interprets the results and determines whether a failure is being predicted . the interpretation could be determined using a variety of mechanisms , for example , statistical analysis , breaches of predetermined thresholds , or propagating a fail / no fail result . the logic then moves to decision block 196 where a test is made to determine whether there is a storage failure to report for the device . if so , the logic moves to block 198 where failure event data is propagated to the management application 62 . if there is no information to report to the management application 62 , or after the information is reported , the logic moves to block 200 where the query interval for the device is reset . the logic of fig6 then ends and processing returns to fig3 a or fig3 b . alternatively , a failure prediction enabled storage driver 75 or a failure prediction port driver 72 , as described above , can communicate directly with the wdm provider 70 instead of via a storage management driver . in this case the failure prediction enabled storage driver and the failure prediction port driver can use any mechanisms available to them to determine the failure prediction status . it will be readily appreciated by those skilled in the art that the logic of fig4 and 6 is similar . one relevant difference between these figures is that the method for obtaining storage device failure information is device specific . while the preferred embodiment of the invention has been illustrated and described , it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention as defined by the appended claims . | 7 |
reference will now be made in detail to the present preferred embodiments of the invention , examples of which are illustrated in the accompanying drawings . wherever possible , the same reference numbers are used in the drawings and the description to refer to the same or like parts . fig1 and 2 are schematic cross - sectional views showing the steps for forming a silicon nitride layer of different thickness over a silicon oxide layer and a substrate simultaneously according to one preferred embodiment of this invention . as shown in fig1 a substrate 100 is provided . the substrate 100 is preferably a semiconductor substrate such as a silicon substrate . since a native oxide layer ( not shown ) can easily form over the substrate 100 surface , a series of cleaning steps are often conducted to remove the native oxide and obtain a pure silicon surface . the native oxide can be removed by placing the substrate 100 onto a tank 10 full of rca cleaning solution using a robotic hand . the rca solution is a cleaning agent that includes ammonium hydroxide ( nh 4 oh ), hot de - ionized water ( hdiw ) and hydrogen peroxide ( h 2 o 2 ). at a common boiling temperature , the native oxide on the surface of the substrate 100 is removed . in the subsequent step , the substrate 100 is dipped into a hot quick - dump rise ( hqdr ) bath . using large quantity of de - ionized water , any residual rca solution from the substrate 100 is removed by rinsing . the substrate 100 is next immersed in a bath full of dilute hydrofluoric acid ( hf ) solution for a dilute hydrofluoric ( dhf ) acid treatment that removes not only the native oxide layer but also organic material and micro - particles . a silicon oxide layer 102 is formed over a portion of the substrate 100 . the silicon oxide layer 102 is formed , for example , by thermally oxidizing a portion of the substrate 100 . as shown in fig2 a nitrogen - containing gas , preferably an ammonia ( nh 3 ) gas , is used to perform a surface treatment . the ammonia gas is passed over the silicon oxide layer 102 and the substrate 100 for a pre - defined period . the surface treatment period can be varied according to demand . after treating the surface with ammonia for a period , silicon nitride is deposited over the substrate 100 and the silicon oxide layer 102 to form a silicon nitride layer 104 a and a silicon nitride layer 104 b . in the surface treatment process , a temperature of between 600 ° c . to 1000 ° c . and a pressure of between 0 . 3 torr to 760 torrs is preferably used . in the process of forming the silicon nitride layers 104 a and 104 b , a depositing pressure equal to or smaller than 0 . 3 torr is preferably used . if ammonia ( nh 3 ) and dichloro - silicon hydride ( sih 2 cl 2 ) is the reactive gas for depositing silicon nitride , the ratio of the gas flow rates between the two can be equal to or greater than 3 : 1 . according to experimental results , after treating a surface with ammonia for a defined period , the silicon nitride layer 104 a has a greater thickness than the silicon nitride layer 104 b . thickness difference ratio between the silicon nitride layer 104 a and the silicon nitride layer 104 b ranges from 50 % to 120 %. the thickness difference ratio is computed using the formula : ( tsi − tox )/[( tsi + tox )/ 2 ], wherein tsi is the thickness of silicon nitride on the substrate surface , that is , thickness of the silicon nitride layer 104 a ; tox is the thickness of silicon nitride on the silicon oxide layer , that is , thickness of the silicon nitride layer 104 b . to increase the thickness difference ratio between the silicon nitride layer 104 a and the silicon nitride layer 104 b further , depositing pressure can be lowered and / or flow rate of the gaseous reactants can be increased . in addition , the treatment period using ammonia can be increased or decreased according to actual need . fig3 is a bar chart showing the relationship between the treatment conditions with nh 3 and the ratio of thickness of the silicon nitride layer formed over an oxide layer and substrate . as shown in fig3 thickness difference ratio of the silicon nitride layer with ammonia treatment is much greater than one without ammonia treatment . the thickness difference ratio is computed using the formula : ( tsi − tox )/[( tsi + tox )/ 2 ]. tsi is the thickness of silicon nitride on the substrate 100 surface , that is , thickness of the silicon nitride layer 104 a . tox is the thickness of silicon nitride on the silicon oxide layer 102 , that is , thickness of the silicon nitride layer 104 b . fig4 is a bar chart showing the relationship between the pressure used in the deposition of silicon nitride and the ratio of thickness of the silicon nitride layer formed over an oxide layer and a substrate . as shown in fig4 the thickness difference ratio of the silicon nitride layer is the greatest at a pressure of 0 . 125 torr . in other words , the lower the depositing pressure , the greater will be the thickness difference ratio of the deposited silicon nitride layer over a silicon oxide layer and a substrate . fig5 is a bar chart showing the relationship between the relative gas flow rates in the deposition of silicon nitride and the ratio of thickness of the silicon nitride layer formed over an oxide layer and a substrate . as shown in fig5 the relative gas flow rate is between ammonia and dichloro - silicon hydride . according to experiment , the higher the relative flow rates of the two gaseous reactants , the greater will be the thickness difference ratio of the deposited silicon nitride layer over a silicon oxide layer and a substrate . in this invention , ammonia nh 3 is used to perform a surface treatment of the substrate surface and the silicon oxide surface . after the surface treatment , a single deposition step can be used to deposit silicon nitride to a different thickness over the silicon oxide layer and the substrate . since there is no need to perform separate deposition steps to form a silicon nitride layer over the silicon oxide layer and the substrate , manufacturing is simplified . it will be apparent to those skilled in the art that various modifications and variations can be made to the structure of the present invention without departing from the scope or spirit of the invention . in view of the foregoing , it is intended that the present invention cover modifications and variations of this invention provided they fall within the scope of the following claims and their equivalents . | 7 |
there are at least four major approaches to making aba polymers according to the invention . they are : ( 1 ) start with a monofunctional initiator and polymerize in three steps , gma first , which makes the first a segment , followed by methyl methacrylate ( mma ) which adds onto the a segment and makes an ab polymer , and finally gma again which completes the aba structure ; ( 2 ) start with a difunctional initiator and polymerize the monomers in two steps , mma first , which creates the middle b segment , followed by gma which will add onto both ends simultaneously because of the difunctional initiator , making the aba polymer ; ( 3 ) start with monofunctional initiator , polymerize in two steps , gma first , making the a segment , followed by mma , making an ab polymer , and finally coupling the polymer to unite the two ab polymers at the b end and create an aba polymer ; ( 4 ) start with an epoxy containing initiator , the a segment , polymerize the mma , making an ab polymer , and finally , couple the polymer which unites the two ab polymers at the b end and creates an aba polymer . monomers which can be used to prepare the center section include , for example , alkyl methacrylates and acrylates that can be used to prepare acrylic polymers . included are methyl methacrylate , ethyl methacrylate , butyl methacrylate ( bma ), hexyl methacrylate , 2 - ethylhexyl methacrylate , nonyl methacrylate , lauryl methacrylate , stearyl methacrylate , cyclohexyl methacrylate , isodecyl methacrylate , propyl methacrylate , phenyl methacrylate , isobornyl methacrylate , ethyl acrylate , propyl acrylate , isopropyl acrylate , butyl acrylate , isobutyl acrylate , hexyl acrylate , 2 - ethylhexyl acrylate , nonyl acrylate , lauryl acrylate , stearyl acrylate , cyclohexyl acrylate , isodecyl acrylate , phenyl acrylate , isobornyl acrylate , blocked ( meth ) acrylic acid monomers which can be unblocked after polymerization , including trimethyl silyl methacrylate and 1 - butoxyethyl methacrylate , and the like . both the end and center sections can include other functionality , such as for crosslinking , so long as it does not interfere with polymerization . example 1 describes ( 3 ), supra , how one might make gma // bma // gma using monofunctional initiator , two monomer feeds , and a coupling agent . example 2 describes ( 4 ), supra , how one might make gma // bma // gma using an epoxy initiator , a monomer feed , and a coupling agent . the coupling agent is preferably diphenyl terephthalate , but it could be other suitable materials . following are definitions of terms used in the summary of the invention , supra . by &# 34 ; acyl &# 34 ; is meant the moiety which remains after removal of a hydroxy group from an organic carboxylic acid . by &# 34 ; sulfonyl &# 34 ; is meant the moiety which remains after removal of a hydroxy group from an organic sulfonic acid . by &# 34 ; hydrocarbyl radical &# 34 ; is meant a radical consisting essentially of hydrogen and up to about 20 carbon atoms . by &# 34 ; substituted hydrocarbyl radical &# 34 ; is meant hydrocarbyl which contains one or more functional substituents that are inert under reaction conditions and / or one or more ether oxygen atoms within aliphatic segments thereof . by &# 34 ; polymeric radical &# 34 ; is meant a polymeric radical containing more than 20 carbon atoms ; the radical may contain the intra - chain heteroatoms o , n or s and / or non - functional or functional substituents that are inert under reaction conditions . by &# 34 ; aryl &# 34 ; is meant an aromatic radical having at least six carbon atoms . by &# 34 ; substituted aryl &# 34 ; is meant aryl which contains one or more aliphatic substituents or functional substituents that are inert under reaction conditions . by &# 34 ; a selected anion or oxyanion &# 34 ; is meant a fluoride , difluorotrimethylsilicate , bifluoride , cyanide or azide anion , or an oxyanion which forms a conjugate acid having a pka ( dmso ) of about 5 to about 24 , preferably about 6 to about 21 , more preferably 8 to 18 as defined in u . s . pat . no . 4 , 588 , 795 , column 5 , lines 15 - 18 . by conjugate acid is meant the acid formed by protonating the catalytic oxyanion . by pka ( dmso ) of the conjugate acid is meant the negative logarithm of the acidity constant of the conjugate acid , measured in dimethylsulfoxide at 25 ° c . ( u . s . pat . no . 4 , 588 , 795 , column 5 , lines 24 - 30 ). the catalysts which are sources of a selected anion or oxyanion also include the group transfer polymerization catalysts described in the aforesaid gtp patents and applications , especially in u . s . pat . nos . 4 , 508 , 880 and 4 , 588 , 795 , which are incorporated herein by reference . representative examples of the catalysts which are sources of a selected oxyanion in &# 39 ; 795 are given in col . 6 , line 52 to col . 7 , line 6 . the catalysts which are sources of a selected anion in &# 39 ; 880 , at col . 11 , lines 45 - 54 , in part , include : tris ( dimethylamino ) sulfonium difluorotrimethylsilicate , tris ( dimethylamino ) sulfonium cyanide , tetraphenylarsonium cyanide , tris ( dimethylamino ) sulfonium azide , tetraethylammonium azide , alkali metal fluorides , alkali metal cyanides , alkali metal azides , tris ( dimethylamino ) sulfonium difluorotriphenylstannate , tetrabutylammonium fluoride , tetramethylammonium fluoride , and tetraethylammonium cyanide . lewis acids are not catalysts for the present process . it is believed that the selected anion or oxyanion of the catalyst starts the reaction by associating with and activating the silicon of part of the silylketene acetal . as a result of this activation , it is believed , the silylketene acetal reacts with the sulfonyl or acyl compound generating free group y (-- f or -- oar ) or &# 34 ; silicon activating group &# 34 ; x . it is believed that groups x or y sustain the reaction by further associating with and activating silicon on the remaining , as yet unreacted , part of the silylketene acetal . by &# 34 ; silicon activating group &# 34 ; ( x ) is meant a leaving group which is capable of displacing silicon from the silylketene acetal under reaction conditions . it is believed that free x is generated during the reaction and sustains the reaction in the manner described above . because suitable silicon activating groups , which include -- f , -- oar or -- oc ( o ) r 6 , sustain the reaction , as described , they reduce the amount of added catalyst required for the reaction . in the above formula r 6 is hydrocarbyl or substituted hydrocarbyl . by &# 34 ; leaving group &# 34 ; is meant a group which can be released from the acyl compound . the term &# 34 ; leaving group &# 34 ; is described in j . march , &# 34 ; advanced organic chemistry : reactions , mechanisms and structure &# 34 ;, mcgraw - hill , new york ( 1968 ), pp . 199 - 200 . it is exemplified in that reference for alkyl compounds on pp . 251 - 252 and for acyl compounds on pp . 274 - 275 , in particular with reference to the group &# 34 ; x &# 34 ; in equations 1 and 2 at the top of page 275 . the following preferred embodiments are within the scope of the invention as described in the summary of the invention , supra . q is -- r 1 , and r 1 is c 1 - 8 alkyl or aryl , most preferably methyl ; r 4 is a polymeric radical , more preferably a substituted polymeric radical ; still more preferably the substituent is ester or protected hydroxyl ; preferably the polymeric radical is comprised of acrylic monomer units , most preferably methyl methacrylate units . most preferred silylketene acetals are &# 34 ; living &# 34 ; acrylic polymers prepared by group transfer polymerization ( gtp ). preferred acyl compounds are those of the formula [ xc ( o )] n r 5 wherein : x is -- f , -- oar or -- oc ( o ) r 6 wherein ar is phenyl or substituted phenyl , and r 6 is c 1 - 8 alkyl , aryl or substituted aryl ; preferred catalysts are sources of fluoride , bifluoride or selected oxyanions ; bi - oxyanions , especially biacetate , are most preferred . the beta - ketoester or beta - sulfonylester products of the invention process are of the formulas [ r 2 o 2 c -- c ( r 3 )( r 4 )-- c ( o )] a r 5 [ c ( o ) x ] n - a and [ r 2 o 2 c -- c ( r 3 )( r 4 )-- s ( o ) 2 ] a r 5 [ s ( o ) 2 y ] n - a , respectively , wherein the symbols are defined as above ; preferably a is 1 or 2 . the ketoester or sulfonylester products wherein r 4 is limited to r 8 , defined above as a polymer radical comprised of acrylic monomer units , are believed to be novel . it is to be understood that , in the fully converted ketoester or sulfonylester products of a stoichiometric reaction between the acyl or sulfonyl compound and ska , a is essentially equal to n . products prepared by employing a stoichiometric excess of acyl or sulfonyl compound will contain -- c ( o ) x or -- s ( o ) 2 y groups ( n & gt ; a ), provided n is at least 2 . these groups are then available for subsequent reaction with other , different , silylketene acetals and / or with other reagents , as discussed hereinafter . silylketene acetals are &# 34 ; capped &# 34 ;, &# 34 ; coupled &# 34 ;, or branched , or combinations thereof , by reaction with acyl or sulfonyl compounds according to the invention process , depending on the magnitude of n , and on the molar ratios of the reactants employed , as discussed hereinafter . especially preferred polymers can be prepared by coupling protected hydroxyl - functional polymeric silylketene acetals ( ska ) by means of diacyl compounds wherein n is 2 , or by capping polymeric ska with monoacyl compounds wherein n is 1 . substituents that are , in most cases , unreactive under reaction conditions include , but are not limited to , -- co 2 r , -- oc ( o ) r , -- n ( r 1 ) 2 , -- c ( o ) n ( r 1 ) 2 , -- cn , -- ch ═ ch 2 provided such groups are not conjugated with carbonyl or cyano groups , -- p ( o )( or 1 ) 2 , -- c ( o ) r 1 , and -- oh and -- co 2 h if chemically protected . in these substituents r is hydrocarbyl other than aryl and r 1 is defined as above . as indicated above , most preferred ska are &# 34 ; living &# 34 ; acrylic polymers prepared by group transfer polymerization , as described in the foregoing patents and applications , the disclosures of which have been incorporated herein by reference . particularly useful polymeric ska of this type also contain terminal silyl ether groups at non - living ends ; these groups are introduced , e . g ., by use of an appropriate gtp initiator containing at least one ska moiety of the formula & gt ; c ═ c ( osi [ q ] 3 )( or 2 ) wherein q and r 2 are defined as above , the r 2 group containing a trialkylsiloxy group . in the polymerization process , this group becomes located at a non - living end of the polymer chain . an example of such an initiator is [( 2 - methyl - 1 -[ 2 -( trimethylsiloxy ) ethoxy ]- 1 - propenyl ) oxy ] trimethylsilane ( tteb ). in the invention process , a solvent is desirable but is not essential unless neither reactant is a liquid . suitable solvents are those described in the aforesaid gtp patents and applications ; aprotic liquids such as tetrahydrofuran ( thf ), toluene , benzene and the glymes are preferred . solvent mixtures may be especially suitable . total reactant concentration should be at least about 1 % ( w / v ), preferably in the range 5 - 60 % ( w / v ). the process of the invention is carried out at a temperature of about - 100 ° c . to + 150 ° c ., preferably about - 15 ° c . to about 80 ° c ., most preferably 10 ° to 60 ° c . silylketene acetal concentration can vary from about 0 . 1 % to 100 % ( w / w ). polymeric ska which are viscous liquids or solids can be used at concentrations of about 25 - 80 % ( w / w ), depending on molecular weight . the acyl or sulfonyl compound can be used at a concentration such that the molar ratio of acyl or sulfonyl compound to ska is about 0 . 01 to about 100 , preferably about 0 . 25 to about 10 , more preferably about 0 . 5 to about 5 . catalyst concentration can be about 0 . 0001 to about 50 mol % of the ska present , preferably about 0 . 001 to about 10 mol %. as already indicated , the invention process leads to capping and / or coupling of ska molecules , depending on functionality and concentration of acylating or sulfonating compound employed . in general , to cap an ska , a monofunctional ( n is 1 ) acylating or sulfonating compound is employed at a molar ratio to ska of at least 1 : 1 . for coupling , a polyfunctional ( n is 2 or more ) acylating or sulfonating compound is employed at a molar ratio to ska of not more than 1 : 2 . a mixture of capped and coupled ska products can be produced by employing a mixture of mono - and polyfunctional acylating or sulfonating compounds . preferred telechelic polymers are prepared in the present invention process by coupling a polymeric ska containing a suitable functional group , such as a protected hydroxyl , e . g . trialkylsiloxy , as described above , using a difunctional acyl or sulfonyl compound in the molar ratio to ska of about 1 : 2 in the presence of catalyst . the polymer product contains approximately two trialkylsiloxy groups per molecule ; these can be converted to hydroxyl by hydrolysis with , e . g . hydrochloric acid in methanol . the telechelic polymer is recovered by precipitation in non - solvent . the telechelic polymer prepared by ska coupling , as described above but with difunctional compound in slight molar excess of 1 : 2 can , before precipitation , be &# 34 ; finished &# 34 ; to give more precisely two terminal functions per molecule by following the above acylation - coupling procedure with the addition of a stoichiometric excess of a -- c ( o ) x or -- s ( o ) 2 y reactive compound such as ethylene glycol , to convert residual -- c ( o ) x or -- s ( o ) 2 y polymer end groups to oh , together with an organic base such as an amine to consume by - product hx or hy , thus driving the reaction to completion . -- c ( o ) x or -- s ( o ) 2 y ends introduced by capping a ska with a stoichiometric excess of di - or polyfunctional acylating compound can also be used to provide other functional end groups , e . g ., oh , co 2 h , sh and nh 2 , for later use in chain extension or coupling , by subsequent reaction of -- c ( o ) x or -- s ( o ) 2 y ends with appropriate reagents such as glycols , water , dimercaptans , aminoalcohols and diamines . -- c ( o ) x or -- s ( o ) 2 y end groups can also be reacted (&# 34 ; finished &# 34 ;) by use of monofunctional reagents containing the above functions . such reactions will be well known to those skilled in the art . telechelic polymers can also be prepared by a combination of coupling and finishing wherein the ska is reacted with slightly more than 0 . 5 mole of difunctional acylating compound per mole of ska . -- c ( o ) x or -- s ( o ) 2 y groups present in the product are then finished as described above . if only -- c ( o ) x groups are required , with minimal coupling , the ska can be reacted with a large excess of acylating agent , followed by sufficient finishing agent to react all -- c ( o ) x ends plus residual acylating compound . in general , such reactions are preferably carried out in solution . the process of the invention is believed to proceed according to the following illustrative equation : ## str8 ## it will be understood that the ( n - a ) residual -- c ( o ) x ( or -- s ( o ) 2 x ) moieties can react with other ska molecules in the presence of catalyst , or with other reactants as discussed above . in the following examples of the invention process , and in comparative experiments , parts and percentages are by weight and temperatures are in degrees celsius unless otherwise specified . a 250 ml round bottom flask , equipped with a mechanical stirrer , thermometer , and nitrogen inlet , is charged with dimethoxyethane -- glyme --( 18 . 6 g ), 1 - trimethylsiloxy - 1 - i - butoxy - 2 - methylpropene ( 2 . 1 g , 0 . 0097 mole ), and glycidyl methacrylate ( 5 . 6 g , 0 . 0394 mole ). the flask is cooled to 10 ° c . tetrabutylammonium m - chlorobenzoate tbacb ( 200 μl of a 1 . 0m solution in acetonitrile ) is injected into the flask . feed i consists of glyme ( 3 . 0 g ) and tetrabutylammonium m - chlorobenzoate ( 200 μl of a 1 . 0m solution ). it is started 10 minutes after the first injection of tbacb . it is added over 56 minutes . feed ii is methyl methacrylate ( 20 . 0 g , 0 . 20 mole ). it is started simultaneously with the start of the feed i . feed ii is added over 35 minutes . twenty minutes after feed ii is completed , diphenyl terephthalate ( 1 . 54 g , 0 . 0048 mole ) is added and the reaction is allowed to remain at room temperature overnight . this couples living polymer chains together . then methanol ( 4 . 0 g ) is added . this should be an aba block polymer ( gma // mma // gma 4 // 40 // 4 ) with 4 epoxy groups on each end of the polymer chains . a 250 ml round bottom flask , equipped with a mechanical stirrer , thermometer , and nitrogen inlet , is charged with tetrahydrofuran ( 18 . 6 g ), and 1 - trimethylsiloxy - 1 - glycidoxy - 2 - methylpropene ( 2 . 16 g , 0 . 010 mole ). the flask is cooled to 10 ° c . tetrabutylammonium m - chlorobenzoate ( 100 μl of a 1 . 0m solution in acetonitrile ) is injected into the flask . feed i consists of tetrahydrofuran ( 4 . 0 g ) and tetrabutylammonium m - chlorobenzoate ( 100 μl of a 1 . 0m solution in acetonitrile ). it is started 10 minutes after the first injection of tbacb . feed ii is methyl methacrylate ( 20 . 0 g , 0 . 20 mole ). it is started simultaneously with feed i and is added over 30 minutes . twenty minutes after feed ii is completed , diphenyl terephthalate ( 1 . 08 g , 0 . 005 mole ) is added and the reaction is allowed to remain at room temperature overnight . this couples the living polymer chains together . this should be an aba block polymer ( gma // mma // gma 1 // 40 // 1 ) with one epoxy group on each end of every polymer chain . the following discussion is relevant to examples 3 to 18 which are provided hereinbelow . all glassware , including syringes , and syringe needles were dried in a 165 ° c . oven overnight prior to use . rubber septa , teflon parts , and other polymeric materials were dried overnight in a vacuum oven at 65 ° c ., with a slight nitrogen purge . argon ( air products ) was purified by passage through a molecular sieve trap for drying and a reduced girdler g - 33 nickel oxide catalyst trap from united catalyst , inc ., for removal of oxygen . glassware was assembled while hot , flushed with argon with additional external heating , and then maintained at room temperature ( rt ) under a slightly positive pressure of argon . the joints of the glassware were connected without grease and wrapped with parafilm ® m laboratory film . serum caps , for syringe introduction of solvents and reagents , were secured onto openings in the glassware by tightly - wrapped nylon ties . methyl methacrylate ( mma , aldrich chemical co .) was purified and dried by passage through a column of anhydrous alumina , neutral grade ( woelm ), exiting the column through a syringe needle into a serum - capped bottle kept under a slightly positive pressure of argon . tetrahydrofuran ( thf ) was dried over sodium and distilled from sodium benzophenone ketyl immediately before use . acetonitrile was dried by distillation from p 2 o 5 . initiators were distilled in a 12 - inch spinning band column . dried solvents , initiators , and catalyst solutions were stored in &# 34 ; aldrich &# 34 ; bottles in drierite - packed desiccators . 1 h - nmr spectra were recorded with a nicolet 360wb spectrometer . molecular weights were determined by gel permeation chromatography ( gpc ) using a waters associates gpc with a 590 pump , 401 r . i . detector and 4 microstyrogel columns , 100 , 000 , 10 , 000 , 500 , and 100 . polydispersity ( d ) is given by the formula d = mw / mn where mw and mn are , respectively , weight and number average molecular weight . hydroxy - pmma and a , ω - dihydroxy - pmma content of the product was determined by high pressure liquid chromatography , employing a du pont instruments series 800 gradient controller and chromatographic pump and a waters associates r401 refractive index detector . a 100 - ml 3 - neck r . b . flask was outfitted with a magnetic stirring bar , argon inlet adapter , serum cap , and thermowell . the apparatus was dried as usual and maintained under a slight positive pressure of argon . to the flask were added dry thf ( 30 ml ), mts ( 1 . 6 ml , 8 . 0 mmol ), benzoyl fluoride ( 0 . 87 ml , 8 . 0 mmol , aldrich , 99 % pure ), and , last , 0 . 5m tetrabutylammonium biacetate ( bu 4 noac . hoac )/ ch 3 cn ( 40 μl , 0 . 25 mol % of mts ). within one minute , the temperature rose from 25 ° c . to 36 ° c ., then receded . stirring was continued for 2 h , and then the solvent and volatile silyl fluoride by - product were removed with a rotary evaporator . the liquid product was dissolved in deuterochloroform ( cdcl 3 ) for proton nmr analysis , which showed it to be virtually pure methyl 2 - benzoylisobutyrate . nmr ( cdcl 3 , δppm ): 1 . 5 ( s , 6 . 0 h , ch 3 ), 3 . 6 ( s , 2 . 9 h , ch 3 o ), and 7 . 4 , 7 . 5 and 7 . 8 ( m , 5 . 1 h , c 6 h 5 ). the reaction described in example 3 was repeated except that acetyl fluoride ( aldrich ) was used in place of benzoyl fluoride and 1m tris ( dimethylamino ) sulfonium bifluoride ( tashf 2 )/ ch 3 cn ( 40 μl , 0 . 5 mol %) in place of biacetate . the acetyl fluoride was delivered from a cylinder into 15 ml of thf in a serum - capped erlenmeyer flask . the amount of acid fluoride was measured by difference in weight , and thereby its concentration in solution determined . thus , 1 . 37 g of reagent was added to the thf , which required 5 . 9 ml of solution to be syringed into the reaction flask in order to deliver 0 . 50 g of acetyl fluoride ( 8 . 0 mmol ). the nmr of the liquid product showed it to be virtually pure methyl 2 - acetylisobutyrate . nmr ( cdcl 3 , δppm ): 1 . 3 ( s , 6 . 0 h , ch 3 ), 2 . 1 ( s , 3 . 3 h , ch 3 co ), and 3 . 65 ( s , 3 . 0 h , ch 3 o ). methyl methacrylate ( 25 ml ) was polymerized by group transfer polymerization ( gtp ) in a 250 - ml , 4 - neck r . b . flask , equipped with an argon inlet , thermocouple well , serum cap , and magnetic stirring bar , charged with dry thf ( 75 ml ), [( 2 - methyl - 1 -[ 2 -( trimethylsiloxy ) ethoxy ]- 1 - propenyl ) oxy ] trimethylsilane ( tteb ) ( 2 . 5 ml , 7 . 9 mmol ), 0 . 5m bu 4 noac . hoac / ch 3 cn ( 8 μl , 0 . 051 mol % of tteb ). the mma was added by syringe pump at 0 . 5 ml / min only after an incubation period of 20 min . upon addition of mma , the temperature rose from 24 . 2 ° c . to 39 . 4 ° c . in 36 min ( 18 ml mma added ) and declined slowly thereafter to 38 . 8 ° c . the polymer solution was stirred for 1 h , and benzoyl fluoride ( 1 . 7 ml , 15 . 6 mmol , aldrich , 99 % pure ) was syringed in . the temperature rose only from 24 . 5 ° c . to 24 . 8 ° c ., so an additional 30 μl of biacetate catalyst was added ( net catalyst = 0 . 24 % of tteb - derived living ends ). within 3 min , the temperature rose to 25 . 7 ° c ., then declined very slowly thereafter , falling to 24 . 7 ° c . 45 min after addition of the last measure of catalyst ( 55 min after benzoyl fluoride addition ). the reaction was left unstirred overnight , concentrated to dryness on a rotary evaporator , dissolved in about 50 ml of ch 2 cl 2 , and precipitated in a large excess of stirred ( magnetic bar ) hexane ( hexane : solution = 10 : 1 , v / v ). the precipitate was filtered on a vacuum filter funnel , rinsed three times with hexane , partially dried on the funnel , and dried overnight in an evaporating dish in a fume hood . a sample was dissolved in cdcl 3 for proton nmr analysis , the remainder dried for 24 h at 65 ° c . in a vacuum oven , to constant weight . the dry sample was weighed and a portion dissolved in thf for gpc analysis . the weight of recovered poly ( methyl methacrylate ) ( pmma ) was 21 . 08 g , the calculated tteb residue 1 . 7 g . the mma conversion was thus 83 . 7 %, theor . mn ( 100 % basis ) was 3260 . gpc analysis gave mn = 2840 , mw = 3100 , mw / mn = 1 . 09 . duplicate vpo ( thf ) gave mn = 3200 . compared with the theoretical mma / end - group value of 29 . 4 , nmr gave 34 . 4 ( meo / phco ) and 37 . 2 ( meo / me 3 sio ). the mma / benzoyl - capped end ratio was calculated from proton nmr spectra , by comparing peak areas for the mma resonance at δ 3 . 55 ppm ( meo ) and benzoyl resonance at δ 7 . 2 - 7 . 7 ppm ( ph ). as an internal check , the mma / initiator fragment ratio was also calculated from δ 3 . 55 ppm ( meo ) and the initiator fragment &# 39 ; s δ 0 . 1 ( me 3 sio ) peaks . the procedure of the previous example was repeated except that 1 . 7 g ( 27 . 4 mmol ) of acetyl fluoride dissolved in about 17 ml of thf was used in place of benzoyl fluoride . the acetyl fluoride caused a temperature rise from 25 . 1 ° c . to 25 . 7 ° c . after 10 min , the temperature began to decrease , and 30 μl of biacetate was added . the temperature rose to a peak of 26 . 7 ° c . in another 3 min . the recovered pmma weighed 23 . 81 g , a conversion of 96 . 7 %. theor . mn ( 100 %) was 3200 . gpc gave mn = 2660 , mw = 2890 , mw / mn = 1 . 09 . compared with the theoretical mma / end - group value of 29 . 4 , nmr gave ca . 27 ( meo / ch 3 co ) and 27 . 5 ( meo / me 3 sio ). the monomer / end - group ratio was calculated from nmr resonances for mma at δ 3 . 55 ( meo ), acetyl cap at δ 2 . 05 ( overlapping slightly with polymer resonances ), and initiator fragment at δ 0 . 1 ( me 3 sio ). the procedure of example 5 was repeated with the following changes : mma was polymerized using 50 μl of 0 . 045m bu 4 noac . hoac / thf , all of which was added at the start . mma was fed in over a 55 - min period , from a pressure - equalizing dropping funnel instead of a syringe pump . the polymer solution was stirred thereafter for 4 h and then capped by a solution of 3 . 1 g phenyl benzoate ( 15 . 6 mmol ) in 25 ml of very dry thf , transferred by cannula . the temperature rose very little and more catalyst was added ( 100 μl of 0 . 045m bu 4 noac . hoac / thf and 100 μl of 0 . 2m bu 4 noac . hoac / ch 3 cn ). the temperature rose 0 . 5 ° c . and the solution slowly acquired a slight yellow color . total recovered pmma was 25 . 0 g , a 93 . 3 % mma conversion . theor . mn was 3260 and gpc gave mn = 2800 , mw = 3200 , mw / mn = 1 . 14 . the theoretical mma / end - group ratio was 29 . 4 ( 100 % conversion basis ) and nmr on polymer purified by re - precipitation gave 41 . 3 for mma / capping fragment ( meo / ph ) and 35 . 6 for mma / initiator fragment ( meo / me 3 sio ). the procedure described in example 5 was repeated with the following changes : mma was polymerized using 35 μl of 0 . 04m bu 4 noac . hoac . 6 h 2 o / thf and mma was fed in over a 65 min period , from a pressure - equalizing dropping funnel . the polymer solution was stirred thereafter for 21 / 2 hours and then capped by a solution of 3 . 6 g benzoic anhydride ( 15 . 9 mmol ) dissolved in 10 ml of very dry thf and transferred by cannula . after 200 μl catalyst was added , the temperature rose 2 . 3 ° c . the recovered pmma , 32 . 6 g , was dried only at room temperature ( rt ), then dissolved in 70 ml ethyl acetate and mixed with 2 . 3 g koh in 70 ml deionized water , to remove unreacted benzoic anhydride . after vigorous stirring for 30 min ., the mixture was shaken in a separatory funnel and the aqueous phase removed . the ethyl acetate layer was extracted with three 70 - ml portions of deionized water , dried 2 h over anhydrous mgso . sub . 4 and filtered . the filtrate was poured into well - stirred hexane to precipitate the polymer . the polymer was dried only at rt and after 3 days weighed 26 . 7 g . theor . mn ( 100 % basis ) was 3300 and gpc gave mn = 2900 , mn = 3400 , mw / mn = 1 . 15 . the theoretical mma / end - group ratio was 29 . 4 and nmr gave 32 . 7 for mma / capping fragment ( meo / ph ) and 66 . 8 for mma / initiator fragment ( meo / me 3 sio ); the high latter value arose from hydrolytic loss of me 3 si end groups caused by koh treatment . the procedure of example 5 was repeated except for the replacement of benzoyl fluoride by 1 . 8 ml benzoyl chloride ( 2 . 2 g , 15 . 5 mmol ). the temperature rose from 27 . 4 ° to 27 . 6 ° c . when the chloride was added , but did not rise further upon addition of 30 μl of biacetate catalyst solution . the recovered pmma weighed 23 . 8 g , a 95 . 4 % conversion of mma . theor . mn ( 100 % basis ) was 3260 and gpc gave mn = 2580 , mw = 2900 , mw / mn = 1 . 12 . nmr analysis showed no resonance for a benzoyl cap at δ 7 . 2 - 7 . 7 , indicating that acid chloride , which is usually more reactive than acid fluoride , failed to react with ska . a 250 - ml r . b . flask , fitted with magnetic stirring bar , serum cap , reflux condenser and argon inlet tube , was flushed with argon and then loaded with : a solution of 18 - crown - 6 ( aldrich , 99 %, 3 . 0 g , 0 . 011 mol ), in ch 2 cl 2 ( fisher , reagent grade , 60 ml ), prepared in a bottle in the dry box . when the mixture was stirred , it began to reflux . it was maintained at reflux for two hours and stirred at rt for 1 h , under slight argon pressure . the kf / kcl residue was removed by vacuum filtering the solution under nitrogen and rinsing the residue three times with 50 - ml portions of ch 2 cl 2 , also under nitrogen . the solvent was removed from the filtrate on a rotary evaporator with house vacuum . the solid was sublimed three times , under strong vacuum , at 100 ° c . the sublimer was assembled and disassembled in a glove bag , under nitrogen . the product from the respective sublimations was weighed and its m . p . measured : 20 . 5 g ( 90 °- 108 ° c . ), 20 . 0 g ( 115 °- 123 ° c . ), and 18 . 1 g ( 115 °- 124 ° c .). the product from the third sublimation was recrystallized overnight from 70 ml dry toluene / 150 ml petroleum ether . the mother liquor was removed from the solid by transferring it via a cannula to a serum - capped flask , under argon . the solid was rinsed five times with 50 - ml portions of 1 : 2 . 2 toluene - petroleum ether , the rinsings removed each time by cannula transfer to the mother liquor . the solid was blown dry by a nitrogen sweep through the flask used for the recrystallization . a second crop was taken by concentrating the combined mother liquor plus rinsings with a nitrogen sweep applied to the heated liquid . the volume of the concentrate was tripled by the addition of petroleum ether , and the solution allowed to cool to rt and then set aside for 3 days . the product / solvent mixture was chilled 1 h in ice water and the mother liquor transferred away by cannula . the solid was rinsed at rt with four 30 - ml portions of petroleum ether and dried as above . the crops were weighed and portions placed in melting point tubes , in a dry box . the combined yield was 14 . 2 g , 71 % of theory ( 20 . 0 g ). a 250 - ml 4 - neck r . b . flask was outfitted with a magnetic stirring bar , pressure - equalizing dropping funnel , thermowell ( for thermocouple ), and argon inlet tube . after being heated with a heat - gun under argon flush , the apparatus was allowed to cool to rt and kept under a slight argon pressure . ______________________________________thf ( distilled from sodium benzophenone 75 mlketyl ) tteb 5 . 0 ml ( 15 . 7 mmol ) 0 . 041 m bu . sub . 4 noac . hoac . 6 h . sub . 2 o in thf 25 μl______________________________________ the mixture was stirred and 25 ml mma was dripped in over a 50 min period , from the dropping funnel . additional biacetate solution ( 25 μl ) was added 30 min into the monomer addition . the mixture was stirred for an additional 41 / 2 h to complete polymerization ( polymeric ska ) prior to the coupling reaction . a solution of terephthaloyl fluoride ( 1 . 34 g , 7 . 88 mmol ), prepared in part a , in still - dried thf ( 10 ml ) was cannula - transferred to the polymeric ska prepared above and a 0 . 1 ° c . temperature rise was observed . biacetate catalyst solution ( 200 μl ) was added to the stirred mixture and a 3 . 5 ° c . temperature rise observed over the next 13 minutes . the reaction was left to stir an additional 1 h , then left unstirred at rt for 16 h . the solution slowly yellowed . an aliquot of the α , ω - di ( trimethylsiloxy )- pmma product was removed and precipitated in a 20 - fold excess of hexane in a stirred beaker -- sample a . the remaining solution was treated with 6 . 0 ml of 10 % ( w / w ) hcl -- meoh and stirred for 3 h at rt to hydrolyze trimethylsiloxy end groups . the solution became colorless . the solution was concentrated and polymer precipitated when it was poured slowly into a 20 - fold excess of hexane , rapidly stirred in a large beaker -- sample b . recovered weights ( excluding 0 . 3 g remaining on glassware )-- a : 1 . 4 g ; b : 24 . 2 g ( dried 32 h / 65 ° c ./ vac oven ). gpc analysis : a -- theor . mn ( 100 % conversion and 100 % coupled )= 3500 . mn = 3400 , mw = 4000 , mw / mn = 1 . 19 ; b -- theor . mn ( 100 % basis )= 3300 . mn = 3300 , mw = 4000 , mw / mn = 1 . 19 ; nmr analysis : a -- theoretical mma / end - group = d . p . before coupling = 14 . 7 ; theoretical mma / coupling agent ( assuming 100 % coupling )= 2 × d . p . before coupling = 29 . 4 actual mma / end - group ( from meo at δ 3 . 55 and initiator me 3 sio fragment at δ 0 . 1 )= 15 . 7 actual mma / coupling agent ( from meo at δ 3 . 55 and c 6 h 4 at δ 7 . 65 )= 33 . 0 . the procedure of example 9b was repeated but without adding more biacetate catalyst during coupling . the temperature rose only 0 . 3 ° c . during coupling . recovered pmma ( dried 48 h in a 65 ° c . vacuum oven ) weighed as follows ( excluding 0 . 3 g remaining on glassware ): a -- 1 . 2 g , b -- 24 . 8 g . the overall mma conversion was 94 . 5 %. nmr analysis : a -- actual mma / end - group = 14 . 6 ( theor 14 . 7 ) actual mma / coupling agent = 36 . 6 ( theor . 29 . 4 ) the three analyses show a substantial level of coupling even when no further catalyst is used for acylation . the procedure of example 9b was repeated with the following changes : mma was polymerized with 50 μl of 0 . 033m bu 4 noac . hoac . 6 h 2 o / thf catalyst , all of which was added at the start , and mma feed took 1 h . coupling was started 2 h after the completion of mma feed , with 2 . 50 g diphenyl terephthalate ( 7 . 85 mmol ) in 150 ml of very dry thf . the solution yellowed but there was little exotherm . biacetate catalyst solution ( 100 μl , 0 . 033m ) was added and the color darkened and the temperature rose 0 . 4 ° c . over the next 5 min . all the polymer ( sample a ) was isolated , washed , and dried ; recovery 26 . 1 g ; 93 . 8 % mma conversion . twenty g of a were dissolved in 100 ml of very dry thf and converted to α , ω - dihydroxy - pmma ( sample b ) by treatment with 5 . 1 ml of 10 % ( w / w ) hcl / methanol for 3 h at rt . the polymer was isolated by precipitation in excess hexane , washing , and drying at rt and in a 65 ° c . vacuum oven . a 3 - neck , 500 - ml r . b . flask , equipped with a magnetic stirring bar , reflux condenser connected to nitrogen , and a pressure - equalizing dropping funnel , was flushed with nitrogen and held under a slightly positive nitrogen pressure . the flask was charged with 200 ml chcl 3 ( e . merck ), 20 . 0 g terephthaloyl chloride ( aldrich , 97 %, mw = 203 . 0 , 0 . 099 moles assuming 100 % purity ), and 24 . 1 g benzoic acid ( aldrich , 99 +%, mw = 122 . 1 , 0 . 197 moles ). triethylamine ( 20 . 0 g , fisher , 0 . 198 moles ) was dripped slowly into the stirred flask , and stirring continued 11 / 2 h thereafter . after 7 ml of solution was consumed in solubility tests , the remainder was extracted with three 250 - ml portions of deionized water , the lower chloroform layer filtered . concentrating the chloroform solution with a rotary evaporator gave 34 . 5 g of product ( theor . yield 36 . 9 g ). after small - scale recrystallization trials , which consumed 1 . 4 g of product , the solid was dissolved in 200 ml hot benzene and left at rt for 21 / 2 days . the first crop was obtained by vacuum filtration . the mother liquor was concentrated to about 150 ml and a second crop obtained by filtration . a third crop was obtained after concentrating the mother liquor to ca . 75 ml . in all cases , an unusual melting point behavior of the samples suggests decomposition . at fast heating rates , the solids melt at about 140 °- 150 ° c . and resolidify , melting again only at about 280 °- 310 ° c . at slow heating rates , a slight amount of melting occurs at ca . 140 ° c ., but most melts only at 280 °- 320 ° c . theory for c 22 h 14 o 6 : c , 70 . 6 %, h , 3 . 8 %, o , 25 . 6 %. 1 h nmr ( cd 2 cl 2 , δppm ): 7 . 55 ( t , 3 . 9h , c 6 h 5 - meta h ), 7 . 7 ( tt , 2 . 1h , c 6 h 5 - para h ), 8 . 15 ( d , 4 . 0h , c 6 h 5 - ortho ), and 8 . 3 ( s , 4 . 0h , c 6 h 4 ). the procedure of example 9b was repeated with the following changes : mma was polymerized with 2 . 5 ml tteb initiator ( 7 . 9 mmol ) and 20 μl 0 . 04m bu 4 noac . hoac . 6h 2 o / thf catalyst , and mma feed took 55 min . coupling was started 3 h thereafter , with 1 . 47 g of tdb ( first crop , 3 . 93 mmol ) in 60 ml of very dry thf . the temperature rose 0 . 1 ° c ., and 0 . 2 ml of biacetate catalyst was added . the temperature rose another 0 . 1 ° c . no aliquot was removed before hydrolysis to hydroxyl ends . recovered pmma ( dried 48 h in a 65 ° c . vacuum oven ), 23 . 8 g . gpc analysis : theor . mn ( 100 % conversion and coupling )= 6400 . m n = 3700 , mw = 4900 , mw / mn = 1 . 33 ; a 300 - ml r . b . flask , equipped with a magnetic stirring bar was charged with 7 . 85 g sodium hydroxide ( fisher , 0 . 197 moles ) in 75 ml of deionized water and then , to the stirred solution , 27 . 40 g of p - nitrophenol ( aldrich , 98 %, 0 . 197 moles ) was added . the solution turned orange and a considerable amount of yellow solid was present . a solution of 20 . 04 g of terephthaloyl chloride ( aldrich , 97 %, 0 . 0987 moles assuming 100 % purity ) in methylene chloride was dripped into the flask from a dropping funnel . the flask was stirred another 15 min and the mixture filtered through a whatman &# 39 ; s # 1 filter paper disk on a buchner funnel . the filtrate was almost clear and the solid on the filter was washed with a few portions of water in the funnel and with two small portions of acetone . the solid was dried by briefly drawing air through it in a vacuum funnel and then , broken into finer pieces , in a 65 ° c . vacuum oven . the crude product weighed 36 . 1 g ( theory , 40 . 2 g ) and melted at 228 °- 243 ° c . fifteen g of the product was dissolved in 2275 ml of thf at reflux ; the solution was slightly cloudy . solid slowly crystallized on the walls of the flask upon cooling to rt and a first crop was obtained by vacuum filtration after leaving the flask overnight . the solid was dried 1 h in a 65 ° c . vacuum oven . a second crop was obtained by concentrating the mother liquor to about 200 ml and allowing the solution to cool . first crop : 10 . 6 g , mp = 245 °- 7 ° c . ( lit . 242 ° c . ; m . j . s . dewar et al ., j . org . chem ., 35 , 2711 ( 1970 )) combined yield ( adjusted for use of only 15 . 0 g of the 36 . 1 g crude product ), 71 . 8 %. elemental analysis ( first crop ): c , 59 . 2 %, h , 4 . 0 %; n , 6 . 2 %, o , 30 . 2 %. theory for c 20 h 22 n 2 o 8 : c , 58 . 8 %; h , 3 . 0 %; n , 6 . 9 %; o , 31 . 4 %. 1 h nmr ( cd 2 cl 2 , δppm ): δ7 . 6 ( d , 4 . 0 h , c 6 h 4 no 2 , h meta to no 2 ), δ8 . 4 ( d and s , 7 . 7 h , terephthaloyl and c 6 h 4 no 2 , h ortho to no 2 ). the procedure of example 12b was repeated except that coupling was begun 2 . 5 h after the mma feed with 1 . 60 g of solid dnpt ( 7 . 9 mmol ). additional biacetate catalyst ( 100 μl ) caused the temperature to rise 0 . 2 ° c . and a yellow color to appear temporarily . much of the solid did not dissolve even overnight . the solid was filtered off and the polymer hydrolyzed to diol and isolated as usual . no aliquot was removed before hydrolysis . gpc analysis : theor . mn ( 100 % conversion and coupling )= 6400 ; mn = 3100 , mw = 3900 , mw / mn = 1 . 26 ; the procedure of example 12b was repeated except that polymerization used 35 μl of 0 . 04m bu 4 noac . hoac . 6h 2 o / thf , and coupling was begun 4 . 5 h after the mma feed , with 1 . 25 g diphenyl isophthalate ( polysciences , 3 . 9 mmol ) in 12 ml of very dry thf . after a temperature rise of 0 . 1 ° c ., 200 μl of biacetate solution was added and the temperature rose an additional 0 . 4 ° c . and the solution yellowed slightly . recovered pmma ( dried 32 h in a 65 ° c . vacuum oven ) weighed 25 . 0 g , a 98 . 1 % conversion of mma . gpc analysis : theor . mn ( 100 % conversion and coupling )= 6400 ; mn = 3600 , mw = 4300 , mw / mn = 1 . 20 ; the procedure of example 12b was repeated except that 35 μl of 0 . 04m bu 4 noac . hoac . 6h 2 o / thf was used for polymerization , mma feed took 45 min and coupling was started 4 . 75 h after the mma feed with 1 . 1 ml triethylamine ( fisher , 99 %, 7 . 8 mmol ) and 0 . 82 g terephthaloyl chloride ( aldrich , 97 %, 3 . 9 mmol ) in 16 ml of very dry thf . the solution turned yellow . there was a 0 . 1 ° c . rise , but 0 . 2 ml of biacetate solution caused no further change , and 2 ml of 0 . 04m bu 4 noac ( fluka )/ thf , added 1 h later , similarly caused no change . recovered pmma ( dried 32 h in a 65 ° c . vacuum oven ) weighed 22 . 2 g , an 86 . 4 % conversion of mma . the above experiment was essentially repeated except that 4 - dimethylaminopyridine in dry thf was used to absorb acidic by - products of a potential coupling reaction . analysis of the recovered polymer again showed that no coupling had occurred . the mixed sulfonic - carboxylic dianhydride , terephthaloyl bis ( p - toluenesulfonate ), was prepared according to c . g . overberger and e . sarlo , j . am . chem . soc ., 85 , 2446 ( 1963 ). a pure sample , mp 173 °- 6 ° c . ( lit . 174 °- 6 ° c .) was obtained . the procedure of example 12b was repeated in a 500 - ml r . b . flask , except that coupling was begun 3 . 5 h after the mma feed with 1 . 86 g of the mixed anhydride described above ( 3 . 9 mmol ) in 190 ml of very dry thf . the temperature rose 1 . 1 ° c . when 0 . 2 ml of biacetate solution was added , there was no further exotherm and so another 0 . 8 ml was added over the next 10 min , without an effect on temperature . these analyses show that no coupling occurred , and that me 3 sio groups were quantitatively converted to oh . sequential terephthaloyl fluoride capping and ethylene glycol finishing of polymeric ska the procedure of example 12b was repeated except for the use of 35 μl of 0 . 04m bu 4 noac . hoac . 6h 2 o / thf at the start of the mma feed , and another 15 μl 10 min into the mma feed , after 7 ml of mma had been fed in . the mma feed took 1 h . five hours after the mma feed was completed , the solution was treated with 1 . 7 g terephthaloyl fluoride ( tf 2 ) ( 10 . 0 mmol ) in 10 ml of very dry thf . the temperature rose 0 . 1 ° c ., and 0 . 2 ml of biacetate solution was added , causing the temperature to rise 1 . 5 ° c . and the solution to yellow slightly . the reaction mixture was left unstirred for 17 h at rt . for other purposes , 50 ml of solution was removed by syringe . the remaining solution was treated at rt with 1 . 8 ml ethylene glycol ( eg ) ( 32 . 3 mmol ) and 1 . 2 ml triethylamine ( 8 . 6 mmol ), causing a 2 . 4 ° c . temperature rise . the solution was stirred 7 h then left unstirred at rt overnight . the solution was then treated , while being stirred , with 4 . 0 ml of 10 % ( w / w ) hcl / meoh ( 11 mmol of hcl ), sufficient to render the mixture acidic . solids were removed by filtration and the solution was concentrated as usual and poured into well - stirred hexane to cause polymer to precipitate . the polymer , dried 48 h in a 65 ° c . vacuum oven , weighed 12 . 3 g . polymer from the 50 ml sample removed earlier weighed 11 . 6 g . recovered pmma was thus 23 . 9 g . gpc analysis : theor . mn ( 100 % conversion and tf 2 and eg capping ; no coupling )= wt mma / moles tteb + fragments of tteb , tf 2 , and eg = 2950 + 132 + 132 + 61 = 3300 . mn = 3400 , mw = 4200 , mw / mn = 1 . 24 ; hplc analysis : pmma 1 . 4 %; pmma - oh 6 . 3 % and ho - pmma - oh 92 . 2 %; the latter showed a double peak representing diol by coupling and finishing . nmr analysis ( cdcl 3 , δppm ): theor . mma / tf 2 end - group = d . p . before capping = 29 . 4 ; actual mma / tf 2 ( meo at δ3 . 55 vs . c 6 h 4 at δ7 . 7 and 8 . 05 )= 24 . 0 the δ7 . 7 multiplet represents tf 2 - coupling ( cf . example 9b ), and perhaps half of the protons of the tf 2 - capping moieties . the δ8 . 0 multiplet represents tf 2 capping . these analyses show that much of the polymer is capped , some is coupled , and most chains have 2 oh termini . sequential tf 2 capping and 1 , 4 - butanediol ( bdo ) finishing of polymeric ska the procedure of example 12b was repeated except for the use of 35 μl of 0 . 04m bu 4 noac . hoac . 6h 2 o / thf and a 70 - min mma feed . the polymer solution was treated with 1 . 34 g of tf 2 ( 7 . 9 mmol ) in 10 ml of very dry thf , 4 . 5 h after the mma feed . after 0 . 2 ml of biacetate was added , the temperature rose 2 . 0 ° c . and the solution yellowed slightly . the flask was stirred 1 h and left unstirred 17 h . the stirred solution was then treated with 2 . 8 ml bdo ( aldrich , 31 . 6 mmol ) and 1 . 2 ml triethylamine ( fisher , 8 . 6 mmol ) and stirred 1 h at rt . a 1 - ml aliquot was removed by syringe , injected into 0 . 5 ml of 10 % ( w / w ) hcl / meoh , evaporated to dryness , and redissolved in ch 2 cl 2 . polymer was isolated by filtration after precipitation in excess hexane -- sample a . the remaining solution was treated with 1 . 1 ml ( 9 . 5 mmol ) of aldrich 5 - amino - 1 - pentanol , then hydrolyzed with 10 ml of 10 % ( w / w ) hcl / meoh and stirred 1 h at rt . it was concentrated to dryness in a rotary evaporator , the residue dissolved in 75 ml ch 2 cl 2 , extracted with three 50 - ml portions of deionized water and then with 50 ml saturated aqueous nacl . the ch 2 cl 2 phase , about 75 ml in volume , was poured slowly into about 1 . 5 l of well - stirred hexane to precipitate polymer . the solid was vacuum filtered , washed 3 times with hexane and dried at rt and then in a 65 ° c . vacuum oven for 56 h -- sample b . the combined pmma samples weighed 24 . 7 g , representing a 91 . 8 % conversion of mma . gpc analysis : theor . mn ( 100 % conversion and tf 2 and bdo capping ; no coupling )= wt mma / moles tteb = fragments of tteb , tf 2 , and bdo = 2950 + 132 + 132 + 89 = 3300 . a -- mn = 3600 , mw = 4600 , mw / mn = 1 . 27 ; b -- mn = 3000 , mw = 3700 , mw / mn = 1 . 24 ; hplc analysis : a -- pmma or impurity 3 . 0 %, pmma - oh 4 . 1 % and ho - pmma - oh 92 . 9 %: b -- pmma or impurity 2 . 5 %, pmma - oh 5 . 2 % and ho - pmma - oh 92 . 3 %. two diol peaks representing capped and coupled products were obtained . nmr analysis ( cdcl 3 , δppm ): theor . mma / tf 2 end - group = 29 . 4 ; b -- actual mma / tf 2 ( δ3 . 55 vs . δ7 . 7 and 8 . 05 )= 29 . 8 ; the δ7 . 7 multiplet represents tf 2 coupling and perhaps half of the protons of the tf 2 - capping moieties . the δ8 . 05 multiplet represents tf 2 - capping . the analyses show that much of the polymer is capped , some is coupled , and most chains have hydroxyl groups at each end . a separate experiment was run to prove that the above telechelic ( dihydroxy ) polymer can be chain - extended by coupling of the terminal hydroxyl groups . a tared , dry 50 - ml r . b . flask was stoppered with a serum - cap and cooled under argon . about 0 . 60 ml of molten bis ( p - isocyanatophenyl ) methane ( mdi , upjohn , isonate 125m ), stored in a 50 °- 60 ° c . oven for 1 week , was injected into the flask with a syringe pre - warmed in the same oven . the weight of mdi , 0 . 622 g , was obtained by re - weighing the r . b . flask . α , ω - dihydroxy - pmma , sample b prepared above , after drying for 3 days in a 65 ° c . vacuum oven , was weighed out quickly while hot . the stopper was briefly removed from the flask while 8 . 57 g of pmma ( ca . 1 : 1 mole ratio ) and a magnetic stirring bar were introduced . stoppered again , and under argon , the flask was charged with 10 ml of very dry thf . the flask was stirred for 15 min to dissolve all ingredients and then 4 drops of dibutyltin dilaurate ( t - 12 catalyst , m and t chemical co . ), were added by disposable pasteur pipette . no viscosity increase was seen after 5 min , but stirring was difficult after 15 min . after 1 h 20 min , a sample ( c ) was removed from the flask with a spatula . the reaction flask was connected to a dried short - path still head and receiving flask , the assembly kept under argon . the reaction flask was heated to reflux to drive off the thf and then held in an oil bath at 115 ° c . for 0 . 5 h and at 107 ° c . for 3 h . it was then left at rt for 12 h . the solid residue was dissolved in the reaction flask in 25 ml thf . the solubility of the solid suggested that cross - linking reactions had largely been avoided . the solution was diluted further with 45 ml thf and dripped into 500 ml of well - stirred hexane , to precipitate polymer . the fibrous product was vacuum filtered and rinsed 3 times with hexane . after drying 40 h in a 65 ° c . vacuum oven , this sample ( d ) weighed 8 . 8 g . samples c and d had a combined weight of 9 . 5 g . gpc analysis : α , ω - dihydroxy - pmma ( sample b ): mn = 3000 , mw = 3700 , mw / mn = 1 . 24 ; c -- mn = 24 , 400 , mw = 72 , 700 , mw / mn = 2 . 98 ; d -- mn = 20 , 700 , mw = 64 , 800 , mw / mn = 3 . 13 ; both c and d have low molecular weight peaks in the range of dihydroxy - pmma representing about 5 % of the peak area of the product . the results show that the dihydroxy - pmma substrate contained a sufficient number of difunctional hydroxyl - terminated chains to be extended to high molecular weight polymer by reaction with mdi . a 1000 - ml round - bottom flask , equipped with a mechanical stirrer , pressure - equalizing dropping funnel , nitrogen inlet tube , and thermowell , was purged with and then held under a slightly positive pressure of nitrogen . the flask was charged with 300 ml of pyridine ( dried over molecular sieves ), and 23 . 2 ml of sebacyl chloride ( 0 . 10 moles , d = 1 . 121 g / ml , mw = 239 . 1 , aldrich , 92 %) were syringed into the stirred solvent . a yellow solid precipitated . the dissolution of 32 . 92 g of 2 , 4 - dichloro - phenol ( 0 . 2 moles , mw = 163 . 0 , aldrich , 99 %) in 100 ml of dry pyridine was accompanied by a small exotherm . the solution was dripped slowly into the flask from the dropping funnel , without heat evolution . the flask was stirred for 6 h thereafter and left unstirred another 72 h . the mixture was slightly acidified with 10 % aq hcl . a fine solid precipitated which was isolated by vacuum filtration , rinsed twice with water on the funnel , and dried in part on the funnel . the slightly wet , waxy crude product weighed 66 . 2 g ( theory , 49 . 2 g ). the produce was tested with a variety of recrystallization solvents , then 31 . 7 g thereof was dissolved in 50 ml of thf and solid impurities removed by gravity filtration of the hot solution . mixing with 500 ml of water gave 28 g of precipitate which was redissolved in about 80 ml of thf , the solution filtered through celite ® to remove additional solid impurities . the clear thf solution was concentrated to about 50 ml and , still hot , brought to the point of just becoming cloudy by adding about 25 ml of methanol . the product which crystallized overnight was isolated by vacuum filtration , rinsed twice with 2 : 1 methanol / thf , and dried 1 h in a 65 ° c . vacuum oven . this first crop weighed 9 . 35 g . the filtrate was concentrated to 20 ml and 10 ml methanol were added . the second crop obtained from overnight crystallization was isolated as above and weighed 1 . 57 g . the 2 crops together weighed 10 . 9 g , a 46 % yield ( theoretical yield , 23 . 6 g , based on 31 . 7 g of crude product ). the products were further purified by dissolving both crops in 50 ml of hot ethyl acetate , filtering out impurities , concentrating to about 15 ml , and adding 8 ml of hexane to reach the cloud point . solids began to appear in 1 h and were voluminous in 3 h . the solid was isolated by vacuum filtration , rinsed with 2 : 1 ethyl acetate / hexane , and dried on the filter and then for 1 h in a 65 ° c . vacuum oven with slight nitrogen bleed . it weighed 4 . 3 g ( 18 . 3 % yield ), its elemental analysis and proton nmr spectrum consistent with theory . calcd . for c 22 h 22 o 4 cl 4 : c , 53 . 7 ; h , 4 . 5 ; o , 13 . 0 ; cl , 28 . 8 . found : c , 54 . 2 ; h , 4 . 7 ; o , 13 . 1 ; cl , 27 . 7 . proton nmr ( cdcl 3 , δppm ): δ1 . 4 ( m , 8 . 6 h ), 1 . 8 ( pentet , 4 . 0 h ), 2 . 6 ( t , 4 . 0 h ), 7 . 0 ( d , 2 . 0 h ), 7 . 2 ( dd , 2 . 2 h ), 7 . 4 ( d , 1 . 8 h ). melting points : first crop -- 95 °- 98 . 5 ° c ., re - recrystallized , 97 °- 98 . 5 ° c . the procedure of example 9b was repeated twice , with changes noted below : ______________________________________ sample a sample b______________________________________tteb initiator , ml ( mmol ) 2 . 5 ( 7 . 9 ) 2 . 5 ( 7 . 9 ) 0 . 04 m bu . sub . 4 noac . hoac . 6 30 60h . sub . 2 o / thf , μlmma feed time , min 65 65coupling begun after ( h ) 2 . 5 3 . 5re - recrystd . dcpseb / thf , 1 . 94 1 . 94g ( mmol )/ ml ( 3 . 9 )/ 50 ( 3 . 9 )/ 20temperature rise , ° c . 0 00 . 04 m bu . sub . 4 noac . hoac . 6 0 . 2 0 . 5h . sub . 2 o / thf , mladditional temperature 0 . 4 1 . 1rise , ° c . ______________________________________ the solutions were left for 18 h and then the polymer was hydrolyzed to hydroxyl end - groups by stirring each with 5 ml of 10 % hcl / methanol for 1 h at room temperature . no aliquot was removed prior to hydrolysis . the polymer was precipitated and isolated as above and dried to constant weight in a 65 ° c . vacuum oven , yielding 24 . 6 g of sample a . only a portion of sample b was so isolated for gpc and hplc analysis . gpc analysis : theor . mn ( 100 % conversion and coupling )= 6400 ; sample a -- mn = 3200 , mw = 4500 , mw / mn = 1 . 38 ; sample b -- mn = 3600 , mw = 4500 , mw / mn = 1 . 26 ; hplc analysis : sample a -- pmma 1 . 2 %, unknowns 31 . 7 %, pmma - oh 25 . 9 : and ho - pmma - oh 41 . 2 %: sample b -- pmma 1 . 8 %, unknown 21 . 0 %, pmma - oh 17 . 4 % and ho - pmma - oh 59 . 7 %. the nitrogen - purged apparatus described in example 17a for the preparation of dcpseb was charged with 300 ml of molecular sieves - dried pyridine and 20 . 3 g of terephthaloyl chloride ( 0 . 10 moles , mw = 203 . 0 , aldrich , 97 %), which gave a cloudy , yellow mixture . a solution of 32 . 6 g of 2 , 4 - dichlorophenol ( 0 . 20 moles ) in 100 ml of dry pyridine was dripped into the stirred mixture over 15 min , causing a 1 . 3 ° c . exotherm . the mixture thickened and turned white . it was stirred 6 h more and left unstirred overnight . the mixture was slightly acidified with 10 % aq hcl , the crude product isolated from it by vacuum filtration , then rinsed twice with ethanol on the funnel and dried on the funnel to 62 g of slightly wet solid . the product gave a hazy solution in 1200 ml of hot thf , which was filtered hot . after 2 h , a first crop of recystallized solid was isolated by vacuum filtration and rinsed with a minimum of thf . more solids appeared in the filtrate after concentration to 200 ml . a second crop was taken as above after crystallization . the 2 crops were dried on their respective filtration funnels and then overnight at room temperature in a vacuum oven with a slight nitrogen bleed . the combined weight , 27 . 1 g , was 60 % of the theoretical 45 . 6 g . elemental analysis is consistent with theory . calcd . for c 20 h 10 o 4 cl 4 : c , 52 . 7 ; h , 2 . 2 ; cl , 31 . 1 . found : c , 52 . 8 ; h . 2 . 2 ; cl , 31 . 5 . yields and melting points : first crop -- 21 . 5 g , 220 °- 221 . 5 ° c . second crop -- 5 . 6 g , 219 °- 222 . 5 ° c . the procedure of example 9b was repeated with the following changes . mma was polymerized with 2 . 5 ml tteb initiator ( 7 . 9 mmol ) and 30 microliters of 0 . 04m bu 4 noac . hoac . 6h 2 o / thf catalyst , and mma feed took 80 min . coupling was begun 3 h thereafter with 1 . 80 g ( 3 . 9 mmol ) of the first crop of recrystallized dcpt in 250 ml of very dry thf and 0 . 2 ml of 0 . 04m biacetate catalyst , the temperature rising 1 ° c . because of the warmth of the dcpt solution . after 18 h , the polymer was hydrolyzed to hydroxyl end - groups by stirring 1 h at room temperature with 5 ml of 10 % hcl / methanol . no aliquot was removed prior to hydrolysis . the recovered , 65 ° c . vacuum oven - dried pmma weighed 28 . 5 g . gpc analysis : theor . mn ( 100 % conversion and coupling )= 6400 ; mn = 4800 , mw = 5700 , mw / mn = 1 . 18 ; hplc analysis : pmma 4 . 6 %, unknown 22 . 5 %, pmma - oh 10 . 1 % and ho - pmma - oh 62 . 9 %. | 2 |
in accordance with the present invention , the liquid heat - sterilised food may be , for instance , a dairy product such as white coffee , or cocoa or tea . the heat - sterilisation may be carried out in an air - tight vessel , e . g . when the liquid food is canned or bottled . the ingredients of white coffee may be instant coffee powder , coffee extract , coffee concentrate or roast and ground coffee together with water , sucrose and milk , as well as with small amounts of optional ingredients such as dipotassium phosphate and sodium bicarbonate . preferably , the milk ingredient is a mixture of high - fat cream and skim milk powder . the enzymatically - hydrolysed phospholipid is produced by the action of a phospholipase on the phospholipid to give a lysophospholipid . phospholipids , which may advantageously be used in a powdered or paste form , form a class of chemical compounds comprising phosphatidylcholine ( lecithin ) and phosphatidylethanolamine as the main elements . phospholipase a is an enzyme which may be manufactured from porcine pancreatic glands and which hydrolyses phospholipids by specific cleavage of the bond binding a fatty acid ester to the glycerol part of the phospholipid molecule thereby replacing the fatty acid ester by a hydroxyl group . the hydrolysis results in an increase of free fatty acids and a conversion of the phosphatidylcholine ( lecithin ) and phosphatidylethanolamine into several substrates such as lysophosphatidylcholine , lysophosphatidylethanolamine , phosphatidylcholine glycerol and phosphatidylethanolamine glycerol . phospholipase a - 2 ( sold commercially under the trade name lecitase ) is the preferred enzyme and cleaves the bond binding a fatty acid ester to the glycerol part of the phospholipid molecule , mainly at position 2 . the degree of conversion is the proportion of phosphatidylcholine present before hydrolysis that is converted into lyso - phosphatidylcholine , expressed in mol %. in the present invention , the enzymatically - hydrolysed phospholipid preferably has a degree of conversion of at least 90 % and more preferably , of at least 95 %. the enzymatically - hydrolysed phospholipid is conveniently an enzymatically - hydrolysed lecithin which is produced by the action of phospholipase a - 2 on the lecithin to give a lysolecithin . commercial lecithin is predominantly soybean lecithin obtained as a by - product in the manufacture of soybean oil . lecithin can also be isolated from eggs and can be obtained synthetically . it can be used in a powdered or paste form . one method for the enzymatic hydrolysis of phospholipids is claimed in japanese laid - open patent application no . jp - a - 63 44893 in which the phospholipid is hydrolysed with phospholipase a after adding 0 . 1 to 1 part by weight of water to 1 part by weight of phospholipid . the degree of conversion of phospholipid to lysophospholipid in the practical embodiments varies from 80 to 90 %. it is stated that larger amounts of water and / or agitated conditions give lower degrees of conversion . we have found that by using more than 1 part by weight of water to 1 part by weight of phospholipid in the enzymatic hydrolysis of a phospholipid using agitated conditions , we can obtain a degree of conversion greater than 90 % or even 95 %. in carrying out the hydrolysis process of the present invention , the amount of water present in the aqueous medium is preferably from 1 . 5 to 7 . 5 parts , more preferably from 2 to 6 parts , even more preferably from 3 to 5 parts , and most preferably from 3 . 5 to 4 . 5 parts by weight per part by weight of phospholipid . the water of the aqueous medium may be ordinary tap water , distilled water , or ion - exchanged water . the amount of the phospholipid may be from 5 to 40 %, preferably from 10 to 30 % and especially from 15 to 25 % by weight based on the weight of the reaction mixture . the phospholipid may be added in one , two or more stages . the phospholipase may be used in an amount of from 0 . 05 to 0 . 5 %, preferably from 0 . 1 to 0 . 4 % and especially from 0 . 15 to 0 . 3 % by weight based on the weight of the aqueous medium . the enzymatic reaction is preferably carried with slow or gentle agitation . the presence of a water - soluble calcium salt , e . g . 0 . 01 to 0 . 25 % and preferably from 0 . 025 to 0 . 15 % by weight based on the weight of the aqueous medium , is desirable during the reaction . calcium is a co - factor to the phospholipase enzyme . calcium chloride is the preferred salt and is most preferably used in the dihydrate form . the hydrolysis is carried out conveniently in the aqueous medium at a temperature of from 25 ° c . to 70 ° c ., preferably from 30 ° c . to 60 ° c ., more preferably from 40 ° c . to 55 ° c ., and at a ph of from 5 to 9 and preferably of from 6 to 8 . the duration of the hydrolysis reaction may conveniently be from 30 minutes to 5 hours , preferably from 1 to 4 hours , and more preferably from 1 . 5 to 3 hours . although longer times may be used , e . g . up to 50 hours , there is no special advantage obtained in using such longer periods . after the reaction , the mixture is advantageously pasteurised and then dried . after pasteurisation and before drying , antioxidants such as vitamin c , vitamin e , tea extracts , and / or bha / bht may be added to protect the flavour , and a carrier such as maltodextrin , non - fat dried milk , starch , or gum arabic , may be added to the mixture . the enzymatically - hydrolysed phospholipid may be used in a powder or paste form . as stated above , sterilisation has been carried out usually at a temperature of about 121 ° c ., e . g . 1150 ° to 125 ° c ., over a period of from about 20 - 30 minutes , or under uht conditions , e . g . 140 ° to 150 ° c . for from 5 to 20 seconds , and such conditions may be used in the present invention . however , we have found that , by sterilising at 121 ° c . in the presence of an enzymatically - modified phospholipid in accordance with the present invention , the spoilage of liquid heat - sterilised food preparations is significantly less than by sterilising in the presence of ordinary phosphatides even if the period of the sterilisation is much less than 30 minutes . for instance , we have found that periods as low as 5 minutes , preferably from 6 to 15 minutes and more preferably from 7 to 10 minutes , can achieve reduced spoilage . the amount of enzymatically - hydrolysed phospholipid present in the liquid heat - sterilised food may be from 0 . 005 to 2 %, preferably from 0 . 01 to 1 . 25 %, more preferably from 0 . 025 to 1 . 0 % and especially from 0 . 04 to 0 . 75 % by weight based on the weight of the mixture . in the preparation of canned or bottled white coffee , the coffee ingredients and the enzymatically - hydrolysed phospholipid are mixed in the appropriate proportions , homogenised , canned or bottled , and then sterilised or retorted , followed by cooling to ambient or refrigeration temperatures . the amount of the enzymatically - hydrolysed phospholipid may be from 0 . 1 to 15 %, preferably from 0 . 25 to 10 %, more preferably from 0 . 5 to 7 . 5 % and especially from 1 . 0 to 5 . 0 % by weight based on the weight of the coffee solids . the canned or bottled white coffee is transported and normally stored at ambient or refrigeration temperatures . if used in a vending machine , the storage temperature during the winter months may be from about 55 °- 60 ° c ., and we have found that by sterilising the ingredients in the presence of an enzymatically hydrolysed phospholipid in accordance with the present invention , there is significantly less spoilage of the coffee drink than when sterilising the ingredients alone or in the presence of conventional emulsifiers such as a phospholipid which has not been enzymatically hydrolysed . the coffee drink may be stored for several weeks without spoilage . the following examples further illustrate the present invention . parts and percentages are given by weight . the powdered enzymatically hydrolysed lecithin used in the examples according to the invention was prepared as follows : 100 parts of tap water is slowly stirred in a jacketed kettle at 30 ° c . and at ph 8 . 0 . 1 part of calcium chloride dihydrate and 0 . 22 part of phospholipase a - 2 are added and the ph adjusted to 7 , if necessary , by using 10n potassium hydroxide while the temperature is slowly increased to 50 ° c . 10 parts of powdered deoiled soy lecithin ( half the total ) are slowly added to the mixture , whereupon an immediate drop in the ph is observed which indicates that an enzymatic reaction is taking place . the ph is readjusted to 7 by using 10n potassium hydroxide , and the reaction is allowed to proceed for 30 minutes , after which time a further 10 parts ( the second half ) of the lecithin is added and the reaction is allowed to proceed for a further 90 minutes with the necessary ph adjustment to 8 as before . after the reaction , the product is pasteurised by heating to 95 ° c . for 5 minutes to deactivate the enzyme and then cooled to 75 ° c . 10 parts of maltodextrin is added , and the product is mixed into a homogeneous slurry while being cooled to ambient temperature . the slurried product is finally spray - dried at a rate of about 0 . 3 kg per minute where the inlet temperature is 160 ° c . and the outlet temperature is 95 ° c . a white coffee mix is prepared by mixing the following ingredients in the amounts indicated : ______________________________________water 85 . 815cream , 40 % fat 2 . 260skim milk powder 2 . 160sucrose 5 . 500coffee powder , nescafe classic 1 . 100dipotassium phosphate 0 . 080sodium bicarbonate 0 . 060enzyme modified lecithin powder 0 . 025 ( 50 % maltodextrin ) sucrose ester p - 1670 -- water to standarize 3 . 000total 100 . 000 % ______________________________________ after mixing the ingredients , the mix is heated to 76 ° c ., canned , retorted at 121 ° c . for 8 minutes and cooled to ambient temperature . the canned white coffee is incubated at 60 ° c . for 14 days , after which time the spoilage was less than 1 % ( 0 / 100 cans ), and ph drop was zero . a similar procedure to that carried out in example 1 was followed except that , after canning , the mix was held at 76 ° c . for three hours before retorting . the canned white coffee is incubated at 60 ° c . for 14 days , after which time the spoilage was less than 1 % ( 0 / 100 cans ), and ph drop was zero . a similar procedure to that carried out in example 1 was followed but using 0 . 25 %, instead of 0 . 025 %, of ! powdered enzymatically - hydrolysed lecithin based on the total weight of the coffee mix . the canned white coffee is incubated at 60 ° c . for 14 days , after which time the spoilage was less than 1 % ( 0 / 100 cans ), and ph drop was zero . a similar procedure to that carried out in example 1 was followed , but excluding the powdered enzymatically - hydrolysed lecithin . after incubation of the canned white coffee at 60 ° c . for 14 days , the spoilage was 99 % and the ph drop was 90 / 91 . a similar procedure to that carried out in example 1 was followed , but adding 0 . 25 % of powdered lecithin instead of the powdered enzymatically - hydrolysed lecithin there used . after incubation of the canned white coffee at 60 ° c . for 14 days , the spoilage was 7 . 5 % and the ph drop was 6 / 79 . a similar procedure to that carried out in example 1 was followed , but adding 0 . 2 % of powdered lecithin instead of the powdered enzymatically - hydrolysed lecithin there used . after incubation of the canned white coffee at 60 ° c . for 14 days , the spoilage was 48 % and the ph drop was 42 / 87 . a similar procedure to that carried out in example 1 was followed , but adding a mixture of 0 . 09 % durem 207 ( mono and diglycerides ) supplied by van den berg food and 0 . 01 % tween 80 ( polyoxyethylene sorbitan monooleate ) instead of the powdered enzymatically - hydrolyzed lecithin there used . after incubation of the canned white coffee at 60 ° c . for 14 days , the spoilage was 27 % and the ph drop was 24 / 90 . a similar procedure to that carried out in example 1 was followed , but adding a mixture of 0 . 09 % durem 207 and 0 . 01 % panodan pvk ( diacetyl tartaric acid ester of monoglycerides ) supplied by grindsted ingredients , instead of the powdered enzymatically - hydrolysed lecithin there used . after incubation of the canned white coffee at 60 ° c . for 14 days , the spoilage was 20 % and the ph drop was 18 / 90 . | 0 |
an automobile steering lock in the present invention , as shown in fig1 comprises an inner half housing 1 , an outer half housing 2 , a stop member 3 , an elongate rod 4 , a head bolt 5 , a motor 6 , an electronic alarm set 7 and a cap 8 as main components combined together . the inner half housing 1 has a block portion 16 , a length - wise passageway 10 in an upper section of the block portion 16 , a stop edge 100 of a small size , a chamber 11 formed in a rear end of the passageway 10 , a motor hole 12 in parallel to the passageway 10 in the lower section of the block portion 16 , a cover annular edge formed in an outer end of the motor hole 12 for a cover 63 to fit therein , a vertical deadbolt hole 13 provided in the lower section and communicating with the passageway 10 and the motor hole 12 , an outer annular edge 130 in the deadbolt hole 13 for a cover 55 to fit therein , two vertical bolt holes 14 , 14 are provided in the bottom of a rear end of the block portion 16 for a pair of bolts , to fit upwardly therethrough , and a curved semiround portion 15 formed to abut at a right angle on the block portion 16 and able to fit around an outer surface of a portion of the steering wheel of an automobile . the outer half housing 2 has a curved semiround portion 20 , a vertical wall 21 extending up from a center section of the semi - round portion 20 , a locking rod 22 extending horizontally inward from an upper end of the vertical wall 21 and having a plurality of straight transverse grooves 23 in a bottom surface , an annular groove 24 in the end of the locking rod 22 , and each of the grooves 23 having a sloped face 231 and a vertical face 230 adjacent each other . the curved semiround portion 15 and 20 fit around outer and inner surfaces of a portion of the steering wheel of an automobile so that the two half housings 1 and 2 may surround the portion of the steering wheel in locking engagement therewith . the stop member 3 is shaped as a rectangular ring , having an aperture 31 in one side and a large center hole for engaging annular groove 24 . the elongate rod 4 has two bolt holes 42 , 42 in the front end for the bolts 14 , 14 to fit upwardly therethrough so as to fit through the bolt holes 14 , 14 in the inner half housing 1 to combine the rod 4 with the half semiround housing 1 , a recess 40 in a front end face for disposing a spring 41 therein , a cord hole 43 in the front bottom , a chamber 44 with an upper opening in a rear portion , and a cord hole 440 in a front wall of the chamber 44 . the deadbolt 5 is to be disposed in the vertical deadbolt hole 13 of the block portion 16 of the inner half housing 1 , and has a sloped face 50 and a vertical face 51 at its upper end formed to selectively engage any of grooves 23 , a flat recess 52 cut in an intermediate portion , a spring recess 53 in a bottom to receive a spring 54 therein , and a cover 55 fitting and welded in the opening edge 130 of the deadbolt hole 13 to stop and bias the spring 54 . the motor 6 is disposed in the motor hole 12 of the inner half housing 1 , and has a shaft 60 extending to the front , a semi - round activating block 61 fixed at the front of the shaft 60 , a power cord 62 coming out of the end of the motor 6 , and a cover 63 fitting and welded in the opening edge 120 of the motor hole 12 of the inner half housing 1 . the electronic alarm set 7 is disposed in the chamber 44 of the elongate rod 4 , and has a power cord 70 connected with the power cord 62 of the motor 6 for giving out high decibel sounds in case the steering wheel is rotated or the body of the automobile is touched by a would - be thief after this lock is installed . the alarm set 7 is controlled by a remote controller . the cap 8 is provided to close the upper opening of the chamber 44 to protect the electronic alarm set 7 after the set 7 is disposed therein . in assembling , referring to fig1 and 2 , firstly , the locking rod portion 22 of the outer half housing 2 is fitted the passageway 10 of the inner half housing 1 , with the stop member 3 engaged in the annular groove 24 of the locking rod 22 to secure it in position and preventing it from completely separating from the block portion 16 . then the deadbolt 5 is inserted in the deadbolt hole 13 of the inner half housing 1 , with the vertical face 51 engaging the vertical face 230 of one of the grooves 23 of the locking rod 22 , the spring 53 is disposed in the recess 52 , and with the cover 55 is fitted in the opening edge 130 of the deadbolt hole 13 and welded thereon . next , the electronic alarm set 7 is disposed in the chamber 44 of the elongate rod 4 , with its power cord 70 extending out of the hole 440 of the chamber 44 and out of the cord hole 43 in the front bottom of the elongate rod 4 and connected with the power cord 60 of the motor 6 . after that , the cover 8 is used to close up the chamber 44 , the spring 41 is disposed in the recess 40 , and the front end of the elongate rod 4 is inserted in the chamber 11 of the inner half housing 1 . the two bolts 14 , 14 are threadedly engaged through the bolt holes 42 , 42 and 14 , 14 , thus finishing the assemblage . if this lock is to be applied on the steering wheel of an automobile , referring to fig3 and 5 , firstly , the semiround portion 15 of the inner half housing 1 is fitted around the outer surface of an upper portion of the steering wheel , letting the elongate rod 4 extend to the corner between the gauge panel and the wind shield of the automobile , with the spring 54 pushing the deadbolt 5 upward to always engage one of the grooves 23 of the locking rod 22 of the outer half housing 2 in case of the deadbolt 5 being disposed in a locked condition . when the vertical face 51 of the deadbolt 5 engages a vertical face 230 of one of the grooves 23 , the outer half housing 2 cannot be pulled outward but can be pulled inward because the sloped face 50 of the deadbolt 5 permits it to slide along the sloped face 231 of grooves owing to resilience of the spring 54 , thus permitting the semiround portion 20 of the outer half housing 2 to closely surround the steering wheel , and the end of the locking rod 22 pressing the spring 41 , with the elongate rod 4 having its end sticking to the corner of the gauge panel and the windshield , thus preventing the steering wheel from being rotated . in addition , a remote controller is operated to turn on the electronic alarm set 7 , which is ready to give out a high decibel alarm if the lock being moved by rotating the steering wheel or by contacting the body of the automobile . if this steering lock is to be disengaged from the steering wheel , referring to fig3 and 4 , the remote controller is operated to cut off the electronic alarm set 7 , and the motor 6 is started through the power cord 70 , rotating the shaft 60 and the semiround block 61 for 180 ° degrees to push down the deadbolt 5 so that the vertical face 51 may separate from the vertical face 230 of the groove 23 , letting the spring 41 resiliently push the locking rod 22 outward for such a distance as to enable the outer half housing 2 to be released from the steering wheel . then the stop member 3 will prevent the locking rod 2 from being completely pulled out of the block portion 16 of the inner half portion . as can be understood from the above description , this automobile steering lock has the following advantages . 1 . locking and unlocking this lock is operated by means of the remote controller , this is very convenient and handy . 2 . the deadbolt moves steadily in engagement and disengagement from any one of the grooves of the locking rod , thus assuring that the locking or unlocking action is stable and accurate . 3 . the remote controller makes the locking or unlocking action accurate and convenient , thus preventing the automobile from being stolen , and also providing an alarm . | 8 |
the invention will be described in terms of a glass fiber forming operation , although it is to be understood that the invention can be practiced using other heat softenable mineral material , such as rock , slag , and basalt . as shown in fig1 glass spinner 10 rotates on axis of rotation 12 and is driven by shaft 14 . the spinner is supplied by molten stream of glass 16 which is centrifuged through the walls of the spinner of form glass fibers18 . the glass fibers are maintained in a soft , attenuable state immediatelyoutside the spinner by the heat from annular burner 20 . the radially - traveling glass fibers are turned down by blower 21 into a cylindrically shaped veil 22 of fibers , traveling downwardly , i . e ., in thedirection of the axis of the spinner . the process for creating the downwardly moving cylindrical veil of glass fibers is well known in the art . it is to be understood that the mineral fibers can be established by other means , such as through a spintex or wheel throwing process , or such as an air blown process . in any event , polymeric fibers are directed toward the stream of mineral fibers to cause an intermingling . positioned beneath the glass spinner is a rotatable device for distributingpolymeric fibers into contact with the veil from a position within the veil . the embodiment shown in fig1 includes the use of a second spinner , polymer spinner 24 , for distributing polymeric material into contact with the veil . the polymer spinner can be mounted for rotation in any form . as shown , it can be mounted with supports 26 into direct contact with the glass spinner for rotation . the polymer spinner is supplied with stream 28 of molten polymer material . as shown , this stream can be fed through the hollow portion of the glass spinner shaft . the molten polymer can be produced or supplied by using extruder equipment commonly known to those in the art of polymeric materials , such as pet . depending on the viscosities , surface tension and other parameters of the polymeric material , and on the rotation rate and orifice sizes of the polymer spinner , polymer fibers 30 may be produced from the polymer spinner . the polymer fibers travel radially outwardly where they meet and intermingle with the mineral fibers . since the glass fibers and glass spinners operate at a temperature of around 1 , 700 ° f ., the polymer fibers are rapidly thrust into a region of high temperature , causing the polymer fibers to soften . it has been found that some of polymer fibers melt , forming droplets or other particles which attach themselves to some of the mineral fibers . others ofthe polymer fibers retain their fibrous shape , resulting in the presence ofpolymer fibers in the mineral fiber pack 32 . the reason that some of polymeric material retains its fibrous shape , while other portions of the material form polymeric particles which attach themselves to the mineral fibers is not known . it may be that some of the polymer fibers do not soften to the extent required to cause them to lose their fibrous shape and turn into a more spherical shape . alternatively , it may be that although all polymer fibers are softened , only a portion of them come intocontact with mineral fibers while in a softened condition . in order to make sure that the polymeric material does not experience a temperature exceeding the degradation or oxidation limit , a cooling means , such as water distributor 35 can be used to control the temperature regime which is experienced by the polymer fibers or polymeric material . the water distributor can be any suitable means for supplying finely divided moisture into the vicinity of the traveling polymer material . another example of a cooling means is an air flow device , not shown , which directsair toward the polymer particles or fibers to control temperature at the point where the polymeric material meets the mineral fibers . after the intermingled polymeric material and mineral fibers are collected to form a pack , optionally the pack can be passed through oven 34 to resetthe form of the mineral fiber pack in order to produce mineral fiber product 36 . as shown in fig2 the glass fiber product is comprised of mineral fibers 18 and polymer fibers 30 . some of the mineral fibers have particulate polymer material attached to them , and some of the mineral fibers may be completely coated with polymer material . although the invention shown in fig1 used pet polymer material , it shouldbe understood that other high molecular weight polymeric material can be used in this invention . examples include polycarbonate material , polypropylene , polystyrene , and polysulfide . it should also be understood that various amounts of polymeric material andmineral fiber material can be provided in the ultimate mineral fiber product . for example , typical building insulation has about 5 % by weight of phenol / formaldehyde , and the insulation product resulting from this invention could have a similar weight ratio of polymeric material to the weight of the mineral fiber product . insulation molding media products could have polymeric material within the range of from about 5 to about 40percent , and preferably from about 10 to about 30 % by weight of the mineralfiber product . other mineral fiber products could include amounts of polymeric material exceeding 50 % by weight of the mineral fiber product and possibly even exceeding 70 percent . the method of the invention was employed to make a pet / glass fiber product . the glass fiber spinner had 50 , 000 orifices and was operated at a throughput of approximately 1 , 100 lbs . per hour . the pet material was supplied to a polymer spinner mounted for rotation beneath the glass spinner . the polymer spinner had approximately 7 , 000 orifices , and a throughput of approximately 50 lbs . per hour . the pet material had a molecular weight in excess of 200 , 000 . the spinners were maintained at different temperatures to successfully process the glass and the polymer material , respectively . the resulting product was a uniform blend of glass and polymer fibers , withsome of the polymeric material being attached to the glass fibers , and someof the polymeric material being retained as intermingled polymer fibers . the product from this trial was found to be more flexible and more resistant to breaking under deflection than traditional glass fiber wool molding media . when molded in a typical glass fiber wool molding media apparatus , the product of the invention gave superior results , primarily in terms of resistance to breaking under deflection . this benefit was evident when molded , both as produced , and when post - treated with a resin such as a phenol / formaldehyde . prior to molding , the product also exhibited increased recovery characteristics over that of the standard phenol / formaldehyde products . also , application of ultra - violet light to the product gave a clear indication that the pet / glass fiber product had agreater uniformity of binder distribution than exhibited in typical phenol / formaldehyde products . it will be evident from the foregoing that various modifications can be made to this invention . such , however , are considered as being within the scope of the invention . this invention will be found useful in the production of mineral fiber products , such as glass fiber products , for such uses as thermal insulation and glass fiber structural products . high performance polymer fibers such as pps can be substituted for the mineral fibers to make an all - polymer product . | 2 |
fig1 shows a tag 1 removably attached to a trailer 2 . in an embodiment the tag is mounted in the lower right hand corner on the front end of a trailer 3 - 8 inches from the right and 6 - 18 inches up from the bottom of the trailer . other objects to be tracked may include vehicles such as trucks , intermodal containers , and railcars , as well as containers , packages , baggage , and the like . fig2 is a perspective view of a removable tag 1 . as shown in fig2 the top of the tag is composed of the enclosure 3 , and handles 4 , 5 . in an embodiment the enclosure is designed and constructed from materials that allow the tag to withstand vibration and mechanical shock , for example such as a drop from 6 feet onto a concrete surface , as well as be waterproof , and resistant to uv light and chemical hazards , for example such as sulfuric acid and salt water . further , in an embodiment the enclosure is designed and constructed from materials that allow the tag to deliver excellent performance and reading stability across fluctuating temperatures in operating temperatures at least in the range of about − 40 to + 65 ° c . however , for tags that are used in milder climates less costly materials that do not meet theses temperature range requirements may be used to produce tags for less . in the preferred embodiment the enclosure 3 is constructed of abs plastic , however other materials may be used such as other plastics , metals , papers , and composites . further , those skilled in the art will appreciate that other materials and combination thereof can be used to construct the enclosure . the enclosure , as well as other components of the tag , may be constructed using a material that may be made to a custom color , or may have a coating , such as a paint , applied to it to give it a custom color . the purpose of such custom color may be for military purposes , or for quick visual reference to determine information such as ownership , contents , or point of origin . further in an embodiment the enclosure may glow in the dark . in an embodiment the enclosure is designed to meet or exceed many standards including an environment sealing rating of ip68 and shock and vibration endurance per mil std 810 - f and bs en 60068 - 2 . fig3 shows the bottom side 6 of the enclosure 3 . in an embodiment the bottom side is generally rectangular in shape with rounded ends , however those skilled in the art will appreciate that the bottom side may be of any shape designed to fit in specific spaces . in an embodiment , the enclosure is flush with the surface to which the tag is attached . in the case of a flat surface , the bottom side of the housing is preferably flat , and in the case of a curved surface the bottom side is preferably curved to match the curve of the surface . the enclosure may be constructed to be rigid or it may be constructed to be slightly deformable to be flush when attached to support surfaces that are imperfect or that deflect or change shape during use . this prevents the tag from being inadvertently removed if it is not perfectly flush with such surfaces . further , the bottom side of the enclosure may have a rubberlike coating or layer that increases friction and flushness between the tag and the surface to which it is mounted . further , those skilled in the art will appreciate that the bottom side can be formed to match the shape and surface features of any surface the tag it to be attached . in addition to the bottom side of the enclosure being flush with the surface to which it is attached , it is also desirable for the tag to be generally flush with the object to which it is attached and , in general , to have a low profile . to achieve this in the preferred embodiment , the enclosure 3 has a maximum thickness of 1 inch ( 2 . 5 cm ), this thickness is defined as the distance between the bottom side 6 and the top surface 7 . this thin design prevents the tag from being inadvertently dismounted due to contact with passing objects , as well as being more aerodynamic . further , in an embodiment the enclosure does not have sharp edges and hook - like features that would be prone to snagging and pulling the tag away from the surface to which the tag is attached . in an embodiment , the bottom edges of the enclosure include curved ends 8 , 9 and straight sides 10 , 11 . further , the tag is intended for use outdoors and the tag includes design features that are optimized to slough off accumulation of water and snow . to do this , the top side of the enclosure 3 does not have cavities where water and ice could accumulate . as shown in fig4 , fig5 , and fig6 , the top side includes a beveled and curved surface and edges that allow water to run over the tag . further , the tag may be treated with coatings designed to repel snow or water . in an embodiment , the enclosure 3 has a top surface 7 to which an adhesive label may be affixed . in an embodiment , the size of the face and label allow for seven characters to be visible from a distance of five feet away . further , the housing may contain a space on the side or top surface on which a barcode label may be placed which , in an embodiment a 13 digit barcode . the label and the barcode label are preferably weather resistant . handles are provided to make it easy for a person to place and remove the tag without the use of any special tools . fig2 shows an embodiment with two handles 4 , 5 that are affixed to the enclosure 3 in a way that allows them to be operable to selectively rotate from a deployed position as seen in fig2 to a stowed position as seen in fig4 . in an embodiment , the two handles 4 , 5 are on each end of the enclosure . each handle is composed of a u - shaped member . in an embodiment the u - shaped member has an opening with a diameter that is sufficient to allow access of a gloved finger , which in practice has been found to be about one inch . those skilled in the art will appreciate that the u - shape member and opening may be of other sizes and shapes . the u - shaped member comprises two axels 12 that engage within pivot points 13 located on the enclosure 3 to allow the u - shaped member to pivot relative to the enclosure between a stowed position ( fig4 ) and deployed position ( fig2 ). alternatively , the u - shaped member may comprise two pivot points and the enclosure may contain one or more axels to engage within the pivot points of the u - shaped member . the pivot points and axels may contain detents that allow the handle to remain in a fully deployed position until a threshold holding force toward the stowed position is exceeded wherein the handle may be returned to the stowed position . in the stowed position , the assembly of a handle and the enclosure has a lower profile than the deployed position . as shown in fig4 in an embodiment the handles are flush with the enclosure while in the stowed position . to accomplish this the enclosure 3 has channels 14 which cradle the handles 4 , 5 , when the tag is in the stowed position . in an embodiment , the channel 14 has a u - shape complementary to the handle &# 39 ; s u - shape and extends from a pivot point associated with a handle around the end of the enclosure and to the other pivot point associated with the handle . the stowed position advantageously protects the handles from damage . further , the handles being flush with the enclosure are not susceptible to being snagged open and causing the tag to be inadvertently dismounted . further , the stowed position is more aerodynamic than the deployed position . further , the flush design of the enclosure and handles in the stowed position also prevent accumulation of water , snow , and dirt . to ensure that the handles do not inadvertently become deployed from the stowed position detents on the handle , enclosure , or both hold the handle in the stowed position , until a threshold holding force is exceeded . in an embodiment , each channel contains a channel detent 19 which engages with the inner surface of the u - shape member of the handle to hold the handle in the stowed position until a threshold holding force is exceeded , at which point the channel detent disengages with the inner surface of the u - shaped member . to enable a user to manipulate the handle in a stowed position to exert the threshold holding force on the handle , the enclosure 3 has depressions 15 located on each end of the channels so that the under side of the handle is exposed when in the stowed position and a user can place the tip of a finger under the handle to exert force on the handle toward the deployed position . as shown in fig2 , once in the deployed position the handles are in a position to allow the tag to be manipulated easily by a user to mount and dismount the tag to and from a support surface . in an embodiment , the handles are made of a high strength pc / abs blend or other engineered thermoplastic . the handles may be constructed using the same material or a different material than that of the enclosure . further , each handle may be formed integrally with the enclosure , or each handle may be composed of multiple components . fig3 shows the bottom side of the tag . the tag is to be attached to an object , such as a trailer , truck , railcar , intermodal container , forklift , pallet , or crate by way of an attachment mechanism , which may include magnets , electromagnets , adhesives , suction , or mechanical fasteners such as velcro ®, a slot and groove combination , or a clip and flange combination , or any combination thereof . trucks , semi - trailers , intermodal containers , railcars , and other equipment commonly used in the shipping , transportation , and warehouse industries contain metal surfaces to which a magnet can be attached using magnetic forces . therefore , in an embodiment the attachment mechanism is preferably one or more magnets . as shown in fig3 , an embodiment includes two magnets 16 located toward the ends of the bottom 6 of the tag . the magnets may be encapsulated within the enclosure , or they may be attached to the enclosure inside of a recess . in an embodiment , each magnet has a rating of 18 . 5 lbs , is mounted to the underside of the tag within a recess 17 , and is held in place with countersunk screws 20 . in this embodiment , 20 lbs of force is needed to remove the tag using the handles . with this configuration of magnets , the tag can be mounted and dismounted over 2 , 000 times . in a preferred embodiment , the holding ability of the magnets exceeds any challenges posed by snow , rain , and vibration . in a preferred embodiment , the tag has the holding ability to be placed with a two - inch clearance from a trailer bottom and remains in place for at least three days of use . further , the tag can do this over the entire lifetime of the tag . further , in a preferred embodiment the tag is mountable on a wet surface , or a surface covered with one mm of either ice , mud , or both . however , if stronger magnets are used the tag can be mounted on surfaces with more than one mm of either ice , mud , or both but would require more force for a user to remove . a preferred embodiment is designed so that a 5 ′ 0 ″ person , who weighs 90 pounds wearing gloves could remove the tag from a mounted surface within three seconds . further , the installation of the tag on a wet , iced , or muddy surface averages about 15 seconds . within the enclosure 3 is a rfid device 21 . in an embodiment the rfid device is located within a void in the enclosure . in an embodiment , the rfid device is of the long range uhf passive type . in an embodiment , the rfid device is produced only within the fcc - approved band of 902 - 928 mhz . the rfid device has a read distance of at least 40 - 50 feet on - metal with existing reader and antenna setups . further , off - metal tethered performance is the same as that of current permanent tags . in a preferred embodiment , the rfid device is an alien higgs 3 having 512 bits of user memory , and the epc code is permanently locked in an effort to keep costs down . although the invention is described herein with reference to the preferred embodiment , one skilled in the art will readily appreciate that other applications may be substituted for those set forth herein without departing from the spirit and scope of the invention . accordingly , the invention should only be limited by the claims included below . | 6 |
fig1 schematically illustrates an example gas turbine engine 20 that includes a fan section 22 , a compressor section 24 , a combustor section 26 and a turbine section 28 . alternative engines might include an augmenter section ( not shown ) among other systems or features . the fan section 22 drives air along a bypass flow path b while the compressor section 24 draws air in along a core flow path c where air is compressed and communicated to a combustor section 26 . in the combustor section 26 , air is mixed with fuel and ignited to generate a high pressure exhaust gas stream that expands through the turbine section 28 where energy is extracted and utilized to drive the fan section 22 and the compressor section 24 . although the disclosed non - limiting embodiment depicts a turbofan gas turbine engine , it should be understood that the concepts described herein are not limited to use with turbofans as the teachings may be applied to other types of turbine engines ; for example a turbine engine including a three - spool architecture in which three spools concentrically rotate about a common axis and where a low spool enables a low pressure turbine to drive a fan via a gearbox or fan drive gear system , an intermediate spool that enables an intermediate pressure turbine to drive a first compressor of the compressor section , and a high spool that enables a high pressure turbine to drive a high pressure compressor of the compressor section . the example engine 20 generally includes a low speed spool 30 and a high speed spool 32 mounted for rotation about an engine central longitudinal axis a relative to an engine static structure 36 via several bearing systems 38 . it should be understood that various bearing systems 38 at various locations may alternatively or additionally be provided . the low speed spool 30 generally includes an inner shaft 40 that connects a fan 42 and a low pressure ( or first ) compressor section 44 to a low pressure ( or first ) turbine section 46 . the inner shaft 40 drives the fan 42 through a speed change device , such as a geared architecture also referred to as a fan drive gear system 48 , to drive the fan 42 at a lower speed than the low speed spool 30 . the high - speed spool 32 includes an outer shaft 50 that interconnects a high pressure ( or second ) compressor section 52 and a high pressure ( or second ) turbine section 54 . the inner shaft 40 and the outer shaft 50 are concentric and rotate via the bearing systems 38 about the engine central longitudinal axis a . a combustor 56 is arranged between the high pressure compressor 52 and the high pressure turbine 54 . in one example , the high pressure turbine 54 includes at least two stages to provide a double stage high pressure turbine 54 . in another example , the high pressure turbine 54 includes only a single stage . as used herein , a “ high pressure ” compressor or turbine experiences a higher pressure than a corresponding “ low pressure ” compressor or turbine . the example low pressure turbine 46 has a pressure ratio that is greater than about 5 . the pressure ratio of the example low pressure turbine 46 is measured prior to an inlet of the low pressure turbine 46 as related to the pressure measured at the outlet of the low pressure turbine 46 prior to an exhaust nozzle . a mid - turbine frame 58 of the engine static structure 36 is arranged generally between the high pressure turbine 54 and the low pressure turbine 46 . the mid - turbine frame 58 further supports bearing systems 38 in the turbine section 28 as well as setting airflow entering the low pressure turbine 46 . the core airflow c is compressed by the low pressure compressor 44 then by the high pressure compressor 52 mixed with fuel and ignited in the combustor 56 to produce high speed exhaust gases that are then expanded through the high pressure turbine 54 and low pressure turbine 46 . the mid - turbine frame 58 includes vanes 60 , which are in the core airflow path and function as an inlet guide vane for the low pressure turbine 46 . utilizing the vane 60 of the mid - turbine frame 58 as the inlet guide vane for low pressure turbine 46 decreases the length of the low pressure turbine 46 without increasing the axial length of the mid - turbine frame 58 . reducing or eliminating the number of vanes in the low pressure turbine 46 shortens the axial length of the turbine section 28 . thus , the compactness of the gas turbine engine 20 is increased and a higher power density may be achieved . the disclosed gas turbine engine 20 in one example is a high - bypass geared aircraft engine . in a further example , the gas turbine engine 20 includes a bypass ratio greater than about six ( 6 ), with an example embodiment being greater than about ten ( 10 ). the example fan drive gear system 48 is an epicyclical gear train , such as a planetary gear system , star gear system or other known gear system , with a gear reduction ratio of greater than about 2 . 3 . in one disclosed embodiment , the gas turbine engine 20 includes a bypass ratio greater than about ten ( 10 : 1 ) and the fan diameter is significantly larger than an outer diameter of the low pressure compressor 44 . it should be understood , however , that the above parameters are only exemplary of one embodiment of a gas turbine engine including a geared architecture and that the present disclosure is applicable to other gas turbine engines . a significant amount of thrust is provided by the bypass flow b due to the high bypass ratio . the fan section 22 of the engine 20 is designed for a particular flight condition — typically cruise at about 0 . 8 mach and about 35 , 000 feet . the flight condition of 0 . 8 mach and 35 , 000 ft ., with the engine at its best fuel consumption — also known as “ bucket cruise thrust specific fuel consumption (‘ tsfc ’)”— is the industry standard parameter of pound - mass ( lbm ) of fuel per hour being burned divided by pound - force ( lbf ) of thrust the engine produces at that minimum point . “ low fan pressure ratio ” is the pressure ratio across the fan blade alone , without a fan exit guide vane (“ fegv ”) system . the low fan pressure ratio as disclosed herein according to one non - limiting embodiment is less than about 1 . 50 . in another non - limiting embodiment the low fan pressure ratio is less than about 1 . 45 . “ low corrected fan tip speed ” is the actual fan tip speed in ft / sec divided by an industry standard temperature correction of [( tram ° r )/ 518 . 7 ) 0 . 5 ]. the “ low corrected fan tip speed ”, as disclosed herein according to one non - limiting embodiment , is less than about 1150 ft / second . the example gas turbine engine includes the fan 42 that comprises in one non - limiting embodiment less than about 26 fan blades . in another non - limiting embodiment , the fan section 22 includes less than about 20 fan blades . moreover , in one disclosed embodiment the low pressure turbine 46 includes no more than about 6 turbine rotors schematically indicated at 34 . in another non - limiting example embodiment the low pressure turbine 46 includes about 3 turbine rotors . a ratio between the number of fan blades 42 and the number of low pressure turbine rotors is between about 3 . 3 and about 8 . 6 . the example low pressure turbine 46 provides the driving power to rotate the fan section 22 and therefore the relationship between the number of turbine rotors 34 in the low pressure turbine 46 and the number of blades 42 in the fan section 22 disclose an example gas turbine engine 20 with increased power transfer efficiency . referring to fig2 with continued reference to fig1 , the example fan drive gear system 48 comprises an epicyclical gear box that includes a sun gear 66 that is attached to a connector shaft 62 . the sun gear 66 is engaged to drive intermediate gears 68 that are in turn intermeshed with a ring gear 70 . the intermediate gears 68 are supported for rotation on journal bearings 72 . the journal bearings 72 are in turn supported by a carrier 74 . in this example , the fan drive gear system 48 comprises a star gear system where the carrier 74 remains fixed such that the intermediate gears 68 are driven by the sun gear 66 but remain in a specific location as is fixed by the carrier 74 . the ring gear 70 is driven for rotation about the intermediate gears 68 to drive a fan shaft 64 . the fan shaft 64 extends forward of the fan drive gear system 48 to drive the fan section 22 . as appreciated , although a star gear system is disclosed ; other gear systems such as a planetary gear system are within the contemplation of this disclosure . in a planetary gear system , the carrier is mounted for rotation such that the intermediate gears 68 rotate about the sun gear 66 and the ring gear 70 is fixed . a lubrication system 82 ( fig3 ) provides lubricant to the geared fan drive gear system 48 . in this example , a lubricant manifold 76 ( fig2 ) is mounted to the fan drive gear system 48 to provide lubricant to the journal bearings 72 . lubricant expelled from the fan drive gear system 48 during operation is captured by a gutter 78 . the gutter 78 is circumscribed about an outer periphery of the ring gear 70 . in this specification , the term oil and lubricant are utilized to describe a fluid that supplied to the journal bearings and gears to provide both desired lubricity along with heat removal . any oil or lubricant could be utilized with the example system and are within the contemplation of this disclosure . referring to fig3 and 4 with continued reference to fig2 , the example fan drive gear system 48 is supplied with lubricant by the lubrication system 82 . the example lubrication system 82 comprises a main system 84 and an auxiliary system 86 . the main system 84 includes a main tank 90 and a main pump 92 that pumps lubricant through a main passage 114 to the gears 66 , 68 , 70 and journal bearings 72 . during normal operation , the main system 84 supplies lubricant of sufficient volume to the gears 66 , 68 , 70 and journal pin 72 to remove heat from the fan drive gear system 48 and to provide sufficient lubricant to maintain a desired operability of the gears and journal bearings . the example auxiliary system 86 provides lubricant to the gears 66 , 68 , 70 and journal bearings 72 during interruption in lubricant supplied by the main system 84 . the auxiliary system 86 collects oil that is accumulated in the gutters 78 and supplies that oil to an inlet 104 of auxiliary pump 102 . the auxiliary pump 102 pumps lubricant through auxiliary passage 108 that is in communication with bearing passage 80 that supplies lubricant to the journal bearing 72 . the auxiliary pump 102 utilizes lubricant obtained from the gutter 78 to supply a sufficient amount of lubricant to the inlet 104 of the auxiliary pump 102 such that it remains sufficiently primed . an inlet passage 98 is in communication with the gutter 78 through a port 120 . lubricant that is flung radially outward from the fan drive gear system 48 is captured within the gutter 78 and communicated through the port 120 to the inlet passage 98 then on to the auxiliary pump 102 . the amount of lubricant captured during normal operation of the fan drive gear system 48 exceeds the capacity of the inlet passage 98 and therefore a bypass 100 is provided in communication with the inlet 98 . lubricant overflows from the inlet passage 108 into the bypass 100 where it is directed through openings 122 to a sump 88 or a bearing compartment . a sump pump 94 may be included to pump lubricant to the main tank 90 . the example auxiliary lubricant system 86 includes reservoirs 110 and 112 that maintain a sufficient amount of lubricant within the auxiliary passage 108 to sustain operation of the fan drive gear system 48 for a brief period during intermittent interruptions in operation of the main lubricant system 84 . the example first and second reservoirs 110 and 112 are disposed after the auxiliary pump 102 and are continually charged or filled with lubricant . the example first reservoir 110 is disposed between the outlet 106 of the auxiliary pump 102 and the pressure responsive valve 96 . the second reservoir 112 is disposed between the pressure responsive valve 96 and the bearing passage 80 . because lubricant is stored within the reservoirs 110 , 112 , the auxiliary system 86 includes a sufficient amount of lubricant to compensate for intermittent interruptions of oil flow from the main lubricant system 84 . a volume 116 , 118 of each of the reservoirs 110 , 112 , provides for the storage of lubricant in a quantity determined to continue lubricant flow to the journal bearings 72 for a desired time . the volumes 116 , 118 are greater than a comparable volume within the auxiliary passages 108 . in other words , the reservoir 110 , 112 include a volume over a fixed length greater than a volume of the auxiliary passage 108 over a length equal to that of the reservoir 110 , 112 . as appreciated , although the disclosed example includes two reservoirs 110 , 112 located in different points along the auxiliary passage 108 , any number of reservoirs could be located within the auxiliary passage 108 to store and provide lubricant when required . a pressure responsive valve 96 is provided in the auxiliary passage 108 that directs lubricant flow responsive to a condition in the main lubricant system 84 . in the disclosed example , the valve 96 is responsive to a pressure within the main lubricant passage 114 . when pressure is at a desired level indicative of normal operation , the valve 96 directs lubricant flow from the auxiliary passage 108 back to the main tank 90 , or some other lubricant supply location . however , in response to a drop in pressure within the main lubricant system 84 and passage 114 , the valve 96 will direct lubricant flow to the bearing passage 80 and to the journal bearings 72 . the example auxiliary system 86 supplies lubricant to the journal bearings 72 only , as the journal bearings 72 have limited capacity for operation without lubricant . however , it is within the contemplation of this disclosure that the auxiliary system 86 could direct lubricant to any structure or assembly determined to require lubricant during periods of interruption of main lubricant flow . during normal operation , the main lubricant system will provide lubricant to journal bearings 72 and to the gears 66 , 68 , 70 . the auxiliary lubricant system 86 operates by gathering lubricant expelled radially outward with the gutter 78 . from the gutter 78 , lubricant is communicated through the port 120 to the inlet passage 98 . the inlet passage 98 fills with lubricant to maintain a pressure and supply of lubricant at the pump inlet 104 . excess lubricant is directed into the bypass 100 and out through openings 122 to the sump 88 or bearing compartment . the pump 102 pumps lubricant through the outlet 106 into the auxiliary passage 108 . reservoirs 110 and 112 are filled with lubricant and maintained by a continual flow from the pump 102 . the valve 96 directs lubricant flow back to the main tank 90 for use by the main lubricant system 84 . during interim periods of interruption caused by aircraft maneuvers or conditions such as low , zero or negative g maneuvers , lubricant may not flow as desired from the main lubricant system 84 . accordingly , a pressure within the main passage 114 drops causing actuation of the valve 96 to direct oil from the auxiliary passage 108 to the bearing passage 80 and finally to the journal bearings 72 . the gutter 78 does not recover all of the lubricant communicated to the journal bearings 72 and gears 66 , 68 , 70 , and therefore some lubricant is lost in each pass through the auxiliary system 86 . accordingly , the reservoirs 110 and 112 store additional lubricant to extend the duration that the auxiliary lubrication system 86 can maintain a desired supply to the journal bearings 72 . the example auxiliary lubricant system includes reservoirs that are downstream of the auxiliary pump to provide and push the lubricant in a volume sufficient to maintain operation of the fan drive gear system for an extended amount of time . moreover , the example auxiliary lubrication system includes a gutter fed auxiliary pump that is charged with lubricant from lubricant normally expelled from the fan drive gear system . although an example embodiment has been disclosed , a worker of ordinary skill in this art would recognize that certain modifications would come within the scope of this disclosure . for that reason , the following claims should be studied to determine the scope and content of this disclosure . | 5 |
as used in this disclosure , reference to a vacuum source is to be taken to include a source of suction , and includes a suction or vacuum source or sources , or any other source of suction or vacuum . to refer to the drawings , fig1 shows a typical preform assembly 8 created by the preform assembly method ( pam ) comprising a distance fabric 10 which has a first sheet 12 and second sheet 14 comprising extensible threads 16 extending therebetween . a first face sheet 18 is attached to first sheet 12 by a first thermoadhesive film 20 ; and a second face sheet 22 is attached to a second sheet 14 by a second thermoadhesive film 24 . the attachment of the face sheets 18 and 22 to the distance fabric 10 occurs during pam . the pam process depends strictly on the requirements of the adhesive film used to attach the adjacent sheets . the process to be described is for the adhering of the face sheets 18 and 22 to the distance fabric 10 using two thermoplastic adhesive films 20 and 24 requiring heat and pressure for correct application . fig2 shows the preform 8 in place on a flat base plate 1 . over the plate is placed a vacuum diaphragm 2 . this diaphragm 2 extends beyond the perimeter of the flat base plate 1 . under the diaphragm 2 is placed a vacuum port 36 , breather material 35 , and thermocouple schematically shown as 3 , the thermocouple being to measure the temperature of the adhesive films 20 and 24 . the diaphragm 2 is sealed against the base plate 1 using a sealing bead 4 of mastic . the assembly is then placed in an oven . a vacuum source is applied to the vacuum port 36 to give an appropriate consolidation pressure for the adhesive films 20 and 24 . the oven heats the adhesive films to the appropriate bonding temperature . alternatively , heated pressure rollers and / or a heated press ( with or without pressure ) may be used . when the appropriate temperature is shown by the thermocouple 3 , the temperature is maintained for the recommended bond time for the adhesive film . the base plate 1 and preform assembly 8 are then removed from the oven and allowed to cool . upon cooling , the preform is removed from the base plate 1 and checked for good adhesive film bonding . if the bond is adequate , the preform 8 is ready for infusion . during the following description , all sheets assembled against the first sheet 12 during the preform assembly method will collectively be called the first sheet 12 , and all sheets assembled against the second sheet 14 during the preform assembly method will collectively be called the second sheet 14 . the preform 8 is located in a second portion 26 of a mold generally designated as 30 , which also has a first portion 28 ( fig4 ). the second portion 26 has a peripheral frame 32 , to which is applied a sealing bead 34 . between first face sheet 18 and first portion 28 there is located a diaphragm 38 , which extends to and beyond plate 32 and over the sealing bead 34 . the first face sheet 18 is temporarily bonded to the diaphragm 38 . as is shown in fig5 and 6 , rather than peripheral frame 32 there may be provided a tapered frame 48 around the periphery of second portion 26 to aid the deformation of the diaphragm 38 . both frame 32 and frame 48 assist to create a first chamber 40 between diaphragm 38 and first portion 28 , and a second chamber 42 between diaphragm 38 and second potion 26 . seals 44 may be provided in addition to , or in place of , sealing bead 34 . both first portion 28 and second portion 26 have a vacuum ports 36 which , as shown in fig5 , may be centrally located in the relevant portions 26 , 28 . resin inlet ports 46 are provided in second portion 26 , although they may be in frame 48 , if desired . the resin inlet ports 46 are preferably located between the periphery 50 of preform 8 , and the inner edge 52 of frame 32 , or inner edge 54 of tapered frame 48 . as will be realized from the above description , the frame 48 is used when the frame 32 is not used , and vice versa . therefore , upon first portion 28 engaging with second portion 26 , diaphragm 38 seals on sealing bead 34 and is secured between the peripheries of the first and second portions 26 , 28 . suction ( vacuum ) is then applied to vacuum port 36 in second portion 26 , so that the preform 8 will be securely drawn into second portion 26 , as will be the attached diaphragm 38 ( fig3 ). with an appropriate resinous compound ( not shown ) being fed into second chamber 42 , the reduced pressure in second chamber 42 will draw the resinous compound into and through the chamber 42 and the preform 8 . the resinous compound may have a positive pressure applied to it , if desired . if a positive pressure is used , a higher positive pressure must be applied in the first chamber 40 to restrict the diaphragm 38 from rising . as diaphragm 38 presses on first face sheet 12 , and as second face sheet 14 presses on second portion 26 , the resinous compound is drawn through the preform 8 and thereby coats the infusible surfaces of those sheets , as well as the extensible threads 16 extending therebetween . any surplus resinous compound will exit through vacuum port 36 , where it can be recovered in an appropriate trap . the feed of the resinous compound continues until all threads 16 and the infusible surfaces of first sheet 12 and second sheet 14 are coated . this time will depend on the nature of the resinous compound , the sheets 12 , 14 the number and size of threads 16 , and the size of the preform 8 . when the resinous compound has fully infused the preform 8 , the resin inlet ports 46 are closed and the vacuum port 36 in second portion 26 is closed . the suction ( vacuum ) is then applied to vacuum port 36 in first portion 28 . the second chamber 42 is simultaneously or earlier vented to the atmosphere by the vent port 37 , and / or by resin inlet ports 46 , so that second chamber 42 returns to atmospheric pressure . the vent port 37 may , if desired , be through frame 48 . alternatively , a positive pressure can be applied to second chamber 42 so that the first chamber 40 is at a relatively lower pressure . by virtue of the vacuum applied to vacuum port 36 in first portion 28 , first chamber 40 is of reduced pressure . this therefore creates a pressure differential between first chamber 40 ( low pressure ) and second chamber 42 ( higher pressure ), causing diaphragm 38 to be drawn towards first portion 28 , thus drawing first sheet 12 upwardly and away from second sheet 14 which is non - permanently adhered to the second mold portion 26 so that it will not move relative thereto during the molding process . therefore , the extensible threads 16 are extended . the distance between the first and second face sheets 12 , 14 is that which is desired , as set by the mold cavity height ( the sum of the heights first chamber 40 and second chamber 42 ). this height is usually predetermined by the height of frame 32 or frame 48 . hence , due to the pressure differential the diaphragm 38 and first sheet 12 are drawn up to the first mold portion . the suction ( vacuum ) is maintained in the vacuum port 36 in first portion 38 , and second chamber 42 is sealed to allow the resinous compound to set and cure . alternatively , self - foaming resins can be used to infuse the preform . in this case , the pressure differential between the second chamber 42 and the first chamber 40 is created by the foaming of the resin . in this case , after the resinous compound has fully infused the preform 8 , the resin inlet ports 46 are closed and the vacuum port 36 in second portion 26 is closed . the second chamber 42 is then vented to the atmosphere by the vent port 37 and / or by resin inlet ports 46 , so that the second chamber 42 returns to atmospheric pressure . the first chamber 40 remains at atmospheric pressure . the foaming reaction of the resin , initiated chemically or by the application of heat , creates the pressure differential between the first chamber 40 ( low pressure ) and the second chamber 42 ( high pressure ), causing diaphragm 38 to be drawn towards the first portion 28 . thus , the first sheet 12 is drawn upwardly and away from the second sheet 14 . the distance between the first and second face sheets 12 , 14 is that which is desired , as set by the mold cavity height . the penetration of the first sheet 12 by the foaming resin is resisted by the bonding of the impermeable diaphragm 38 directly on the first sheet 12 during preform assembly . the penetration of the second sheet 14 is similarly resisted by the bonding of the impermeable second portion 26 directly onto the second sheet 14 . when an appropriately engineered foaming resinous compound is used , an excellent quality infusion and finish in the skin in combination with a quality foam core will result . when using this type of foaming resin to create a sandwich structure , the distance fabric 10 may or may not be left out of the preform assembly 8 and , hence , the resulting sandwich structure . in the case of the distance fabric 10 being left out of the preform 8 , the first sheet 12 is bonded to the diaphragm 38 and the second sheet 14 is bonded to the second portion 26 , but they are not bonded to each other . this allows for their separation during the foaming of the resin . maximum separation distance is again set by the mold cavity . if desired , the mold 30 may be heated to assist the setting and curing of the resinous compound . heating may be by heating elements being placed in mold 30 , or by placing mold 30 in an oven . alternatively , hot air could be introduced to second chamber 42 through resin inlet ports 46 and / or venting port 37 in second portion 26 . upon setting , and preferably curing , of the resinous compound , the mold 30 is separated , diaphragm 38 removed , and the expanded composite structure removed . if desired , external caul plates 56 and 60 ( fig8 ) may be used , particularly for the embodiment of fig1 . for the embodiment of fig1 clamping bars 62 , spaced apart by spacer elements 64 , are used to support the separation of the external caul plates 56 and 60 , which in turn give the desired final dimensions of the preform 8 during the later stages of the infusion process and during curing processes . the vacuum ports 36 and / or inlet ports 46 and / or vent port 37 may be beyond the periphery of the preform 8 , if desired . however , the vacuum port 36 and inlet ports 46 should not be adjacent . the diaphragm 38 is preferably a non - porous film capable of holding a vacuum of the order of 100 kpa . it may be elastic or semi - elastic . examples of suitable materials include silicon rubber sheet , latex rubber sheet , and a nylon bagging film , etc . as the resinous compound may contaminate the diaphragm 38 during infusion and / or expansion of the preform 8 , the diaphragm 38 and the resinous compound should be such that there is no chemical interaction between them . if desired , a caul plate 59 may be used ( fig6 ). the caul plate 59 is placed between the first sheet 12 and the diaphragm 38 to aid control , and / or to improve the surface quality of first sheet 12 . in addition , the use of caul plate 59 may assist in reducing peeling - off effects as the diaphragm 38 may initially stretch over the entire area of the caul plate 59 . furthermore , the caul plate 59 may slightly enhance the infusion of the resinous compound as improved flow paths may result . the caul plate 59 is preferably at least as large as the preform 8 and may , if desired , be releasably or securely attached to the diaphragm 38 or first sheet 12 by , for example , double - sided tape . the attachment to the caul plate 59 may also occur during preform assembly method . furthermore , a carrier mesh 58 may also be used to assist the resinous compound to pass from the inlet ports 46 to the preform 8 . the carrier mesh 58 is attached to the interior of second portion 26 at or adjacent the inlet ports 46 and extends to and along the side edges of preform 8 . the carrier mesh 58 may extend totally or partially around the periphery of preform 8 . one example of the production of a composite sandwich structure in accordance with an embodiment of the present invention is described below . the surface of plate 1 is cleaned with acetone , with the surface being flat and free of debris and lumps . a single layer of non - perforated adhesive film is cut to dimensions identical to the preform 8 . this layer 20 is to provide a bond between the outer preform surface 18 and the bagging film 38 . layers of perforated adhesive film 20 are cut to provide a bonding / interleaf layer between all preform - to - preform surfaces . the lower preform surface 22 is placed on plate 1 . alternate layers of perforated adhesive film 20 and preform fabrics are then placed above lower sheet 22 as required . a layer of the perforated adhesive 20 is placed on all preform - to - preform surfaces to bond the preform surfaces and also allow resin to move between the surfaces . a layer of non - perforated adhesive film is placed on top of preform 8 . mastic tape or other similar sealant is applied to the tooling plate , outside of the perimeter of the preform 8 . a thermocouple 3 is placed on the edge of the preform 8 , such that it is contacting the adhesive film 20 . the vacuum source fittings are connected to the vacuum port 36 in plate 1 . a full vacuum (˜ 100 kpa ) is applied to enable checks of vacuum leaks . the oven is preheated to the required temperature for adhesive bonding ( or just above bonding temperature ), and the vacuum is set to the bonding pressure . the plate 1 with preform 8 is placed in the oven and heated until the thermocouple 3 shows that the thermoadhesive film 20 , 24 has reached its / their bonding temperature . the temperature is held for the appropriate time . the plate 1 and preform 8 are removed from the oven and allowed to cool . the vacuum fittings and thermocouple 3 are removed . the bagging / preform is removed from the plate 1 without peeling the bag from the preform 8 . the excess bag / preform is removed to give a net - shape preform with bagging on the skins . all mold surfaces ( inside of mold , caul plate ) are cleaned with acetone , with there being no remains of resin flash on mold surfaces and resin inlet channels . all required hoses are fastened to the appropriate ports in the mold by using compression fittings . strips of double - sided tape are applied to the edges of both sides of the preform 8 and the caul plate 59 . the preform 8 is fixed to the caul plate 59 using this tape . the preform 8 is placed in the center of the second portion 26 of the mold and pressed to achieve a proper bond . the carrier mesh 58 is attached to both inlet ports 46 . mastic tape is applied to the outside of the mold , using extra strips to seal the corners . the diaphragm 38 is fixed to the mold plate , hence , sealing the mold . the vacuum and the first venting hose are connected to a resin trap to catch any excess resin . the vacuum source is then attached to the resin trap lid and the resin inlet and the venting hoses are clamped . the lid is closed and securing bars placed in position , and fastening bolts gently tightened . full vacuum is applied for infusion . an appropriate amount of resin is mixed for a predetermined gel time . the two resin inlet hose ( s ) are inserted into the cup . the infusion time is recorded . at the first sign of resin in the exit line , the vacuum pressure is reduced to 40 kpa for 3 minutes . the resin inlet lines and exit line are then closed . a full vacuum is then applied to the resin trap , and , after connecting in the vacuum line of the lid directly to the vacuum , full vacuum is applied . the venting hoses are opened and the vacuum in the resin trap reduced to zero at a rate of 2 kpa / sec . the resin lines are removed , and the resin cup and excess hoses also removed . after approximately 2 hours the first venting hose is closed and 5 kpa vacuum applied to the first venting hose . this ventilates the mold and accelerates the curing by replacing the styrene . curing for several hours is allowed . the clamps are then removed and excess lines cut . the clamping bars are removed from the tool and the lid opened . the diaphragm is removed and the tooling plate released from the expanded structure . the expanded structure is removed from the mold . although the present invention has been discussed in considerable detail with reference to certain preferred embodiments , other embodiments are possible . therefore , the scope of the appended claims should not be limited to the description of preferred embodiments contained in this disclosure . all references cited herein are incorporated by reference to their entirety . | 1 |
referring now to the drawings in detail , reference is first made to fig1 and particularly to the lower end thereof , wherein there is illustrated a battery , generally designated by the numeral 10 , disposed upon a conveyor 11 , having a plurality of transverse rollers 12 , for movement of the battery 10 from left to right , as viewed in fig1 across the rollers 12 . a plurality of cells ( six in number ), such as those 13 and 14 are illustrated , in which are disposed a plurality of plates 15 extending downwardly from plate straps such as those 16 and 17 , the plate straps 16 and 17 having been already connected to the plate 15 , by any suitable means , such as that described in u . s . pat . no . 3 , 395 , 748 , or by any other means . the cells 13 and 14 are separated by suitable cell partitions 18 , constructed of an inert material , such as plastic or rubber ( due to the presence of battery acid within the cells 14 , 15 , etc .). the partition 18 extends vertically upwardly between posts 20 and 21 of adjacent cells 14 and 13 , respectively , with the partition 18 terminating at its upper end short of the upper ends of the posts 20 and 21 , leaving a space 22 therebetween . it is this space 22 that , upon welding by the use of open flame being applied to posts 20 and 21 , may become filled with molten or liquid lead ( or other post material ) from the upper ends of the posts 20 and 21 , and flow downwardly to solidify in the space 22 just above the separator plate 18 , without application of a proper amount of heat to those portions of the posts 20 and 21 , below the upper ends thereof as illustrated in fig5 a , in the vicinity of the upper end of the cell partition 18 . a templet 23 , constructed of some material ( preferably metal ) having a melting point substantially in excess of that of the material of the posts 20 and 21 , is provided , on the battery , at the upper ends thereof , as illustrated in fig1 with pairs of posts 20 and 21 extending upwardly through voids 24 therein . it will be clear that the voids 24 extend entirely through the templet 23 , and that the voids 24 comprise central portions 25 of a desired size and configuration corresponding to the posts , to easily receive and contain the same . the upper and lower ends of the voids 24 are countersunk as at 26 and 27 , to permit reception of posts 20 and 21 through the lower ends 27 of the voids 24 , and to provide a dished portion 26 at the upper end of each void 24 , to accommodate the reception of molten metal during the welding operation , with the lower countersink or cut - away portion 27 also facilitating the removal of the templet 23 after the welding operation is complete , with the weldments solidified . it will further be noted that the templet 23 is received on the upper lip of the casing 28 of the battery 10 , as illustrated in fig1 . with particular reference to fig5 a , and 5b and 5c , it will be seen that a heated element 30 that has been heated by means later to be described herein , to a temperature sufficient to melt the upper ends of posts 20 and 21 of adjacent battery cells , across the top of a partition 18 , is lowered into engagement with the upper ends of the posts 20 and 21 , and proceeds to melt the same , into a liquid state , and then continue its downward move at , penetrating the liquid portions of the post members 20 and 21 being progressively melted as the element 30 moves downwardly , throughout a predetermined vertically downward stroke of movement of the element 30 , such stroke also including a dwell time at the lower end thereof , as illustrated in fig5 b , if desired ( but such dwell not being required ), followed by retraction , or vertically upward movement of the element 30 , in the direction of the arrow 31 illustrated in fig5 c , whereby the mass of liquid melt displaced into the zone 26 of the templet 23 during that portion of the operation illustrated in fig5 b , is free to fill the zone 25 of the void 24 of the templet 23 , above the upper end of the partition 18 , as illustrated in fig5 c , for cooling and solidification of the melt in the zone 25 . it will be noted that a plurality ( five in number ) of such elements 30 may be utilized simultaneously , in order to simultaneously effect five different welds , between posts of adjacent battery cells , or in fact any desired number of such weldments may be effected , for battery cells , or for any other purpose , by the above - mentioned method of maintaining a constant temperature for the element 30 and delivering such temperature completely throughout the zone of the posts 20 and 21 , or other members , in which the weldment is desired . furthermore , it will be noted that the voids 24 , and particularly the central portions 25 thereof , comprise molds for the welds , during solidification and cooling thereof . after the welds are solidified , the templet 23 may be removed from the casing 28 of the battery 10 , for reuse , as desired . with particular reference to fig5 d , it will be apparent that a battery cover 32 , having an annular cylindrical protrusion 33 , for each pair of battery posts welded together , may be disposed over the upper end of the battery , with each weld 34 being received within a corresponding annular protrusion 33 , for purpose of aligning the battery cover 32 , if desired , and for facilitating the covering of the welds 34 and retention of the cover 32 on the battery 10 . it will further be noted that the welds 34 are simultaneously effected , for a given battery , and are all uniform , as regards their electrical qualities , and as regards their general height and other physical characteristics . particularly as regards the height of the same , it will be noted that , all being of the same general height , the battery cover 32 will more easily fit thereover , with posts having welds 34 at the upper ends thereof , all being uniformly received in uniformly sized annular protrusions 33 of the covers 32 . referring now to the welding apparatus of this invention specifically illustrated in fig1 through 4 , it will be seen that an apparatus 40 is presented , for carrying a plurality of heating elements or heat sinks 30 protruding outwardly ( downwardly ) from the lower end thereof . the apparatus 40 comprises a post 41 of cylindrical configuration , connected by any suitable means , such as threading or the like , as at 42 , through a manifold head 43 , and through a base member 44 , to be secured by means of a nut 45 therebeneath . the base member 44 is of channel - like construction , being generally of inverted u - shape in transverse cross - sectional configuration , as best illustrated in fig2 and 4 . the manifold head 43 is secured to the upper end of the base 44 , by any suitable means , such as screws or the like . the manifold head 43 is provided with a pair of conduits 46 and 47 extending longitudinally therethrough , each connected at one end to an associated gas distribution conduit 48 or 50 , provided with associated on - off inlet valves 51 , as desired . the conduits 48 and 50 are connected to suitable sources of gases , such as natural gas and oxygen , respectively , or any other gases that will facilitate and support combustion at the desired temperatures . thus , acetylene gas may replace the natural gas if desired , as may a mixture of other gases , such as air , replace the oxygen , if desired . the left - most end of each of the manifold channels 46 and 47 is closed , as blind conduits ( not illustrated ). five element heating means , generally designated each by the numeral 42 are provided , each of substantially identical construction , so that only one need be described in detail , and each of which is carried at the lower end of the base member 44 , by a suitable horizontal plate 53 , secured by means of a cap headed screw 54 or the like extending therethrough , in engagement within a nut 55 disposed within the base 44 . thus , the position of any given element heating means 52 may be altered by loosening the screw 54 , and repositioning such desired element heating means by moving the plate 53 longitudinally of the base member 44 . each of the heating means 52 is constructed as an independent torch , being provided at its upper end with a mixing device 57 , having upper inlets 58 and 60 for receiving for example gas and oxygen therein from respectively associated hoses 61 and 62 that , in turn are respectively connected to associated manifold ducts 46 and 47 , for supplying gas and oxygen to a chamber 63 disposed within the device 57 , in which they are mixed . accordingly , the inlets 58 and 60 communicate respectively with the chamber 63 . a pair of needle adjustments 64 and 65 are provided , associated with respective inlets 58 and 60 , each comprising a thumb screw or the like 66 , operative through a boss 67 in threaded engagement with the device 57 at 68 , for adjusting the position of a needle 70 in the associated inlet , for regulating the amount of gas to be mixed with oxygen , and the converse . upon arriving at a desirable gas - oxygen mixture , the mixture passes through the conduit 71 , to discharge from the device 57 , through a distribution line 72 , that in turn is connected to an element holder 73 , by suitable nuts 74 or the like in threaded engagement with threads 75 , wherein the delivery line 76 is bifurcated at 77 , into a pair of delivery lines 78 and 80 that are inwardly bent at the lower ends , and have nozzles 81 and 82 respectively carried thereby , in the vicinity of the upper ends of the elements 30 , for heating the elements at a location spaced above the lowermost , or free ends thereof . the elements 30 are connected within bores or recesses 83 , by suitable screws 84 , for ease of replacement . thus , the application of open flame due to the elimination of gas and oxygen from nozzles 81 and 82 , to the elements 30 , will heat the elements 30 as aforesaid . it will be noted that elements 30 may also be heated by induction heating ( not illustrated ), or by other suitable means , if desired . in any event , heat is built up and stored in the element 30 , and in order to facilitate this end the element 30 may be constructed of a high temperature alloy , ceramic , or any other suitable material . it will be noted that the flame may continually be applied to the element 30 during the descent thereof and its retraction , as illustrated in fig5 b and 5c , throughout its engagement with and projection into the material of the battery posts 20 and 21 , if desired , or the heat may be applied to the elements 30 only when the same are in their uppermost or retracted positions , as desired . in any event , there will be a transfer of heat from the elements 30 to the upper ends of the battery posts 20 and 21 , that will be constantly replenished by the application of heat to the elements 30 , by virtue of the application of open flame thereto as described above , or by induction heating , or the like . furthermore , it will be noted that the heating elements or tips 30 may take on various desired physical configurations and sizes , depending upon the particular application . another feature of this invention resides in the use of a plate 90 secured to the member 44 , by a pair of screws such as 91 and 92 , for ease of removal of the same , with the plate 90 having a plurality of openings , voids , notches or the like , disposed in a uppermost set 93 , and a lowermost set 94 . the lowermost set 94 is arranged to accommodate plates 53 , in accordance with a desired predetermined spacing of element 30 relative to each other , as measured horizontally , and relative to posts 20 and 21 of a battery 10 to be welded therebeneath , and also relative to the templet 23 mounted on the battery 10 and disposed therebeneath . accordingly , placement of the plates 53 , in desired ones of the notches 94 , will readily accurately position the elements 30 , in accordance with the desired position for welding the posts of a given battery , for example . however , the assembly illustrated in fig4 may readily accommodate an alternative placement of the elements 30 , by merely removing the plate 90 , and inverting the same such that the notches 93 are disposed downwardly , whereby another placement of the element 30 relative to each other may readily be effected quickly and economically , with minimum set - up time . with particular reference to fig1 it will be noted that the rod 41 is either mounted to , or comprises , the piston rod of a piston ( not shown ), disposed within a piston cylinder 96 , mounted on a suitable frame 97 . the cylinder 96 is provided with suitable fluid inlets 98 and 100 , respectively for providing a downward driving force , for lowering the elements 30 , or for retracting the same , depending upon the position of the two way valve 101 . it will be noted that the fluid supplied through the lines 98 and 100 may be any desirable hydraulic , pneumatic fluid or the like , and that the piston within the cylinder 96 would be driven either upwardly or downwardly , depending upon the setting of the valve 101 . it will be noted that the stroke of the piston contained within the cylinder 96 is controlled to automatically re - set the valve , upon the piston disposed therein reaching the lower end of a predetermined stroke , in order that the elements 30 may be retracted prior to striking the separator plates or partitions 18 . however , in the event of misalignment of elements 30 relative to posts 20 , 21 , or relative to the templet 23 , or relative to anything else wherein it is desired to prevent a striking of the same by the element 30 , or even in the event that a battery 10 is raised , for example at one end , due to the presence of a foreign item between the lower end of the battery and the conveyor rollers 12 , such that the battery is &# 34 ; cocked &# 34 ;, upon the striking of the elements 30 against any solid member , a sensor of pressure , force or the like 102 , which is particularly responsive to pressure required to lower the piston contained within the cylinder 96 , and consequently responsive to resistance to vertical downward movement that the elements 30 may meet , will be operative to actuate the valve 101 , to cause an upward movement , or retraction of the assembly 40 , and consequently of the elements 30 carried thereby , in order to prevent damage of the apparatus , or to batteries being welded . also , with reference to fig1 it will be noted that the rod 41 is provided with a guide , comprising a plate 103 having a boss 104 disposed about the rod 41 , and carried by the plate 103 , and with a guide rod 109 being provided , mounted in a suitable bushing 105 carried by a plate 106 , such that , upon downward movement of the rod 41 , the same is guided against undesirable lateral mvoement , due to the presence of the guide plate and rod 103 and 109 . it will thus be seen that the apparatus of this invention is adapted toward accomplishing its desired ends , both in broad respects , and in specific respects , regarding the construction of multiple - cell lead - acid storage batteries . it will further be noted that the particular inwardly bent orientations of the nozzles 81 and 82 , present the application of heat to adjacent areas , thereby concentrating the heat on the elements 30 themselves . it will also be noted that the element 30 may be adjustably positioned vertically within the blind hole 83 , by merely loosening the screw 84 and repositioning the element 30 . furthermore , in operation , a proper positioning of the battery can actuate a switch ( not shown ), that in turn will cause the piston within the cylinder 96 to be actuated , if desired . in view of the above - discussed invention , it has been possible to cut down the time necessary for completing a weld from thirty seconds to four seconds . accordingly , aside from accomplishing improved welds , both insofar as their physical appearance and construction is concerned , and insofar as improving the uniformity and electrical conductivity of the same is enabled , the overall economics of battery manufacture is greatly improved , due to the automation of what has previously been a manual function . an additional advantage over prior techniques of battery post weldment is also made possible with weldments of this invention . such resides in the formation of a homogeneous weldment of adjacent battery posts . spectrographic analysis of battery posts welded by conventional application of gas and oxygen flame directly to the post results in a tendency toward concentration of antimony from the posts at or near the bond of the weld , apparently caused by more severe heat at such locations relative to less heat applied to other areas of the weld . in thermal relay welding as taught by the instant invention , spectrographic analysis will reveal similar grain structures throughout the weld , in that the entire post area is heated uniformly and therefore cools evenly , without causing an antimony precipitation that would result in an antimony concentration . consequently , the possibility of electrolysis at the antimony interface that forms the junction of dissimilar metals upon use of the battery in an electrical circuit is avoided by this invention , along with any corrosion attendant thereto . furthermore , the structural strength of the post weldment is better , because of the absence of substantial discontinuities that would be formed by such antimony precipitation . the foregoing discussion has emphasized the structure of the heating elements and the apparatus whereby combustible gases are delivered for the heating thereof . fig6 through 9 show an alternate illustrative embodiment wherein the heating elements are integrated with the templets lowered over the battery to form molds for the foregoing heating and melting process of the terminal posts . moreover , the embodiment of fig6 through 9 features the heating elements and the molds in an integral adjustable configuration such that batteries having widely disparate structural characteristics may be processed efficiently without requiring extensive overhaul of the processing mechanism . in the following description , many elements are identical both in structure and in function to corresponding elements in the foregoing discussion . many of these are numbered similarly to the identical corresponding element , but further including a prefixed &# 34 ; 7 &# 34 ;. thus , for example , heating elements 730 in fig6 and 7 correspond identically to the heating elements 30 in fig1 through 5d . unless otherwise specified , these identical elements shall not be discussed in detail , but shall be assumed to be disclosed completely in the foregoing . in fig6 a welding mechanism is set up for forming two terminal posts for batteries . thus , while the foregoing embodiment included six welding mechanisms for cell to cell relays in batteries , the embodiment of fig6 through 9 is configured only to form the positive and negative terminal posts . it is to be understood , however , that any desired number of heating elements might be included in order to fulfill the desired welding requirements for given batteries . likewise , the embodiment of fig6 through 9 includes several features which enhance the adaptability and therefore the utility of thermal welding apparatus embodying the principles of the present invention . in the figures , a pair of heating elements represented generally as 752 are affixed to a pair of mounting blocks 612 and 613 , which in turn are slidably mounted on a transverse rod 611 . this transversely movable mounting permits lateral adjustment of the heating elements 752 to accomodate batteries having terminal posts located at different points . the transverse rod 611 upon which the blocks 612 and 613 are mounted is terminated at either end by a pair of elements 610 . overlaying both of the mounting blocks 612 and 613 and affixed to the elements 609 and 610 is a plate 623 which affords control of the adjustability function and which shall be described in more detail hereinafter . also mounted on the rod 611 is a fixed block 930 which is in turn connected to the piston 830 of a pneumatic or hydraulic cylinder 630 . together , the blocks 609 , 610 , 612 , 613 and 930 , with the rod 611 and the plate 623 , form a &# 34 ; carriage &# 34 ; to which the heating elements 752 are attached , by means of which the heating elements may be moved vertically ( such as shown in phantom in fig7 ) and upon which the respective heating elements may be adjusted transversely . the terminating blocks 609 and 610 of the carriage upon which the heating elements 752 are mounted are in turn slidably mounted on posts 607 and 608 , respectively , by means of bearings , not shown . thus , under the control of the cylinder 630 and piston 830 , the carriage arrangement including the heating elements 752 is moved vertically on the posts 607 and 608 which are connected at their tops and bottoms , as shown , to elements 616 , 617 and 631 . topmost element 631 in turn is mounted on posts 632 and 633 , which constitute part of a structural fframe for the mechanism . also fixedly mounted on the posts 607 and 608 is a manifold head 743 which defines conduits 746 and 747 fed by lines 601 and 602 with a combustible gas for flame heating of the heating elements 730 . as in the foregoing embodiments , the gases pass through the conduits 746 and 747 , through hoses 761 and 762 and into mixing devices 757 , and thence downwardly into the heating means 752 . as shown , only two sets of hoses connect the heating means 752 with the manifold head 743 , but it is clear that any number , as desired , might similarly be connected . also mounted on he manifold heads 743 is the cylinder 630 whereby the mounting carriage for the heating means 752 is movable . an aspect of the embodiment of fig6 through 9 which exhibits substantial operational efficiency but which was not shown in detail in the foreging embodiments is the inclusion of a pair of molds 619 and 620 which respectively are connected to the mounting blocks 612 and 613 for the heating means 752 . the molds 619 and 620 are slidably mounted on a transverse post 618 through bearings such as 818 and are respectively mounted on shafts 626 and 627 which are slidably movable through the blocks 612 and 613 . it may therefore be seen that the molds 619 and 620 are movable as a unit with the upper mounting carriage for the heating means 752 but furthermore are separately movable together by means of the sliding of shafts 626 and 627 through the mounting blocks 612 and 613 . the molds 619 and 620 are advantageously constructed to provide superior operational efficiency , which in turn is enhanced by their adaptability to process batteries of variable size . this may appreciated by consideration of the various cutaway views in fig7 and 8 . the principal structural member of the molds 619 includes a hollow channel 834 which is fed and exhausted by a pair of lines 634 and 934 . the channel 834 provides a circulation route for water or other similar cooling fluids to be passed through , and thereby to prevent damage due to the extreme amounts of heat applied by the heating elements 730 to make the molten terminal posts . centrally located on the flat portion of the structural housing 619 is a mold member 621 which mates with the structural housing and which actually forms the voids in which the melting and casting process takes place . the mold members 621 and 622 fit into a hole through the structures 619 and 620 and are locked therein by means of a slotted key 901 which locks the mold member 621 in place when situated as shown in fig7 and 8 , but which allows for removal of member 621 when rotated 180 ° because the slot 905 then clears the outer periphery of the member 621 . lever arm 903 on the key 901 limits the rotary motion of the key by cooperating with extension members 902 and 904 . the mold members 621 and 622 are configured as shown to define voids 721 having an upper portion which is countersunk . thus , when the heating member 730 is lowered as shown in phantom in fig7 to heat and melt the terminal posts as shown in fig1 a through 10d the level of the molten metal rises up into the countersunk portion , but when the heating element 730 is removed , the level settles back into the lower portion of the void 721 to dry in the standard configuration of a terminal post . in accordance with standardized procedures , positive andd negative terminals of batteries are of different dimension in order to facilitate proper connection with external apparatus . in order to accommodate the wishes of various customers , the mold members 621 and 622 may have different sized voids 721 , and may be re - arranged between the molds 619 and 620 as desired . moreover , the molds 621 and 622 shown may be freely interchanged with other similar members of different inner - configuration to process battery elements of varying size and configuration , as desired . fig9 shows a view of the overlying plate 623 which is affixed in the carriage assembly to end blocks 609 and 610 by means of cam means 624 and 625 , and which , when so situated , determines the lateral position of the heating means 752 . more particularly , the securement means 624 and 625 fit through slots 906 and 911 in the plate 623 and screw or bolt into the terminating blocks 609 and 610 . the face of the plate defines first and second sets of openings 907 and 910 , and a plurality of sets of openings such as 908 and 909 extending across the face of the plate . once the securement members 624 and 625 mount the plate into the carriage assembly , set screws such as 912 through select ones of the end holes 907 and 910 establish the vertical location of the plate 623 . thereupon , a position is established for the support blocks 612 and 613 because they are affixed to the plate 623 by screws 628 and 629 through appropriate ones of the holes 908 and 909 . thus , use of particular ones of the holes 907 and 910 establish which of the holes 908 and 909 ( or any other such sets of holes , as desired ) to which the blocks 612 and 613 shall be mounted . it is to be understood that by alteration of the holes such as 908 and 909 , any desired position of the heating means 752 on the shaft 611 may be established . since the molding apparatus 619 and 620 is affixed to the respective blocks by means of posts 626 and 627 , similar positioning is established for the molding apparatus 619 and 620 on the lower shaft 618 . likewise , in order to accomodate different numbers of heating means 752 , it would only be required to establish correspondingly more sets of holes in the plate 623 . in a preferred mode of operation , the embodiment in fig6 through 9 operates as shown in fig1 a through 10d . in fig1 a through 10d , a bushing 920 is mounted around the post hole of the battery casing 732 as is practiced in the art . thereupon , as the casing is assembled , a terminal post 921 fits into the metallic bushing , to be welded thereto by application of apparatus embodying the principles of the present invention . in order to prepare the machinery of fig6 through 9 for operation , the plate 623 first is adjusted as desired to locate the heating means and the molding means appropriately over batteries to be processed . once a battery is positioned beneath the fig6 apparatus by means of a conveyor or the like , not shown , the cylinder 630 and piston 830 are energized to lower the carriage assembly and the molding apparatus downwardly onto the battery as shown in fig1 a . the first portion to make contact with the battery includes the molding means , which seat as appropriate over the portion to be processed as shown in fig1 b . thereupon , however , the cylinder 630 and piston 830 continues to exert downward force upon the carriage assembly , as shown in fig1 b , and a sliding of the carriage over the downward shafts 607 , 608 , 626 , and 627 results , such as shown in phantom in fig7 . once the heating means 752 are lowered to the desired position , as shown in fig1 c , the melting process of bushing 920 and post 921 as described hereinbefore is conducted , after which the heating means 752 first are withdrawn and sufficient time is allowed for the molten terminal post to set , as shown in fig1 d , and the entire assembly is then withdrawn upwardly . it may therefore be seen that the principles of the present invention provide substantial flexibility , in that variable numbers of heating means 752 may be utilized , but all are freely adjustable in accordance with the established structure of the plate 623 . by utilizing associated molding mechanisms , further adaptability is provided , since , first , unitary mold mechanisms are not needed , and , secondly , the interchangeable mold members 621 and 622 facilitate processes of different types . it will also be noted that , while the invention is described and illustrated above , it is principally for use with multiple - terminal applications , the same may be used for single applications , regarding the welding of batteries , and with respect to other types of welding . furthermore , various changes in the details , materials and arrangement of parts , as well as in the use and operation thereof may be effected , all within the spirit and scope of the invention as recited in the appended claims . | 8 |
in the description herein , numerous specific details are provided , such as examples of components and / or methods , to provide a thorough understanding of embodiments of the invention . one skilled in the relevant art will recognize , however , that an embodiment of the invention can be practiced without one or more of the specific details , or with other apparatus , systems , methods , components , materials , parts , and / or the like . in other instances , well - known structures , materials , or operations are not shown or described in detail to avoid obscuring aspects of embodiments of the invention . fig1 is a block diagram of an apparatus ( system ) 100 that can implement an embodiment of the invention . the apparatus 100 includes two nodes 105 a and 105 b ( generally , node 105 ) that are connected by a link 110 . the nodes 105 a and 105 b are network devices such as , for example , network switches . the nodes 105 a and 105 b includes fault finders 115 a and 115 b , duplex mismatch detect module 120 a and 120 b , event log message generator module 125 a and 125 b , processors 130 a and 130 b , and phy ( physical link layer ) 135 a and 135 b ( generally , phy 135 ), respectively , as shown in fig1 . the phys 135 a and 135 include port 140 a and 140 b , respectively , and include other suitable standard hardware components in network devices and permit the transmission of data over the link 110 . for example , a phy 135 typically includes an mdi ( medium dependent interface ) which is the connection to the link ( medium ) 110 ( i . e ., the direct physical and electrical connection to the link ). auto - negotiation automatically configures duplex and speed . it is also possible to turn off auto - negotiation and forced both speed and duplex . the duplex mismatch detect module 120 and event log message generator 125 can be integrated into a single module which can be called as a duplex mismatch finder . the fault finders 115 a and 115 b , duplex mismatch detect module 120 a and 120 b , and event log message generator module 125 a and 125 b are typically implemented in software and are stored in a memory ( e . g ., memory 132 a and 132 b ) in the nodes 105 . the fault finders 115 a and 115 b , duplex mismatch detect module 120 a and 120 b , and event log message generator module 125 a and 125 b are typically programmed in a suitable programming language , such as , for example , c , and are created by use of known code programming techniques . the processors 130 a and 130 b ( generally , processor 130 ) execute the fault finders 115 a and 115 b ( generally , fault finder 115 ), duplex mismatch detect module 120 a and 120 b ( generally , module 120 ), and event log message generator module 125 a and 125 b ( generally , module 125 ), respectively , and also execute other software or firmware in a node 105 . the fault finder 115 is a module that detects for fault conditions in a network . a fault condition can include , for example , a loop configuration in the network . a fault condition can also include over threshold late collisions and over threshold cyclic redundancy check errors , as described below . an embodiment of the fault finder 115 is implemented in , for example , the procurve 5304 and 5308 switches and other switches which are commercially available from hewlett - packard company . the fault finder , 115 a will check the error counters 145 a and 150 a , while fault finder 115 b will check the error counters 145 b and 150 b . the fault finder 115 a will generate an event log message 155 a , based upon the values in the late collision counter 145 a and crc error counter 150 a exceeding threshold values that are set by the user and based upon whether the port is set to forced mode or auto - negotiation mode , as discussed below . when the collision counter 145 a exceeds a threshold value ( a user - settable boundary ), the fault finder 115 a sets a flag 155 a . when the crc error counter 150 a exceeds a threshold value ( a user - settable boundary ), the fault finder 115 a sets a flag 160 a . the flags 155 a and 160 a are typically values that are set in a memory ( e . g ., memory 132 a ) in the node 105 a . similarly , the fault finder 115 b will generate an event log message 155 b , based upon the values in the late collision counter 145 b and crc error counter 150 b exceeding threshold values that are set by the user , as discussed below . when the collision counter 145 b exceeds a threshold value ( a user - settable boundary ), the fault finder 115 b sets a flag 155 b . when the crc error counter 150 b exceeds a threshold value ( a user - settable boundary ), the fault finder 115 b sets a flag 160 b . the flags 155 b and 160 b are typically values that are set in a memory ( e . g ., memory 132 b ) in the node 105 b . various parameters are then checked by the duplex mismatch detect modules 120 and event log message generator 125 ( i . e ., parameters are checked by the duplex mismatched finder ) in order to detect a duplex mismatch , as discussed below , in accordance with an embodiment of the invention . various standard components and / or software in the nodes 105 a and 105 b ( and in the network 100 ) have been omitted in fig1 for purposes of clarity and for purposes of focusing on the functionalities of embodiments of the invention . it should be appreciated that , in alternative embodiments , the network system 100 may include components and products other than those discussed above . moreover , the network system 100 can be implemented on different hardware . those skilled in the art will recognize that other alternative hardware and software environments may be used without departing from the scope of embodiments of the invention . as such , the exemplary environment in fig1 is not intended to limit embodiments of the invention . fig2 is a block diagram of a method 200 in accordance with an embodiment of the invention . in block 205 , the late collision error flag 155 is set if the late collision error counter 145 exceeds a user settable threshold value , or the crc error flag 160 is set if the crc error counter 150 exceeds a user settable threshold value . the threshold value for late collision error counter 145 and for the crc error counter 150 are typically measured in errors per second and can be set to any suitable values depending on , for example , implementation . the fault finder 115 checks the counters 145 and 150 and sets the flags 155 and 160 if one of the counters 145 and 150 exceeds the user settable threshold value . late collision error is defined in the ethernet specification . late collisions occur when there is a late occurrence of a collision on the link . in an ethernet network , a collision is the result of two devices on the same ethernet network attempting to transmit data at exactly the same time . the network detects the “ collision ” of the two transmitted packets and discards them both . late collision is a very good indication that one node is trying to transmit data , while the opposite node in the link is transmitting data , and therefore , a duplex mismatch may be present . crc is a method of checking for errors in data that has been transmitted on a communications link . a sending device applies a 16 - bit or 32 - bit polynomial to a block of data that is to be transmitted and appends the resulting cyclic redundancy code ( crc ) to the block . the receiving end applies the same polynomial to the data and compares its result with the result appended by the sender . if the devices agree , the data has been received successfully . if not , the sender can be notified to resend the block of data . if there is a duplex mismatch , then a node 115 will see a late collision error or a crc error , depending on whether the node 115 is set for full - duplex or half - duplex . after the late collision error flag 155 is set ( i . e ., the late collisions exceeded a user settable threshold value ) or crc flag 160 is set ( i . e ., the crc errors exceeded a user settable threshold value ), then in block 210 , a check if a node port 140 is connected to a link 110 . if , in block 210 , the node port 140 is not connected to a link 110 , then , in block 215 , the flags 155 or 160 are cleared and a duplex mismatch is regarded as not present or as not possible . in block 220 , the method 200 returns to block 205 where the fault finder 115 will check the late collision error counter 155 and the crc error counter 160 and set the flags 155 or 160 if the collision error counter 155 or the crc error counter 160 , respectively , exceeds a user settable threshold value . if , in block 210 , the node port 140 is connected to a link 110 , then , in block 225 , the port 140 is checked if it is a 100tx port or 1000t port ( i . e ., the port 140 is checked if it is a copper port , since a duplex mismatch can only occur between copper ports ). if , in block 225 , the node port 140 is not a copper port , then blocks 215 and 220 are repeated as discussed above , and a duplex mismatch is regarded as not present or as not possible . therefore , fiber ports are not checked for duplex mismatches . if , in block 225 , the node port 140 is connected to a copper port , then , in block 230 , a check is performed to determine if the port 140 is connected to a gigabit link ( 1000t link ) ( i . e ., the port is up in gigabit mode ). a duplex mismatch will typically not occur in gigabit mode because the gigabit ethernet standard typically only supports full - duplex for connected device ( although the gigabit ethernet standard has the half - duplex mode , it does not use the half - duplex mode ). if , in block 230 , the port 140 is connected to a gigabit link , then blocks 215 and 220 are repeated as discussed above , and a duplex mismatch is regarded as not present or as not possible . if , in block 230 , the port 140 is not connected to a gigabit link , then , in block 235 , a check is performed on the configuration to determine if the port is set in forced mode . the forced mode can be 10hdx ( half - duplex ), 10fdx ( full - duplex ), 100hdx , or 100fdx . if forced mode is set in block 235 , then , in block 245 , the is forced flag ( generally flag 170 , and specifically flags 170 a or 170 b in fig1 ) is set by the duplex mismatch detect module 120 . if forced mode is not set in block 235 , then , in block 240 , a check is performed to determine if auto - negotiation was completed successfully . the duplex mismatch detect module 120 checks the phy 135 to determine if auto - negotiation has failed . the auto - negotiation process is disclosed in the standard ieee 802 . 3 clause 36 , which is hereby fully incorporated herein by reference . if auto - negotiation is not completed successfully in block 240 , then blocks 215 and 220 are repeated as discussed above , and a duplex mismatch is regarded as not present or as not possible . if auto - negotiation is completed successfully in block 240 , then , in block 250 , the autohdx flag ( generally flag 175 , and specifically flags 175 a or 175 b in fig1 ) is set by the duplex mismatch detect module 120 , to indicate that the port 140 is in auto - negotiation mode and in half duplex . note that it may be possible for a port be in auto - negotiation mode and in full duplex . however , in the embodiments described herein , the flag is looking for a possible error condition which can only occur when the port comes up in half duplex while in auto - negotiation mode . the flags 170 and 175 are values that are set in memory in a node 105 . in block 255 ( with the “ return duplex mismatch is possible flags ”), at this point it is known that a duplex mismatch is possible , so a message will be sent which includes the error condition denoted by these flags . the duplex mismatch detect module 120 performs the above - mentioned actions in blocks 210 through 255 . the following blocks then insure that the correct counter has matched the perceived side of the duplex mismatch . when there is a duplex mismatch , one node 115 will detect the late collisions , while the opposite node 115 will detect the crc errors . in block 260 , if the autohdx flag 175 is set and the late collision counter 145 has exceeded the user settable threshold , then , in block 270 , the user is informed of a duplex mismatch and a suggestion is made to the user to set the port 140 to full duplex . the autohdx flag 175 indicates that the port 140 is currently in auto - negotiation mode and in half duplex . in block 280 , the information that is generated in block 270 is provided to the user by sending an event log message 155 , and the method 200 then returns to block 205 where the fault finder 115 will check the late collision error counter 155 and the crc error counter 160 and set the flags 155 or 160 if the collision error counter 155 or the crc error counter 160 , respectively , exceeds a user settable threshold value . the event log message generator 125 ( fig1 ) informs the fault finder 115 to generate an event log message 155 with the information in block 270 . on the other hand , in block 260 , if the autohdx flag 175 is not set or if the late collisions counter 145 did not exceed the user settable threshold , then the method 200 proceeds to block 265 . in block 265 , if the isforced flag 170 is set and the crc error counter 150 has exceeded the user settable threshold , then , in block 275 , the user is informed of a duplex mismatch and a suggestion is made to the user to set the port to auto - negotiation mode . the isforced flag 170 indicates that the port 140 is currently in forced mode . in block 280 , the information that is generated in block 275 is provided to the user by sending an event log message 155 , and the method 200 then returns to block 205 where the fault finder 115 will check the late collision error counter 155 and the crc error counter 160 and set the flags 155 or 160 if the collision error counter 155 or the crc error counter 160 , respectively , exceeds a user settable threshold value . the event log message generator 125 ( fig1 ) informs the fault finder 115 to generate an event log message 155 with the information in block 275 . on the other hand , in block 265 , if the isforced flag 170 is not set or if the crc error counter 150 did not exceed the user settable threshold , then blocks 215 and 220 are repeated as discussed above , and a duplex mismatch is regarded as not present or as not possible . the event log message generator 125 performs the above - mentioned actions in blocks 260 through 275 . therefore , blocks 260 and 265 inform the user of a duplex mismatch and to set ( change ) the port 140 to either auto - negotiation mode or to full duplex . if the user is told to change the port 140 setting to full duplex ( see block 270 ), then this means the link partner to this port 140 ( i . e ., where the link partner is the node 115 on the other end of link 110 ) is in forced mode ( forced full duplex mode ), and this port 140 is in auto - negotiation mode and is in half duplex due to the fact that auto - negotiation did not complete successfully . on the other hand , if the user is told to change the port 140 setting to auto - negotiation ( see block 275 ), then this means the link partner to this port 140 is in auto - negotiation mode , while this port is in forced mode ( forced full - duplex mode ). based on the event log message 155 that is sent to the user of the port 140 , the user can change the port 145 settings in order to eliminate the duplex mismatch . it is also within the scope of the present invention to implement a program or code that can be stored in a machine - readable medium to permit a computer to perform any of the methods described above . reference throughout this specification to “ one embodiment ”, “ an embodiment ”, or “ a specific 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 , the appearances of the phrases “ in one embodiment ”, “ in an embodiment ”, or “ in a specific embodiment ” in various places throughout this specification are not necessarily all referring to the same embodiment . furthermore , the particular features , structures , or characteristics may be combined in any suitable manner in one or more embodiments . other variations and modifications of the above - described embodiments and methods are possible in light of the foregoing disclosure . it will also be appreciated that one or more of the elements depicted in the drawings / figures can also be implemented in a more separated or integrated manner , or even removed or rendered as inoperable in certain cases , as is useful in accordance with a particular application . additionally , the signal arrows in the drawings / figures are considered as exemplary and are not limiting , unless otherwise specifically noted . furthermore , the term “ or ” as used in this disclosure is generally intended to mean “ and / or ” unless otherwise indicated . combinations of components or steps will also be considered as being noted , where terminology is foreseen as rendering the ability to separate or combine is unclear . as used in the description herein and throughout the claims that follow , “ a ”, “ an ”, and “ the ” includes plural references unless the context clearly dictates otherwise . also , as used in the description herein and throughout the claims that follow , the meaning of “ in ” includes “ in ” and “ on ” unless the context clearly dictates otherwise . the above description of illustrated embodiments of the invention , including what is described in the abstract , is not intended to be exhaustive or to limit the invention to the precise forms disclosed . while specific embodiments of , and examples for , the invention are described herein for illustrative purposes , various equivalent modifications are possible within the scope of the invention , as those skilled in the relevant art will recognize . these modifications can be made to the invention in light of the above detailed description . the terms used in the following claims should not be construed to limit the invention to the specific embodiments disclosed in the specification and the claims . rather , the scope of the invention is to be determined entirely by the following claims , which are to be construed in accordance with established doctrines of claim interpretation . | 7 |
fig1 illustrates an example wireless communications network using picocells for facilitating mobile device access . picocells 101 are mounted on overhead , open - air cables 102 connected between utility poles 103 . each picocell 101 provides coverage to a coverage area 104 . a mobile device in coverage area 104 will be able to communicate with the network coupled to picocells 101 . providing continuous access to the network coupled to picocells 101 as a mobile device moves between coverage areas 104 is a goal of the wireless communications network . fig2 illustrates the various aspects of a picocell device . a base band unit 201 controls communication between the larger communications network and mobile devices . the radio processor 202 is configured to transmit and receive signals to and from one or more antennas 203 . antenna 203 is the physical device that broadcasts and receives wireless signals to and from mobile devices . a difficulty in providing an increasing number of picocell devices is that when creating the network , each picocell &# 39 ; s base band unit must be provisioned , commissioned , and managed individually , in a similar fashion to base stations with larger coverage areas . however , since the picocell device &# 39 ; s coverage area 104 is relatively small , many more picocells must be deployed for an equivalent amount of coverage . the result is that the overhead of provisioning , commissioning , and managing the picocell device must be repeated many more times when using picocell devices to cover a large area , when compared to a base stations with a larger coverage area . another difficulty when using picocells is the scalability of network traffic management as the number of picocells grows . in a long term evolution (“ lte ”) wireless communications network , data links are required between every cell in a cluster in order to facilitate fast and seamless hand - off between the different cells as a mobile device moves from one coverage area to another . in addition , a data link is required to connect the picocell to the service provider &# 39 ; s core network . as a result , the number of connections required for n nodes is on the order of magnitude of n squared . managing an exponentially growing number of connections is a scalability problem when considering the large number of picocells required to serve a large network area . a third difficulty when using picocells is that when cascading them in long chains , a mobile device travelling through multiple picocell coverage areas generates multiple hand - offs , requiring action from the network to correctly predict the movement of the mobile device and hand - off the mobile device to the next picocell coverage area . this hand - off requires time and system resources . generally speaking , moving from one picocell coverage area to another picocell coverage area requires an inter - node hard handoff . this requires , for example , finding a new target picocell to connect to the mobile device based on estimations of the mobile device &# 39 ; s location , speed , the original picocell &# 39 ; s signal strength and coverage area , and the target picocell &# 39 ; s signal strength and coverage area . once the new target picocell is determined , the original picocell communicates a handoff order comprising the target picocell &# 39 ; s frequency or time slot to the mobile device . the target picocell informs the communications network and the communication link between the communications network and the mobile device is established through the target picocell . a common possible side effect may be a short loss in communication , or even a dropped communication connection . since a picocell coverage area may be small , a mobile device may experience many handoffs as it moves through many picocell coverage areas . one approach to addressing some of these issues may be to utilize a remote radio head means of implementing a picocell . in such a case , base band unit 201 is separate from the combination of the radio processor 202 and the antenna 203 . the radio processor 202 in this configuration may be known as a remote radio head . in fig1 , each picocell 101 may be replaced by a remote radio head and multiple remote radio heads may be coupled to a single base station 201 . however , when configuring the system to include cascaded chains of remote radio heads coupled to a base band unit , some difficulties remain . for example , the base band unit 201 requires a data connection to each remote radio head , and the resulting data throughput requirements limit the size of cascaded chains . in addition , such connections often occur over a dedicated network line . the present invention contemplates solutions to this problem while achieving the benefits of cascaded radio heads . fig3 illustrates an example embodiment of the present invention for a wireless communications network 301 utilizing distributed cascaded remote radio heads over a shared network . wireless communications network 301 may have one or more base band units 302 . base band unit 302 may be coupled to one or more mobile network clusters 303 via a general purpose , fiber - optic backhaul network 304 and shared network 318 . backhaul network 304 may carry general data telecommunications and / or multimedia traffic to and from networks and devices , such as cable services network 314 , core wireless network 312 , internet service network 316 , land - based service subscribers 311 , mobile devices 308 , and other networks and devices not pictured . backhaul network 304 may comprise a fiber - optic network . shared network 318 may comprise a fiber , electromagnetic , or hybrid transmission lines . shared network 318 may carry general data telecommunications and / or multimedia traffic to and from devices in or in communication with cluster 303 and networks connected to backhaul network 304 . shared network 318 may be coupled to backhaul network 304 by means of an optical switch 305 . in one embodiment , optical switch 305 may comprise an optical add / drop multiplexer . cluster 303 may be coupled to shared network 304 . base band unit 302 may be coupled to multiple clusters 303 . each cluster 303 may comprise one or more remote radio heads 306 cascaded in a chain topology . the one or more remote radio heads 306 may be coupled to one other through optical fiber . each remote radio head 306 may be coupled to one or more antennas 307 . antennas 307 send and receive wireless signals to and from one or more mobile devices 308 . cluster 303 may also be coupled to an optical node 309 . optical node 309 may be configured to transfer signals from an optical fiber to an electromagnetic transmission line 310 . in one embodiment , electromagnetic transmission line 310 comprises a coaxial cable transmission line . optical node 309 may be coupled to one or more land - based service subscribers 311 through electromagnetic transmission line 310 . land - based service subscribers 311 may receive any number of services by being coupled to optical node 309 , including cable television services , voice , or data . the optical fiber coupling optical switch 305 , remote radio heads 306 , and optical node 309 in conjunction with the electromagnetic transmission line 310 coupling optical node 309 and land - based service subscribers 311 may comprise a shared network 118 . the wireless communications network may be coupled to a core wireless network 312 that may transmit voice , data , or other digital information . the core wireless network 312 may comprise one or more wireless or hard - wired networks . core wireless network 312 may provide voice , data , or other digital information services to devices of wireless communications network 301 . core wireless network 312 may provide voice , data , or other digital information connections between remote devices ( not shown ) coupled to core wireless network 312 and devices of communications network 301 . the core wireless network 312 may be coupled to the wireless communications network 301 through shared network 318 via an optical switch 305 . wireless communications network 301 may be coupled to a cable services network 314 that may transmit television data , telephony data , or other data services . cable services network 314 may comprise one or more networks . cable services network 314 may provide television data , telephony data , or other data services to land - based service subscribers 311 . cable services network 312 may be coupled to wireless communications network 301 shared network 318 via an optical switch 305 . wireless communications network 301 may be coupled to an internet service network 316 that may transmit digital data comprising telephony , internet , multimedia , or other services . the internet service network 316 may comprise one or more networks . internet service network 316 may provide services to land - based service subscribers 311 . internet service network 316 may be coupled to the wireless communications network 301 through shared network 318 via an optical switch 305 . in operation , a voice or data connection may be established between a node in wireless communications network 301 ( or in core wireless network 312 ) and mobile devices 308 . for example , mobile device 308 a may send a signal to wireless communications network 301 which is first received by the antennas 307 a of a remote radio head 306 a . other remote radio heads 306 b , 306 c , 306 d may also receive through antennas 307 b , 307 c , 307 d the signal from mobile device 308 a . simultaneously , other mobile devices 308 b , 308 c , may be transmitting to wireless communications network 301 through one or more of the remote radio heads 306 . after receiving a wireless transmission from mobile device 308 a , and possibly other mobile devices 308 b , 308 c , remote radio head 306 a may process the received signals and transmit them via shared network 318 to the next upstream remote radio head 306 b in the cascaded chain . remote radio head 306 b may have also received wireless transmissions through its antennas 307 b from mobile devices 308 a , 308 b , 308 c which are processed by remote radio head 306 b . remote radio head 306 b may also receive a transmission from remote radio head 306 a . remote radio head 306 b may add the signals received through its antennas 307 b to the transmission from remote radio head 306 a . the resulting signal may be transmitted via shared network 218 upstream in the cascaded chain of radio heads to the next remote radio head 307 c . a similar process may occur utilizing remote radio heads 307 c and 307 d . the resulting transmission , representing the received signals from all mobile devices 308 communicating with cluster 303 , may be added to the shared network 218 . shared network 218 may transport the received signals to backhaul network 304 via optical switch 305 , whereupon the transmission reaches base band unit 302 . base band unit 302 may be coupled to core wireless network 312 to provide communication to mobile devices 308 . base band unit 302 may connect each transmitted signal through the backhaul network 304 to the appropriate destination , which may be in wireless communications network 301 or in core wireless network 312 . when data is transmitted from the destination node , which may be in wireless communications network 301 or in core wireless network 312 , back to mobile devices 308 , the data may flow through backhaul network 304 to the cluster 303 by way of optical switch 305 and shared network 318 . several such downstream data connections may be made to multiple mobile devices 308 on the cluster 303 . a single composite signal composed of the multiple downstream connections may be broadcast simultaneously on all remote radio heads 306 in the cluster 303 . remote radio head 306 a may receive the composite signal and broadcast it to relevant mobile devices 308 within range . the ability of a mobile device 308 a to send and receive signals from a remote radio head 306 a may constitute a voice or data connection with the wireless communications network 301 or core wireless network 312 . when a mobile device 308 a moves from the coverage area of one remote radio head 306 a to the coverage area of another remote radio head 306 b , no hand - off , hard or soft , may be necessary . when a mobile device moves from the coverage area of a cluster 303 of remote radio heads to a different cluster , an intra - node hand - off may be used instead of an inter - node hand - off . thus , operation of wireless communications network 301 implemented with distributed radio heads may resemble the operation of a network implemented with macrocells , but with the benefits of a network implemented with picocells . in addition to communicating with mobile devices 308 , communications with land - based service subscribers 311 or other subscribers connected to cluster 303 may be provided by shared network 318 . backhaul network 304 may connect television , multimedia , internet , voice , or other data services to cluster 303 . communications with land - based service subscribers 311 may originate in cable services network 314 , internet service network , or another provider in communication with backhaul network 304 . the television , multimedia , voice , or other data services for land - based service subscribers may 311 be transported by shared network 318 between optical switch 305 and optical node 309 . the data and services between optical node 309 and land - based service subscribers 311 may be transported by electromagnetic transmission line 310 . communications with land - based service subscribers 311 may happen simultaneously with voice and data connections between mobile devices 308 and wireless communications network 301 . a method of communication between remote radio heads 306 may comprise a digital radio interface . in one embodiment , common public radio interface (“ cpri ”) may be utilized . cpri is an interface between radio equipment control ( such as base band units ) and radio equipment ( such as base band units ). the cpri protocol specifies transport , connectivity , and control between these communications devices , specifically for layer 1 and layer 2 . the cpri protocol does not , however , specify how to accomplish a cascaded chain of remote radio heads without the significant data requirements mentioned above in the discussion of fig1 . fig4 illustrates an example embodiment of a system 400 utilizing cpri to communicate between a cascaded chain of remote radio heads . one or more remote radio heads 401 a , 401 b , 401 c may be chained together using cpri . each remote radio head 401 may communicate with a wireless device 402 by sending and receiving wireless signals 403 a , 403 b , 403 c to and from wireless device 402 . each remote radio head 401 a , 401 b , 401 c may utilize a set of one or more antennas 405 a , 405 b , 405 c to send and receive wireless signals 403 a , 403 b , 403 c . remote radio heads 401 a , 401 b , 401 c are coupled to each other and to base band unit 404 through pairs of data links 406 a , 406 b , 406 c . pairs of data links 406 may be configured to carry upstream and downstream communication , and may be physically implemented with optical fiber . pairs of data links 406 may comprise a cpri link . each remote radio head 401 a , 401 b , 401 c may comprise a layer 1 module 407 a , 407 b , 407 c . layer 1 modules 407 may comprise any combination of hardware and / or software configurable to send and receive signals in a physical layer optical interface . each remote radio head 401 a , 401 b , 401 c may comprise a layer 2 module 408 a , 408 b , 408 c . layer 2 modules 408 may comprise any combination of hardware and / or software configurable to provide means of accessing or repackaging information being transported by layer 1 modules 407 . layer 2 modules 408 may comprise any combination of hardware and / or software configurable to implement a data link layer . a layer 1 module 407 a , 407 b , 407 c may be coupled to its respective layer 2 module 408 a , 408 b , 408 c . each remote radio head 401 a , 401 b , 401 c may comprise a processing unit 409 a , 409 b , 409 c . processing units 409 may be coupled to layer 2 modules 408 and to antennas 405 . processing units 409 may be configured to send / receive information about wireless signals 403 to / from antennas 405 . processing units 409 may be configured to send / receive data to / from layer 2 modules 408 , or otherwise access information being transported by layer 1 modules 407 by way of layer 2 modules 408 . processing units 409 may be configured to process information , received or to be sent , in such a way to facilitate cpri communication in the system 400 for between base band unit 404 and wireless device 402 through remote radio heads 401 . in one embodiment , processing units 409 may be partially implemented by the radio processor 202 of fig2 . remote radio heads 401 and base band unit 404 may comprise any system , device , or apparatus configured to interpret and / or execute program instructions and / or process data . in certain embodiments , a remote radio head 401 or a base band unit 404 may comprise a processor , for example a microprocessor , microcontroller , digital signal processor ( dsp ), application specific integrated circuit ( asic ), or any other digital or analog circuitry configured to interpret and / or execute program instructions and / or process data . in some embodiments , a remote radio head 401 or a base band unit 404 may interpret and / or execute program instructions and / or process data stored in a memory . a memory be coupled to a remote radio head 401 or a base band unit 404 and may include any system , device , or apparatus configured to hold and / or house one or more memory modules . each memory module may include any system , device or apparatus configured to retain program instructions and / or data for a period of time ( e . g ., computer - readable media ). in operation , wireless device 402 may broadcast a signal 403 c . remote radio head 401 c may receive the signal 403 c through its antennas 405 c . information about the signal 403 c may be sent to processing unit 409 c . processing unit 409 c may prepare the information for transport to the remainder of the wireless network and may use layer 2 module 408 c to package information about the signal 403 c to be sent by layer 1 module 407 c . information about signal 403 c may be sent to remote radio head 401 b through data link 406 c . remote radio head 401 b may receive information about signal 403 c through layer 1 module 407 b . remote radio head 401 b may receive signal 403 b through its antennas 405 b . information about signal 403 b may be sent to processing unit 409 b . processing unit 409 b may access information about signal 403 c by utilizing layer 2 module 408 b to interface with layer 1 module 407 b . processing unit 409 b may process information about signal 403 c and signal 403 b so as to accurately present the information to base band unit 404 . additional possible implementations of such operation of processing units 409 are given in fig5 , below . processing unit 409 b may use layer 2 module 408 b to package information about signal 403 b , or post - processing information about signals 403 b , 403 c , to be sent by layer 1 module 407 b . the information may be sent to remote radio head 401 a through data link 406 b . remote radio head 401 a may receive information about signals 403 b and 403 c through layer 1 module 407 a . remote radio head 401 a may receive signal 403 a through its antennas 405 a . information about signal 403 a may be sent to processing unit 409 a . processing unit 409 a may access information about signals 403 b and 403 c by utilizing layer 2 module 408 a to interface with layer 1 module 407 a . processing unit 409 a may process information about signals 403 a , 403 b , 403 c so as to accurately present the information to base band unit 404 . processing unit 409 a may use layer 2 module 408 a to package information about signal 403 a , or post - processing information about signals 403 a , 403 b , and 403 c to be sent by layer 1 module 407 a . the information may be sent to base band unit 404 through data link 406 a . fig5 illustrates an example embodiment of a system 500 of upstream cpri communication between cascaded remote radio heads showing example signal processing . one or more remote radio heads 401 a , 401 b , 401 c may be coupled together using cpri . as noted above , each remote radio head 401 may receive a signal 503 a , 503 b , 503 c through its antennas from a wireless device . each remote radio head 401 may comprise elements for processing wireless signals 503 . for example , each remote radio head 401 may comprise a delay compensation buffer 502 a , 502 b , 502 c , as well as an adder 504 a , 504 b for adding the wireless signals 503 a , 503 b received through antennas to signal received from another remote radio head 401 . each remote radio head 401 may be configured to transmit the resultant signal using the cpri protocol upstream to the next remote radio head 401 ; or in the case of remote radio head 401 a , to the base band unit 404 . in operation , remote radio head 401 c receives a wireless signal 503 c through its antennas ( not shown ). because remote radio head 401 c is the last remote radio head in the cascaded chain , it may simply transmit the signal to remote radio head 401 b using the cpri protocol . remote radio head 401 b does not receive the signal from remote radio head 401 c instantaneously ; there may have been some delay 505 c . thus , the received signal 506 c is the wireless signal 503 c with some delay 505 c . remote radio head 401 b may also receive a wireless signal 503 b from its own antennas . to correctly add the wireless signal 503 b to the received signal 506 c , delay compensation buffer 502 b may add an estimation of delay 505 c to wireless signal 503 b , resulting in delay - compensated wireless signal 507 b . delay compensation buffer 502 b may be configured at installation , taking into account the distance between remote radio heads 401 b , 401 c , the equipment used , and any other factors that contribute to delay . alternatively , the delay 505 c may be measured during installation and delay compensation buffer 502 b set accordingly . the two signals , delay - compensated wireless signal 507 b and received signal 506 c , may be added using digital signal bits addition . the resulting signal 508 b may comprise wireless signals 503 b , 503 c adjusted for time or phase associated with delay 505 c . the resulting signal 508 b may be transmitted using cpri to the next upstream remote radio head 401 a . similarly , remote radio head 401 a may receive received signal 506 b that comprises the resulting signal 508 b and some delay 505 b . remote radio head 401 a may also receive a wireless signal 503 a from its own antennas . to correctly add the wireless signal 503 a to the received signal 506 b , delay compensation buffer 502 a may add an estimation of delays 505 b , 505 c to wireless signal 503 a , resulting in delay - compensated wireless signal 507 a . delay compensation buffer 502 a may be configured at installation , taking into account the distance between remote radio heads 401 a , 401 b , 401 c , the equipment used , and any other factors that contribute to delay . alternatively , the delays 505 b , 505 c may be measured during installation and delay compensation buffer 502 a set accordingly . the two signals , delay - compensated wireless signal 507 a and received signal 506 b may be added using digital signal bits addition . the resulting signal 508 a may comprise wireless signals 503 a , 503 b , 503 c adjusted for time or phase associated with delays 505 b , 505 c . the resulting signal 508 a may be transmitted using cpri to the base band unit 404 . in one embodiment , the digital signal bits addition may be accomplished by sampling , at each remote radio head , a particularly frequency of the wireless signal with an accuracy of twelve bits . using digital signal bits addition , three bits may be allocated for carry - over bits , resulting in the ability to cascade up to eight remote radio heads with a 1 . 2 gbps fiber connection for bidirectional traffic . in a further embodiment , cascading remote radio heads may be based upon the cpri standard , version 4 . in yet a further embodiment , additional remote radio heads may be supported with a larger word size . fig6 is a diagram illustrating an example embodiment of a method 600 of upstream communication for a cascaded chain of remote radio heads over a shared network . simultaneously , upstream communication with wireless mobile devices , as well as bi - directional communication with land based service subscribers , may be possible . upstream communications may be of the form wherein a wireless device may send a signal , packet , or transmission to a device in the core wireless network through a remote radio head . downstream communications may be of the form wherein a device in core wireless network may send a signal , packet , or transmission to a wireless device through a remote radio head . for upstream mobile communications , in step 601 wireless signals may be obtained from one or more mobile devices in one more remote radio heads in a single cluster . each remote radio head may receive the wireless signals through its own antennas . for all the remote radio head devices in a single cluster , obtaining wireless signals may happen simultaneously . in step 602 , the wireless signal may be compensated for the cumulative delay occurring in all upstream wireless signal acquisitions . the compensation may be configured at installation , taking into account the distance between the remote radio head and the downstream remote radio heads . as a result , the compensated wireless signal will have minimal time or phase differences from signals received in step 603 . if the remote radio head is at the bottom of the cascaded chain of remote radio heads , no compensation may be necessary . in step 603 , the remote radio head may receive a signal from a downstream remote radio head , the signal containing the received wireless radio signals received by all downstream remote radio heads . if the remote radio head is at the bottom of the cascaded chain of remote radio heads , the remote radio head might not receive a signal from a downstream remote radio head . in step 604 , the delay compensated wireless signal and the received signal may be added together using digital signal bits addition . in step 605 , it may be determined whether or not the top of the chain of remote radio heads has been reached . if the top of the chain of remote radio heads has been reached , then in step 606 , the resulting signal may be transmitted to the base band unit . the resulting signal in this step may represent the received signals from all mobile devices communicating with the cluster . if the top of the chain of remote radio heads has not been reached , then in step 607 , the resulting signal may be transmitted upstream to the next remote radio head via the cpri protocol . steps 602 - 607 may be repeated for the next upstream remote radio head . for downstream mobile communications , an inbound signal to a wireless device in communication with a cluster may be routed over the backhaul network to the appropriate cluster . the signal may be routed to each remote radio head in the cluster using a single cpri link . the signal may be broadcast simultaneously through each remote radio head &# 39 ; s antennas and received by the wireless device . for communications with land based service subscribers , an inbound signal to a land based service subscriber coupled to an optical node , the optical node coupled to a cluster , may be routed over the backhaul network to the appropriate cluster . the signal may be transported over fiber through remote radio heads . the signal may then be routed over an electromagnetic transmission line to the target land - based service subscriber . these steps may describe a downloading process ; an uploading process may be accomplished simply by reversing the order of the steps . although fig6 discloses a particular number of steps to be taken with respect to an example method 600 , method 600 may be executed with more or fewer steps than those depicted in fig6 . in addition , although fig6 discloses a certain order of steps to be taken with respect to method 600 , the steps comprising method 600 may be completed in any suitable order . for example , steps 602 - 606 may be conducted in parallel , simultaneously or at different times , at each remote radio head within the cascaded chain of remote radio heads . in addition , step 603 may be completed before completing step 602 , since both steps are independent of each other and are predicate to step 604 . method 600 may be implemented using the network of fig3 , the system of fig5 , or any other system operable to implement method 600 . in certain embodiments , method 600 may be implemented partially or fully in software embodied in computer - readable media . for the purposes of this disclosure , computer - readable media may include any instrumentality or aggregation of instrumentalities that may retain data and / or instructions for a period of time . computer - readable media may include , without limitation , storage media such as a direct access storage device ( e . g ., a hard disk drive or floppy disk ), a sequential access storage device ( e . g ., a tape disk drive ), compact disk , cd - rom , dvd , random access memory ( ram ), read - only memory ( rom ), electrically erasable programmable read - only memory ( eeprom ), and / or flash memory ; as well as communications media such wires , optical fibers , and other electromagnetic and / or optical carriers ; and / or any combination of the foregoing . although the present disclosure has been described in detail , it should be understood that various changes , substitutions , and alterations can be made hereto without departing from the spirit and the scope of the disclosure as defined by the appended claims . | 7 |
the invention is explained in more detail in the following drawings and examples . as indicated schematically in fig1 , the most important parts of the coating device are the pouring plates ( 1 ) with the laterally mounted lateral limiter plates ( 2 ). the free fall of the curtain ( 6 ) begins at lip ( 4 ) of the pouring front plate ( 5 ). from this point , the curtain ( 6 ) is stabilized by the lateral guides ( 7 ). the coating device further comprises a web ( 8 ), which is guided around the pouring roll ( 9 ) in the indicated rotational direction and underneath the coating device in order to be coated . in the coating device according to the invention , the laterally limiting liquid film ( 11 ) is supplied transversally to the curtain , as shown in fig2 . the supplying slit ( 12 ) has such a shape that the flow direction of the liquid film ( 11 ) at the exit of the slit is the same as for the falling curtain ( 6 ) in order to minimize disturbances of the speed profile of the falling curtain . the lateral flow liquid consists mainly of water , eventually containing surfactants , inorganic or organic salts , polymers , pigments or ingredients of the coating solutions . it is also possible to use non - aqueous liquids as lateral flow liquid . the width l of the groove ( 13 ) in fig3 , the real guide surface of the curtain , is from 4 mm to 15 mm , preferably from 6 mm to 8 mm . within this range of widths of the groove ( 13 ), an optimal stability of the curtain is obtained with very small quantities of lateral flow liquid as measured by the amount of the coating solutions minimally necessary for curtain formation and where the curtain just does not detach from the lateral guides . the physical properties of the surface of the groove ( 13 ) are of utmost importance . rough surfaces are preferred , in particular surfaces with incorporated channels in the flow direction of the curtain . the channels may be of sinusoidal , triangular or rectangular profile or a mixture of these profiles , independent of the fact that such rough surfaces are considerably more difficult to clean than smooth surfaces . the incorporated channels are arranged in the direction of the falling curtain , either continuously or discontinuously . the distance between the channels is from 10 μm to 1000 μm , in particular from 100 μm to 250 μm . the depth of the channels is from 1 μm to 500 μm , in particular from 30 μm to 100 μm . a stable coating process is possible with amounts of the lateral flow liquid lower than 3 l / h with this device according to the invention . in contrast all devices known up to now , as for example the combination of the lateral guides described in patent application ep 0 &# 39 ; 740 &# 39 ; 197 with the suction device described in patent application ep 0 &# 39 ; 841 &# 39 ; 588 , need high amounts of lateral flow liquid , typically from 8 l / h to 24 l / h . the device according to the invention and the method according to the invention unexpectedly need considerably lower amounts of lateral flow liquid using the same coating solutions , due to the optimized surface structure and width of the groove compared to the same device and method without the optimized surface structure and width of the groove . the stability of the border area of the curtain near the lateral guides has been considerably improved by this optimized width and surface structure of the groove . there is therefore no longer a need to remove the border areas of the curtain by a separation device during the coating process . at the lower ends ( 14 ) of the lateral guides ( 7 ), the whole amount of the coating solutions and of the lateral flow liquid are deposited on the moving web ( 8 ), as is illustrated in fig4 . in order to prevent the separation of the curtain from the lateral guides , the angle α between the two sides of the protruding edge needs to be between 0 ° and 90 °, in particular between 10 ° and 60 °. the added , mainly aqueous lateral flow liquid at the lateral guides leads to a more or less pronounced dilution of the border areas of the curtain resulting in local reductions of the viscosity of the coating solutions and higher coating weights in the border areas . furthermore air may be entrapped below the falling curtain , inducing further coating defects . in order to prevent this air entrapping , in particular with low coating weights and low viscosities of the coating solutions , the lower ends of the laterals guides need to be of optimal shape . the lower ends ( 14 ) of the lateral guides ( 7 ), directed towards the curtain , have the shape of a downward protruding edge , as illustrated in fig4 . this edge may be sharply defined or slightly rounded . the size of the height and of the width of this edge is in the region of some millimeters . the angle β between the horizontal line and the side of the protruding edge facing the curtain is from 0 ° to 90 °, in particular from 30 ° to 90 °. at the lowest ends of the lateral guides , the falling curtain separates from the lateral guides and falls unguided onto the moving web below the lateral guides . in this unguided region , the curtain shows the tendency to contract due to the surface tension forces of the coating solutions . this leads to a more or less pronounced bead at the border of the coating with all the devices known up to now in the curtain coating process . such beads have to be prevented , because the higher amounts of coating solutions in these regions do not dry sufficiently fast , which may lead to sticking of the different loops on the wound rolls . in order to minimize the size of the formed beads , the distance d between the protruding edge at the lower ends ( 14 ) of the lateral guides ( 7 ) and the moving web ( 8 ) to be coated needs to be from 0 . 05 mm to 3 mm , in particular from 0 . 4 mm to 1 . 5 mm , as shown in fig4 . liquids in the border region of the curtain ( a mixture of lateral flow liquid and coating solutions ) may be drawn below the elements of the lateral guides , depending on the coating weights and viscosities of the coating solutions , leading to strong soiling in the region of curtain impingement . in order to prevent this soiling , the distance d has to be adapted to the coating weights and viscosities of the coating solutions . the surfaces of the undersides of the lower ends ( 14 ) of the lateral guides ( 7 ) need to be hydrophobic . the free surface energy of these undersides has to be in the range of 10 mnm to 60 mnm , in particular in the range of 20 mnm to 45 mnm . suitable surface coatings of the underside consist of amorphous carbon or teflon ( polytetrafluoroethylene ). a particularly preferred surface coating is teflon ( polytetrafluouroethylene ). it is to be understood that the device according to the invention may be varied with respect to the indicated dimensions and adapted to a wide variety of coating conditions occurring during coating processes . while each measure individually allows considerable improvements with respect to coating quality , the combination of the improvements described above for the lateral guides ( suitable angles a and β , optimal surface structure and width of the groove and a suitable surface coating of the undersides of the lower ends ) gives a method and a device , where separation and suction devices are no longer needed and where the quality of the coating on the moving web is nevertheless impeccable . there is no need for a costly infrastructure for separation and drainage systems for the separated coating solutions . there are less coating interruptions caused by obstruction of sucking devices , because these trouble prone devices are no longer necessary . it is possible to coat highly reactive coating solutions . the device according to the invention will be compared with a device representing the state of the art in the following examples . however , it has to be understood that the present invention will not be restricted or limited in any way by these specific examples . a first coating solution containing the ingredients of table 1 was prepared . the quantities , with the exception of water , are those of the coated and subsequently dried layer . the lanthanum - doped aiooh was prepared according to the method described in patent application ep 0 &# 39 ; 967 &# 39 ; 086 , example 1 . polyvinyl alcohol a is mowiol 26 – 88 , polyvinyl alcohol b is mowiol 56 – 98 , both available from omya a g , oftringen , switzerland ; plasticizer 1 is 1 , 1 , 1 - tris -( hydroxymethyl )- propane , available from fluka - chemie , buchs , switzerland ; plasticizer 2 is glycerol ; the surfactant is triton x - 100 , available from christ chemie ag , reinach , switzerland . a second coating solution containing the ingredients of table 2 was prepared . the quantities , with the exception of water , are those of the coated and subsequently dried layer . the gelatin is a limed bone gelatin , available from deutsche gelatinefabriken , eberbach , germany ; the bactericide is 4 - chloro - m - cresol , available from chemia brugg a g , brugg , switzerland ; surfactant b is niaproof 04 , available from fluka chemie gmbh , buchs , switzerland and surfactant c is olin 10g , available from arch chemicals , norwalk , usa . a curtain was formed with these two coating solutions using the curtain coating device incorporating the lateral guides according to the invention . the stability of the curtain was evaluated by determining the minimal quantities of the coating solutions that were necessary for the formation of a stable curtain between the lateral guides according to the invention . water with a small addition of sodium chloride was used as lateral flow liquid . the addition of sodium chloride is necessary in order to allow the adjustment of the flow rates by magneto flows . results obtained with the device according to the invention are presented in table 3 . the width of the groove ( 13 ) was 7 mm , the angle α was 45 °, the angle β was 90 °, surface structure of the groove consisted of continuous channels of serrate profile with a depth of 50 μm at a distance of 150 μm of each other . results obtained with the device described in patent application ep 0 &# 39 ; 841 &# 39 ; 588 are presented in table 4 . in this case , the width of the groove ( 13 ) was 17 mm , the angle α was 45 °, the angle β was 90 ° and the groove had a smooth surface . a comparison of the results in tables 3 and 4 immediately shows that the minimal quantities of the two coating solutions necessary for the formation of a stable curtain are considerably lower with the device according to the invention compared to the device forming the state of the art . the needed quantity of lateral flow liquid is also much lower . the prepared coating solution was applied to a commercially available polyethylene coated paper support with the aid of a curtain coating device . water with a small addition of sodium chloride was used as lateral flow liquid . the distance d between the lower end of the lateral guides and the moving web was varied in the range between 0 . 4 mm and 3 . 0 mm . the underside of the lateral guides had a teflon ( polytetrafluoroethylene ) surface coating . the quality of the of the border areas ( beads ) and of the amount of liquid entrapment ( coating solution and lateral flow liquid ) below the elements of the lateral guides were evaluated using the following five - grade scale : regular border , width of the bead from 3 . 5 mm to 5 mm the results obtained for the quality of the border areas ( beads ) and the tendency for liquid entrapment below the lateral guides are presented in table 5 for different distances between the lower ends of the lateral guides and the moving web to be coated . the results of table 5 immediately show that the optimum distance between the lower ends of the lateral guides and the moving web to be coated is between 0 . 4 mm and 1 . 5 mm . the prepared coating solution was applied to a commercially available polyethylene coated paper support with the aid of a curtain coating device . water with a small addition of sodium chloride was used as lateral flow liquid . the distance d between the lower end of the lateral guides and the moving web was 1 . 0 mm . the surface of the underside of the lateral guides was coated with different materials . the results obtained for the quality of the border areas ( beads ) and the tendency for liquid entrapment below the lateral guides are presented in table 6 for the surface of the undersides of the lower ends of the lateral guides coated with different materials . the results in table 6 immediately show that teflon polytetrafluoroethylene ) is an especially suitable material for the surface coating of the underside of the lower end of the lateral guides according to the invention . finally , variations from the examples given herein are possible in view of the above disclosure . therefore , although the invention has been described with reference to certain preferred embodiments , it will be appreciated that other coating solutions may be devised and used in the method and device described herein , which are nevertheless within the scope and spirit of the invention as defined in the claims appended hereto . the foregoing description of various and preferred embodiments of the present invention has been provided for purposes of illustration only , and it is understood that numerous modifications , variations and alterations may be made without departing from the scope and spirit of the invention as set forth in the following claims . | 8 |
a preferred embodiment of the present invention will now be described with reference to the drawings . in the following description , particular reference is made to one specific circuit configuration — the ica0000035 — used by the assignee of the present invention . it will of course be understood by those skilled in the art that various modifications may be made in the design of the audio mux asic without departing from the spirit and scope of the present invention . one version of the asic of the present invention , shown schematically in fig1 , contains 28 pins which are described next . this input is the master system clock for the ica0000035 circuits . it is used for the internal microcontroller core clock and also is divided down by four for to generate the internal sampling clock for the delta sigma this input is aserted every time the ica0000035 circuit is powered - up this signal will initialize all critical internal registers and counters . it also will document . it is an open - drain bidirectional signal . external pullup of 4 . 7k interupt input for embeded pic microcontroller . this interupt may be level this input is normally bumpered to irq and t x r x so that the fir circuit this analog input is an input which is internally filtered and scaled filtered . it available through mux selection at either the tx output or the rcvr output . one level of filtered synth signal is available at the tx output and three levels are available for output at the rx out output pin . this input is buffered by a pre - amp and provides an unfiltered gain output if selected at four different gain levels . the actual gain selected is this input is buffered by a pre - amp and provides an unfiltered gain output this signal is normally the dtmf signal from the micro asic ( 40a ). like the modem signal , this input may be selected for output without this input accepts a modem input for multiplexed selection to the tx output . when selected it is unfiltered and fed directly to the tx output . it auxiliary audio input . this input is filtered and gained to three different levels for selection at the rx out . output and filtered and gained at one level for output to the tx output . see table 1 for signal details . output may be used by external circuits but must be buffered if it is to this pin is an output which is set under program control by the embedded plc microcontroller formware . it is used as a reference to compare to this is on of two mux outputs for different audio inputs . it is generally used to output a scaled and filtered audio input and feed it to the phone receiver ( handset ). this is an audio output but is in bitstream form and therefore must be filtered using a second or third order filter . this is on of two mux outputs for different audio inputs . it is generally used to output a scaled and filtered audio input and feed it to the phone transmit circuits ( line ). this is an audio output but is in bitstream form and therefore must be filtered using a second filter which can also developed for this purpose and is presented in the interface requirements this output provides zero crossing information if an incoming audio tone . in the case where this output is being used for modem carrier , mark or bitstream . the analog value of this bitstream output is determined by the value written to portc of the internal pic microcontroller . this value is general purpose digital i / o point . this input / output pin may be used as an input1 output or bidirection i / o as programmed by the microcontroller via the one wire serial interface . if bit 4 of creg1 is ’ 0 &# 39 ; then this pin is used to control the pic clock . a high enables the clock input and a low will drop the clock input frequency by 64 , 536 thus reducing the cpu poer general purpose digital i / o point . this input / output pin may be used as an input , output or bidirection i / o as programmed by the microcontroller general purpose digital i / o point . this input / output pin may be used as an input , output or bidirection i / o as programmed by the microcontroller the purpose of the ica000035 circuit is to provide selection and conditioning of audio signals in protel &# 39 ; s payphones . these signals are divided into two categories , receive circuits and transmit circuits . the receive circuits are those that eventually get transmitted ( via the rx out pin ) to the handset receive device ( ear piece ). signals that are available for output on to the handset receive circuits are : rcv audio signal from the phone line interface dtmf confidence tone for phone generated dtmf signaling , and synth voice synthesis signal form icd0000050a asic . aux an auxiliary analog input to the chip tone output from an onchip dual tone generator xmtr transmitter signal fed back to the receiver ( typically for sidetone ) transmit circuits are those that eventually are output ( via the tx out pin ) to the two - to - four - wire phone line interface . signals that are available for output to the two - to - four - wire phone line interface are : fig2 a and 2 b provide a detailed block diagram of the ica000035 internal circuits and fig3 and 4 show the details of receive and transmit selection circuits . the design philosophy chosen for this design was to transform audio inputs into digital bitstreams that have ben noise shaped using delta - sigma technology . this approach will allow for easy and area efficient manipulation of the audio analog signals . any mention in the rest of this document to bitstreams will mean an analog signal that has been noise shaped using delta - sigma technology . the heart of the control of the analog signals is provided by an imbedded microcontroller that has been customized for the specific requirements of the ica0000035 circuits . see section 3 for detailed description of the imbedded microcontroller . one of its primary purposes , however , is to provide the command interpretation for signals present on the one - wire chip interface . the one wire interface is described in section 4 of this document . all communication with the ica0000035 circuits is performed over this interface . microcode to provide this functionality is permanently programmed into the chip via on board rom circuits . refer to section two for details on the interface protocol . additional code may be ‘ downloaded ’ via this same interface into on chip ram which will allow the user to modify existing code or add additional code for the imbedded microcontroller . other , on chip , non - audio circuits which provide added capabilities are described in section 1 . 4 of this document . cr2 7 cr2 6 input selected 0 0 xmtr 0 1 dtmf 1 0 modem 1 1 aux cr4 7 cr4 6 xmt signal selected 0 0 xmtr_ds 0 1 rcv_ds 1 0 synth 1 1 tone note , that the selected bitstreams may be additionally attenuated via control register bits cr 4 5 . 3 and cr 5 5 . 3 for the . this attenuation is described in more detail in section 2 . 1 of this document . the final output bitstream is filtered by a passive lrc two pole lowpass filter which is designed to provide line impedance matching ( 600 ohm ) as well as noise filtering , additional signal selection is provided for both the transmit and receive circuits before the tx — out and rx — out signals are output from the chip . for the transmit circuit the tx_ds output may be directly output by setting bit 3 of control register 3 to a ‘ 0 ’ state . setting this bit to a ‘ 1 ’ will select the transmit bitstream attenuator output as the signal to be output on the tx — out pin . this option is provided primarily for full duplex fsk modem operation where dual use of the xmtr output is required . ( see description of modem operation in this section below ). normally bit 3 of control register 3 is set high and the transmit bitstream attenuator is selected for output to the tx — out pin . as described above the ica0000035 circuit functions to provide signal conditioning and selection of 10 different audio signal types . these signals are aux , dtmf , rcv , modem , synth , xmtr , and a in0 . . . a in3 . table 1 below provides a description of these signal characteristics . source source name signal level voltage type frequency impedance aux 2 . 5 volts ac - sine wave 660 hz to 1 . 6 khz ≈ 200k ohms dtmf 2 . 5 volt p - p ac - sine wave 600 hz to 1 . 6 khz & lt ; 100 ohms rcv 3 . 0 volts audio voice ( bw = 3 khz ) & lt ; 100 ohms modem 5 volts ac sine wave & lt ; 2400 hz & lt ; 100 ohms synth 5 volt bitstream 890 & lt ; 100 ohms khz ( bw = 3 khz ) xmtr & lt ; 500 mv audio 600 hz to 1 . 6 khz & lt ; 100 ohms a in0 . . . a in3 . 5 to a vdd −. 5 analog & lt ; 100 hz & lt ; 1k ohms audio input selection multiplexers are provided on the chip for selection of both analog audio inputs as well as off - chip and on - chip bitstream generated audio signals . sections 1 . 2 and 1 . 3 describe the details of these signal selection for the tx out and rx out circuits . fig3 and 4 show details of the signal flow for audio input signals that may be selected for output on the tx out and rx out output pin . the tx out pin is connected to a passive lrc filter for noise filtering if the output signal or bitstream . as shown seven audio input selections may be made . five of these signals are input into the chip as analog and then modulated before being fed to the digital signal selection logic . tw of the signals are in digital ( bitstream form ). the first is the synth pin which is a bitstream signal for voice encoding from the protel 50a series asic the other is a bitstream output from an on - chip dual tone generator . the selection of these signals are controller by control register 4 bits 7 and 6 for the transmit circuits and control register 5 bits 7 and 6 for the receive signal selection . the analog inputs are selected by controlling control register 2 bits 7 and 6 . additionally the rx out circuits allow for side - tone cancellation . this is accomplished as shown in fig2 by adding in a portion of the audio signal being output to the line to the receive circuits . control register bit cr5 7 determines whether or not the side tone circuit is used , see table below : the level of the sidetone is controlled by the bitstream delay register ( control register 6 – 7 : 0 ) and phase control bit ( bit 1 of control register 3 ). normally this bit is set to a ‘ 1 ’ so that the bitstream adder subtracts a scaled portion of the transmit signal from the incoming receive in the case where the protel 65c02 microprocessor is being used to perform 300 / 1200 fsk modem operation this sidetone circuit may be used for carrier cancellation . the operation is as follows , dtmf is transmitted by the 65c02 , the transmit selection logic selects the dtmf in its bitstream form . this bitstream is selected and attenutated and delayed such that when it is added back to the rcv signal it exactly cancels that portion of the rcv signal that is due to the transmitted carrier . this nulled rcv signal is then fir filtered by the limiter circuit of fig3 and the rxc signal is output which is an indication of the phase of the nulled and filtered rcv signal . in addition to selection control of audio input and output circuits , the ida0000035 design also provides an auxiliary a / d circuit independent of the audio circuits . this circuit is four channel a / d measurement circuit and its operation is described below . the four channel a / d measurement circuit is comprised of a four - channel analog multiplexer circuit which selects one of four analog inputs . an additional input reference pin is provided to this circuit . this reference pin is typically connected to a low pass filtered version of on chip d / a modulator output ( see below ). the selected pin is successively compared with the current modulator d / a output . this d / a output is thus ‘ ramped ’ up or down until the comparitor trips . it is at this point that the current digital value in the d / a register may be read . the read value reflects the current value of the selected analog signal . port mapping of the signal selection is as follows : three digital i / o lines are also available for other phone functions . these signals are programmed and controlled via the one - wire serial interface . these pins are mapped to porta bits 0 – 2 of the imbedded microcontroller . an on chip da converter is provided whose output is available to the mod out pin of the ica0000035 asic . this converter also uses second order delta - sigma modulation techniques . digital values written to port c of the imbedded pic microcontroller are modulated into a second order noise shaped bitstream . this bitstream is the signal that is output on the mod out pin . to recover the analog signal a simple multi - pole rc filter may be used . an on chip tone generator is provide for the user to use for future applications requiring a stable tone or sine wave generator . the sine wave generation does not use the standard look - up - table method . it is a circuit implementation of the solution to the differential equation for a sine wave give by which is the circuit shown in fig4 . the frequency is determined by the input divide - by - n clock divider and the sine wave circuit itself . the sine wave circuit has been designed so that there are 25 . 1 clocks per cycle . this is accomplished by accomplishing the 1 / ω 2 multiplication of the output as a 4 bit shift . therefore therefore the frequency of the final sine wave is given by the inverse of the output of the divide - by - n counter times 25 . 13 . or two of these sine wave generators are provide as part of the tone generation circuit . the value of n for each tone is set by control registers cra and crb . the amplitudes may be set by setting the initial condition on the first integrator of each tone generation circuit . the amplitude setting requires eight bits from control registers cr8 and cr9 . the table below summarizes the use of control registers cr8 , cr9 , cra and crb for amplitude and frequency control of the two tone generators . the tones from the on chip tone generator may be selected for output using the following selection logic : several on chip clocks are required to operate the circuit blocks described in this document . one master clock is provided to the chip and all internal clocks are derived from this single master clock . the required on chip clocks and their relationship to the master clock are summarized in the table below : clock description clk imbedded pic microcontroller clk ph1 clk + 4 ph1a ph1 clock with trailing edge advanced ph1b ph1a clock with trailing edge advanced ph2 clk + 4 , ph1 inverted and non overlapping ph2a ph2 clock with trailing edge advanced ph2b ph2a clock with trailing edge advanced bitclk clk + 4 , bitstream clock for bitstream building blocks the timing diagrams of fig4 c show the clocks and their timing . all analog signals which are processed on - chip are converted to bitstream which are noise shaped . this conversion is accomplished via modulators which modulate analog signals into a bit - density modulated format whose nose characteristics are such that noise in the signal band is suppressed and out - of - band noise is shaped such that it increases at a rate of 15 db per octave . it is important that as the signals are manipulated that noise shaping is maintained . on - ship bitstream function blocks are provided which will perform analog equivalent functions on the bitstreams without requiring the bitstreams to be converted to parallel data structures . this bitstream manipulation will maintain the required second order noise shaping of the original signal . the table below shows these building blocks ( and the addition of the modulator ) and their equivalent analog functions : the sections below give detailed explanations of these building blocks as well as details on port mapping required for control and monitoring . it should be noted that , throughout the bitstream building block descriptions , the scaling is such that all one &# 39 ; s is considered positive full scale , all zero &# 39 ; s is considered negative full scale and 50 % density ( equal number of one &# 39 ; s and zero &# 39 ; s ) is considered to have a signal value of zero . fig5 show a block diagram of the bitstream modulator . two of these building blocks are provided on the ica0000035 asic . one is dedicated for receive circuits and the other is dedicated for transmit signals . these modulators are identical in design with the exception of the specific port mapping used to control these modulators . the modulators , as shown , may be partitioned into two stages . first a programmable gain stage is provide which will precondition the input signal for the proper dynamic range of the modulator . second the pre - conditioned signal is then modulated with the second order delta - sigma modulator . the result is a bitstream output who &# 39 ; s bit density is proportional the analog value . scaling is such that an analog value of mid - reference will produce a 50 % bit stream density . the pre - amp is a switched capacitor , double sampled capacitive reset circuit . this circuit will cancel any circuit offsets , 1 / f noise and errors due to finite amplifier gain to a first order approximation . simulations show that these input signal errors are reduce by a factor of about − 60 db or better . non - overlapping and delayed phased clocks are provided to operate the switched capacitor circuits in a way so as to reduce the effects of charge injection as well . the clock timing is described in section 1 . 4 . 5 “ clock generation ”. gain selection is the only control ( other than clocks ) required by the modulator block . this is accomplished via control register bits of the imbedded microcontroller . the tables below show the available gain selections and their corresponding control register bits for each of the two modulators . maximum signal range into the modulator should be kept at 15 % to 85 % of full scale for best modulator performance . full scale is defined as the difference of a vdd and a vss . for a 5 volt system this would reflect to a signal range of 2 . 5 volts ± 2 . 125 volts . a good practice would be to design for a maximum input of ± 2 . 0 volts to the modulator after the signal has been pre - scaled by the programmable gain input stage . these recommended maximum operating signal ranges for each gain setting are shown in the last column of the tables above . the modulator output is buffered . this helps to isolate any output signal loading in the digital portion the chip from the modulator itself . additionally the buffer is driven from d vdd and d vss so as not to cause any analog supply noise which may get folded back into the analog signal . the bitstream attenuator is comprised of two main components , the signal selection mux and the attenuation circuits ; this is shown in block diagram form by fig6 . this block is entirely digital . the input signal selection mux is 4 - to - 1 signal selector and is controlled by select bits sel 1 , and sel 0 . in the current form of the ica0000035 only two inputs are required for either the receive circuit or the transmit circuit , however control bits from the imbedded microcontroller are still connected to allow for test features which will allow the bitstreams to be set high or low . like the modulator blocks there are one of these blocks for the receive circuit and one for the transmit circuit . the tables below show the available signal selections and their corresponding control register bits for each of the two attenuation blocks . the attenuation portion of the circuit produces an output bitstream who &# 39 ; s density is the input density times the attenuation gain factor or more explicitly with scaling taken into account , where gain is the digital value of bits cr 4 5 . 0 and cr 5 5 . 0 for the transmit and receive circuits respectively . there is a slight delay and noise penalty for passing a signal through this attenuation block . therefore a special case has been provided for which will allow the signal to pass straight through unmodified . this exception to the above gain equation occurs when gain = 63 . according to the formula above the resultant gain would be 63 / 64 . however to allow signals to be ‘ passed - through ’ the block additional circuitry has been provided to look for the special case of gain = 63 and produce a gain value of 1 . it is important to note here that the convention of signal value of zero being a 50 % duty - cycled bitstream is maintained . this means that an attenuation of gain = 0 will produce a bitstream density of 50 % not a constant stream of “ 0 &# 39 ; s ” s . fig7 shows a simplified version of the bitstream adder block . the current bit value of the ‘ a ’ input is added to the current value of the ‘ b ’, input and the remainder from add . there is an arbitrary scaling performed which therefore allows the output to be defined as note that the noise shaping is maintained since the residual is fed back for the next computation and is not thrown away . in actuality the circuit is a bit more complex than what is shown . in the actual implementation there are two stages of integration ( the adder and latch compose a single stage integrator ). the integrator bit sizes become multi - bit in nature and add circuits are required to keep these integrators from overflowing . the size that the integrators are allowed to ‘ wind - up ’ determines the range of the input signal before clamping . this bitstream adder will allow signals from 10 % to 90 % before any noise is introduced as a result of clamping . it should be noted that with the convention of bitstream zero being a 50 % duty cycle waveform that the bit stream adder may become a bitstream subtractor simply by inverting the input to be subtracted or for example when the ‘ b ’ input is inverted before being input to the bitstream adder the result is : other than the input clock , which must be at the bit rate , no control registers are required for the bit stream adder . in the ica000035 asic this bitstream adder is used in two ways . first during normal voice communication a small part of the handset transmit signal is partially nulled out to provide partial sidetone cancellation to the handset receiver . this level can be set by controlling the gain input of the transmit bitstream attenuator ( see section 2 . 2 — bitstream attenuator ). secondly this circuit is used when the protel 65c02 processor us used as a 300 / 1200 fsk modem . in this case the entire transmitted signal ( carrier ) is canceled so that the receive signal may be discriminated carrier free . in this case the phase an magnitude of the transmitted carrier must be exactly matched and subtracted from the receive signal . this requires the use of a delay circuit ( to match phase ) as well as the bit stream attenuator . ( refer to section 1 . 4 bitstream delay circuits and section 1 . 5 — bit stream comparitor for further details . the bitstream delay circuit is intended to provide enough delay in the transmitted modulated dtmf bit stream so as to exactly equal the phase shift experienced by the modulated dtmf bitstream through the output lrc filter . the phase shift will be different from phone installation to phone installation even though the filter remains constant due to different line impedances . the output of this filter is fed back to the receive input and remodulated . once the phase is matched it is a simple take to adjust the amplitude to exactly cancel out the original dtmf carrier . referring to fig8 , the circuit operation is as follows . the input bitstream is fed into a 256 bit shift register . with a one megahertz clock this will provide over 90 ° of phase shift ( well more than what is expected in the field ). each bit of the shift register is then input to a 256 to 1 selector and the eight bit control register input c9 ( 7 .. 0 ) then selects the appropriate phase shift . this procedure requires support from the firmware form the phone microprocessor . this delay is set - up once automatically at installation and the need not change any more the control value register however must be stored in the system nonvolatile ram . fig9 shows the block diagram of the comparator . this block is used to detect the incoming fsk modem signal and well as tone detection . its bitstream input is fed into a low pass fir filter . this filter will pass signals up to 20 khz but will reject signals and nose above 30 khz with over 60 db rejection . this filter also maintains the scaling principal set forth for bitstream scaling in that a 50 % output value will be equivalent to a 50 % a bitstream input . the fir filter outputs a 12 bit value and hbyte control signal will select either the high byte ( creg3 bit 7 high ) or the low byte ( creg3 bit 7 low ) for output on on filter value register ( sreg3 bit 7 to 0 ). the value select input will determine if the value output is the actual filter value ( creg3 bit6 high ) or the derivative of the value ( creg3 bit 6 low ). the remaining three control bits ( creg3 bits 5 , 4 & amp ; 3 ) are used for changing the method of deglitching used on the zero crossing detector . except for very special filtering applications these may be left in the default state . see the register map in section 3 for more details on this functionality . the state machine for the ica0000035 has been implemented using a microcontroller core . this microcontroller core has been modeled after the microchip pic architecture . this core is very similar to the pic16c56 microcontroller but has been optimized for the protel application . this section will describe the details of operation of the protel pic core . features which have been added , modified or enhanced from the microchip version are : one clock cycle for all instructions internal timer timer interrupt external interrupt built - in dallas 1 - wire serial port 256 words of downloadable program memory ram d / a port 4 channel a / d the protel pic core ( ppc ) is a high performance risc like architecture microcontroller modeled after the microchip pic16c56 ( pic ) microcontroller . unlike the pic the ppc is able to execute all instructions , including program branches , in a single machine cycle . the ppc also differs from the pic in that a machine cycle is only a single clock whereas the pic machine cycle is four clocks . both the pic and the ppc utilize a 12 bit data / instruction word . the ppc has been designed specifically to provide an interface between protel audio circuits fn the ica0000035 asic and the main phone microprocessor . the ppc also provides for general purpose digital i / o for future phone applications . from an i / o point of view the ppc has the following i / o interfaces ; clock input master clock input for ppc . each instruction executes in one clock period . max clock frequency 20 mhz mrstn master reset - reset the ppc core and initializes all non - general purpose registers . and preset the d / a port to 2 . 5 volts ( mid supply ) irq_in irq input , edge triggered interrupt input . the ppc is programmable to trigger an interrupt on either edge . the default ( initialized upon mrstn ) is negative edge trigger . this interrupt is maskable and is shared with the timer interrupt . 8 bit d / a port c of the ppc is mapped to a 8 bit first order delta sigma modulator , its output is a single density modulated bitstream . the minimum duration for a one or zero is one clock cycle . to obtain the analog form of this output a simple 2nd order passive filter is all that is required . more specific details on this output are provided in section 1 . 4 . 4 . single - wire port the single - wire port is in one embodiment a dallas one wire protocol compatible interface . this is a dallas semiconductor proprietary interface supported by a large number of devices such as silicon serial numbers , distributed i / o , temperature sensors and serial eerom to mention a few . the implementation of this port is a super set of the dallas &# 39 ; s published protocol and may coexist with other dallas devices . the protel 50a asic currently has a hardware state machine controlled by the phone &# 39 ; s microprocessor which acts as the master dallas controller on the 1 - wire bus . 3 digital i / o in its current configuration three digital i / o lines are available for general purpose use . these lines are controlled by the software . since they are general purpose in nature their use would require program memory to operate out of the downloadable ram . dio2 and dio1 are configured as an outputs and dio3 is configures as an input . when creg1 ( r17 ) bit 4 is high then dio3 controls the pic clock when in this state a high on dio3 rins the cpu at full clock speed ; when dio3 is low it runs at a 61 hz rate conserving power . 8 pic registers eight of the internal registers are reserved for the ppc operation . these registers include such things as indiredt addressing register , program counter , status register and register mapped i / o . for more details on register specifics refer to section 3 . 3 . 0 “ operational registers ”. 11 ppc general registers r8 through r15 and registers r28 - r31 are available to purpose registers the ppc firmware . see section 3 . 4 . 0 general purpose registers ” 12 amx configuration twelve eight - bit configuration registers are supported by the ppc registers design . these registers are used for configuring operating parameters of the amx chip that control the phone audio circuits . see section the ppc is a register based architecture in which the instruction ‘ opcode ’ and ‘ data ’ share the same memory word and are fetched together . most instructions use the ‘ w ’ or working register for data operations however certain data operation such as bit testing and register to register moves may be performed without the use of the working register . each instruction opcode is decoded and directs the appropriate data through and on chip alu to the proper result register . the ppc is comprised of four basic building blocks . the cpu , the alu the register / file block and timer . the cpu logic provides all of the ppc instruction decode and control functions . it is responsible for decoding all signal and providing proper file selection addresses and data . it also provides the proper control and data selection for the ppc alu unit . instructions are not latched , but rather are permitted to ‘ ripple through ’ in a combinatorial manner . this allows for faster speed of operation since it will essentially permit access times of up to one full clock period . the overall approach to the cpu control is to maintain all decode , select and control as combinatorial logic and allow data to ‘ ripple ’ through the alu . then once everything is settled the result of the instruction ( execution ) is latched along with the program counter . the alu is also non sequential , allowing for maximum use of the clock bandwidth . the alu contains both arithmetic as well as logical functions . the alu is also responsible for determining the state of the status flags for each instruction . in non arithmetic / logical functions such as movlw ( move literal . . . ) the alu is used as a data pipeline allowing data to flow through unmodified , but directed to the proper register file input . the register / file ( regs ) block is organized into four types of registered data . the first group is the ‘ operational ’ register files . there are eight of these files : the next group of registers are the general purpose working registers the address space for these are split as follows . the third group of registers are the ‘ read - only ’/‘ write - only ’ registers . these two sets of registers share the same address space but are physically two separate sets of registers ; one for the read - only and the other for the write - only data . they occupy the register / file address space show below : f16 read register 10h f16 write register 10h f17 read register 11h f17 write register 11h f18 read register 12h f18 write register 12h f19 read register 13h f19 write register 13h the fourth group of registers are actually part of the cpu and are non addressable registers with control the program flow , these registers are : 1 program counter 9 bits 4 stack registers 10 bits ( top bit is a ram / ram flag ) 1 stack pointer 2 bits 1 prescale counter 5 bits 1 rtc counter 8 bits the program memory maintains a paged architecture where page 0 is designated as rom program memory and page 1 is designated as ram program memory . for the goto and call instructions the upper address bit ( page selection bit — pc ( 8 )) of the pc is set by the page select bit ( b 5 ) of the status register . pc ( 8 ) for normal program execution assumes its proper incremented value when the pc is simply incremented . ( for example — pc = 0 ffh will over flow to 100 h if a call , goto or interrupt is not encountered at 0 ffh . the lower eight bits of the program counter are determined by the direct setting of the pc by the goto , call instructions or incrementing during normal program execution . the lower 8 bits of the pc may also be affected indirectly by one of two methods : 1 ) direct file operation to register f 2 — if a file operation ( eg . movwf f 2 ) is performed on the program counter register f 2 then the results of that operation are loaded into the lower eight bits of the pc . 2 ) interrupt — if an interrupt occurs the lower 8 bits of the pc are loaded with the value of the register pointed to by bits 4 though 0 of the interrupt control register f 1 . program rom is executed when pc ( 8 )=‘ 0 ’ and program ram is executed when pc ( 8 )=‘ 1 .’ note : this program memory map is significantly different than the pic in that the pic uses all nine bits from the goto to set pc ( 8 : 0 ) and pc ( 8 )=‘ 0 ’ for all call operations . this mapping leaves ‘ memory holes ’ for call operations and is not desirable for our application . this register is not actually implemented but rather signals the cpu that indirect data addressing is to take place . if a file operation is performed with ‘ f 0 ’ as the destination the actual register affected is the register pointed to by bits 4 : 0 of the file selection register ( fsr ). because this register is not physically implemented , an attempt to read to it ( by setting fsr = 0 ) will result in ‘ 00 ’ for data and a write will be the equivalent of a nop instruction where no flags or registers are affected . bits 4 : 0 of this register provide the pointer to the register which contains the lower eight bits of the interrupt vector . bit 5 of this register is the page select bit for the interrupt vector pc ( 8 ), bit 6 contains the interrupt enable status (‘ 1 ’= interrupt enable , ‘ 0 ’ = interrupt disable { default state }). bit 6 is automatically set to ‘ 0 ’ when an interrupt is detected . bit 7 of this register is unused . the program counter register f 2 is actually the bottom eight bits of the pc mapped into the ppc register address space . read operations on f 2 will return pc ( 7 : 0 ). write operations to register f 2 will place the result into the lower eight bits of the pc . the pc register is normally incremented after each instruction is executed , exceptions to this are as follows : branch instructions - pc ( 7 : 0 ) & lt ;= [ pc + 2 ]( 7 : 0 ) & lt ;== page offest pc ( 8 ) & lt ;= [ pc + 2 ]( 8 ) & lt ;== page select btfss btfsc incfsz decfsz direct writes to f2 - pc ( 7 : 0 ) & lt ;= new computed value of f2 pc ( 8 ) & lt ;= pc ( 8 ) ( unaffected ) all byte oriented file register operations with f2 as destination . call instruction - pc ( 7 : 0 ) & lt ;= instr ( 7 : 0 ) pc ( 8 ) & lt ;= status ( 5 ) goto instruction - pc ( 7 : 0 ) & lt ;= instr ( 7 : 0 ) pc ( 8 ) & lt ;= status ( 5 ) retlw - pc ( 8 : 0 ) & lt ;= current stack ( 8 : 0 ) interrupt ( rtc / ext ) pc ( 7 : 0 ) & lt ;= fx ( 7 : 0 ) where ‘ x ’ is register pointed to by bit 4 : 0 of f1 . pc ( 8 ) & lt ;= f1 ( 5 ) preassigned bits of the status register are mapped to current cpu status information . the bit assignment is as follows : status ( 7 ) unused status ( 6 ) interrupt enable flag status ( 5 ) pc ( 8 ) for call and goto instructions status ( 4 ) unused status ( 3 ) unused status ( 2 ) z flag status ( 1 ) dc flag status ( 0 ) c flag status information is pushed into a status holding register when an interrupt occurs . this allows transparent saving of all pre - interrupt status information . this status holding register is not readable . the status register is restored with the value of the status holding register when a retlw instruction is executed at the end of an interrupt routine . the status register is unaffected by a retlw from within a called subroutine . this register may be used to as a pointer to an indirect register address for instructions that designate f 0 as a destination . bits 4 : 0 contain the address of one of the 32 file registers and a file operation with f 0 as a destination will use the register who &# 39 ; s address is fsr ( 4 : 0 ). bits 7 : 5 are unused and may be used for program specific flags . if indirect addressing is not used this register may be used as a general purpose register . fsr is pushed into an fsr holding register when an interrupt occurs . this allows transparent saving of the pre - interrupt fsr value . the fsr holding register is not readable . the fsr register is restored with the value of the fsr holding register when a retlw instruction is executed at the end of an interrupt routine . the fsr register is unaffected by a retlw from within a called subroutine . f 5 porta is a bidirectional tristateable port . all but three of these bits are dedicated for ica0000035 asic specific functions . the mapping is as follows : porta ( 7 ) dallas 1 - wire input porta ( 6 : 4 ) general purpose bidirectional / tristateable i / o porta ( 3 : 0 ) upper program data bits ( 11 : 8 ) for program ram write operations . f 6 portb is a bidirectional tristateable port . all bits are dedicated for ica0000035 asic specific functions . the mapping is as follows : portb ( 7 : 0 ) lower program data bits ( 7 : 0 ) for program ram write operations . if program ram is not used this register may be used as a general purpose internal working register . this may also be done after program ram data has been successfully downloaded into the on chip program ram . f 7 portc is a reserved port which is mapped to the delta sigma d / a converter . the eight bit value loaded into this register is first - order - modulated into a bitstream , which when filtered will produce an analog value proportional to the current value of f 7 portc . the filtered analog value will be determined by equation 1 below : the general purpose registers are read / write registers which can be used for general program data space . the ppc has 16 such registers divided into two address ranges : reg08 through reg15 file addresses 08h through 0fh reg29 through reg31 file addresses 1dh through 1fh the table on the next few pages describe the register mapping of all registers including the registers r 8 through r 31 which are used by the amx circuit for configuration and status reporting . ref0 ( x00h ) d7 .. d0 indirect addressing “ xxxxxxxx ” not a real register reg2 ( x02h ) d7 .. d0 program counter “ 00000000 ” pc ( 7 : 0 ) reg4 ( x04h ) d7 .. d0 file select register “ 00000000 ” indirect addr . register d7 .. d5 unused “ 000 ” d4 .. d0 points to register with “ 00000 ” value for pc ( 7 : 0 ) when f0 is specified as the file register reg5 ( x05 ) d7 .. d0 ( see below ) “ zzzzzzzz ” pic porta d7 txrx output pine ‘ z ’ d6 dio3 / pic clk ctrl when bit4 of r17 is ‘ 1 ’ dio3 = ‘ 1 ’ =& gt ; clk = clk ‘ 0 ’=& gt ; clk = clk / 65536 d5 dio2 general purpose out d4 dio1 general purpose out d3 .. d0 d11 .. d8 for ram used during ram fill reg7 ( x07h ) d7 .. d0 portc “ 10000000 ” modout - dsout - 1pin ref9 ( x09h ) d7 .. d0 general purpose reg . “ xxxxxxxx ” not initialized reg11 ( x0bh ) d7 .. d0 general purpose reg . “ xxxxxxxx ” not initialized reg13 ( x0dh ) d7 .. d0 general purpose reg . “ xxxxxxxx ” not initialized reg15 ( x0fh ) d7 .. d0 general purpose reg . “ xxxxxxxx ” not initialized reg16 ( x10h ) d7 .. d0 real time clock ( rtc ) “ 11111111 ” not initialized d7 .. d0 write puts invert of rtc counts up file data in rtc d7 .. d0 rtc current count read only reg18 ( x12h ) d7 .. d0 preamp control “ 01001001 ” write only data creg2 d7 , d6 tx_mux_sel “ 01 ” ‘ 00 ’ sel xmtr ‘ 01 ’ sel dtmf ‘ 10 ’ sel modem ‘ 11 ’ sel aux d5 .. d3 tx_gain ( 2 : 0 ) ‘ 001 ’ gain = b ( 2 : 0 ) + . 5 d2 .. d0 rcv_gain ‘ 001 ’ gain = b ( 2 : 0 ) + . 5 reg18 ( x12h ) d7 .. d0 a / d compare & amp ; “ xxxxxxx ” ( read only register ) security code sreg2 d7 a / d comparitor out n / a comp input - read only d6 unused d5 .. d0 security code 1 of 64 codes programmed at time of chip bonding r20 ( x14h ) d7 .. d0 xmtr attenuator ctrl “ 00111111 ” creg4 - r / w reg d7 , d6 signal selection ‘ 00 ’ sel ‘ 01 ’ select rcv mod xmtr ‘ 10 ’ select synth ‘ 11 ’ select tone gen d5 .. d0 bitstream attenuation ‘ 111111 ” attn = b ( 5 : 0 )/ 64 r21 ( x15h ) d7 .. d0 xmtr attenuator ctrl “ 00111111 ” creg5 - r / w reg d7 , d6 signal selection ‘ 01 ’ sel ‘ 00 ’ select xmtr mod rcv mod ‘ 10 ’ select synth ‘ 11 ’ select tone gen d5 .. d0 bitstream attenuation ‘ 111111 ” attn = b ( 5 : 0 )/ 64 r22 ( x16h ) d7 .. d0 delay register “ 00000001 ” creg6 , r . w register delay = b ( 7 : 0 ) us r24 ( x18h ) d7 .. d0 tone 0 ampl . control not set creg8 , r / w register ampl = b ( 7 : 0 )/ 256 r26 ( x2ah ) d7 .. d0 tone0 freq control not set crega , r / w register freq = 895khz 25 . 13 ·( n + 1 ) r28 ( x2ch ) d7 .. d0 a / d sig sel & amp ; pic lim not set cregc , r / w register d7 .. d3 unused d2 pic lim circuit not set d1 : d0 signal selection not set ‘ 00 ’ select ain0 ‘ 01 ’ select ain1 ‘ 10 ’ select ain2 ‘ 11 ’ select ain3 r30 ( x2eh ) d7 .. d0 general purpose reg not set crege , r / w register the ‘ w ’ register in the ppc acts an accumulator and holds the second operand in two operand operations . in file register operations the w register may be specified as the destination rather than the file itself . this allows a file operation result to be used as a second operand in the following instruction and allows the original file value to remain unmodified . the w register is pushed onto a temporary holding register after an interrupt and will be restored automatically when a retlw instruction is executed at the end of an interrupt routine . the w register is also used as the program ram address during program ram write operations . note : this means that the value of w specified in the retlw instruction , when issued at the end of an interrupt routine , will be ignored . two register not in the register map are provided which control the tristate state of ports a and b . both of these registers are eight bit with each bit corresponding to the tristate control line on the respective port bit . a bit value of logic 1 will tristate the appropriate port bit and allow that port bit to be used as an input . porta bits 3 : 0 and portb bits 7 : 0 must be configured as outputs when modifying program ram . a two bit stack pointer register is provided to keep track of the current stack level . the stack level is incremented each time an interrupt occurs or a call instruction is executed . the stack pointer register is decremented each time a retlw instruction is executed . a stack pointer value of “ 00 ” indicates that program execution is in the main program code and not in any called subroutines or interrupt service routines . the max level of the stack is 3 this allows interrupts to be enabled in subroutines and still be able to call a subroutine from within an interrupt service routine . the stack registers are ten bit registers , the lower nine bits store the current value of the pc + 1 ( which is a 9 bit value ). the upper bit of each stack registers stores a flag which indicates whether the program branch was caused by a call instruction or an interrupt . if the program branch was initiated by a call instruction then the 10th bit statusx ( 9 ) of stackx is cleared . if the program branch was initiated by an interrupt ( external or timer ) then the statusx ( 9 ) bit is set . this flag bit ( when set ) is used when a retlw is executed to signal the control circuits to restore the fsr , status and w registers to their pre - interrupt values . if the flag bit is cleared when a retlw is executed the w value specified in the retlw operand is loaded into w and the status and fsr registers are left unchanged . the prescale counter register is a 5 bit divide by 18 counter . it is preset by mrstn or an overflow of the prescale counter . setting the rtc_en bit ( b 3 of f 17 ) will also preset the prescale register to its initial value . the overflow of the prescale register is used as a timer tic for the main rtc counter . using a color burst crystal of 3 . 579 mhz produces a tic time of approximately 5 us . note : the prescale register is not settable ( other than resetting it with rtc_en ) and it is not readable . the realtime counter is an eight bit counter initialized to 00 h upon power - up and once enabled it will produce wrap around every 256 tic times . thus for a 3 . 579 mhz clock the max timer over flow time will be 1 . 28 ms . if interrupts are enabled an interrupt will occur each time the rtc counter overflows . the current value of this register may be read by reading the read only port from file register f 16 . the rtc may be set to produce shorter roll over times simply by writing to the write only rtc register , at file register write address space f 16 . the number of prescale tics to produce an overflow is given by n + 1 where n is the value loaded into the write only rtc register . once a value is written to file register f 16 the rtc register may be loaded in one of three ways . first if rtc is already enabled loading a new count value into f 16 will not take effect until the current value in the rtc has completed timing out . thus if the lat value in rtc was set to 1 ms and the new value is set to 0 . 5 ms the rtc will complete the 1 ms time out before setting itself for the new 0 . 5 ms value . secondly , if the rtc is already enabled and it is desired that the new value take effect immediately ( next prescale tic ) then a clrwdt instruction may be issued and the new value will start timing immediately . finally , if rtc is not enabled and a new timer value is loaded by writing f 16 the new time will start timing on the next rising clock edge of the system clock . enabling the rtc also reinitializes the prescale counter register . file register f 17 , address 11h , provides control and status information for the rtc and irq circuits . this address actually contains two separate 4 bit registers . one is read only which provides status information , the other is write only which provides control information for the rtc and irq circuits . if this read only register ( f 17 ) is accessed , two bits of information are provided as shown by the port map below : f17 ( 3 ) ‘ 0 ’ f17 ( 2 ) ‘ 0 ’ f17 ( 1 ) ext_irq flag (‘ 1 ’ = external interrupt has occurred ) f17 ( 0 ) rtc_irq flag (‘ 1 ’ = rtc overflow has occurred ) note : reading this port will clear both flags . ( see interrupt operation for further details ) if the write only register ( f 17 ) is modified , then action is taken according to the bit map show below : f17 ( 3 ) rtc_en (‘ 1 ’ enables rtc and starts timer ) f17 ( 2 ) irq_ext_edg (‘ 0 ’ sets irq to occur on falling edge ) f17 ( 1 ) irq_ext_en (‘ 1 ’ enables external interrupts f17 ( 0 ) irq_rtc_en (‘ 1 ’ enable rtc to interrupt cpu upon overflow ), all bits in both the registers are initialized to ‘ 0 ’ on power - up ( mrstn =‘ 0 ’). two methods of interrupting the ppc are provided , external - edge - triggered and real time counter overflow . both of these signals share the same internal interrupt . if both are enabled then if either signal occurs the cpu is interrupted and vectored to a predetermined interrupt handling routine . a register is provided which can be read to find out which interrupt occurred . either or both of the interrupts may be disabled . the cpu has a separate master irq enable which will globally disable or enable irq activity . this is controlled by bit 6 of the interrupt control register f 01 ( 01h ). if this bit is set , interrupts are enabled , if it is cleared interrupts are disabled . each time an interrupt occurs the cpu automatically disables interrupts by clearing this bit ; this prevents additional interrupts from occurring until the present one has been properly handled . the user must re - enable interrupts by setting this bit before any other interrupts can occur . the user must also read the rtc / irq status register f 17 ( 11h ) before reenabling the cpu interrupt or another interrupt will occur . when an interrupt occurs the current instruction is executed and the next instruction will be an internally generated irq instruction . this internally generated irq instruction takes one clock cycle just like all other ppc instructions . the following actions occur as part of the irq instruction : 1 ) no status flags are affected . 2 ) the current status , w and fsr registers are pushed onto temporary holding registers and are restored when a retlw is issued at the end of an interrupt handling service routine . 3 ) the stack level pointer is incremented by one . 4 ) the current pc value + 1 is placed in the proper stack register . the interrupt flag bit of this stack register is set ( stackn ( 9 )=‘ 1 ’) to indicate to the retlw instruction that the return is from an interrupt and not a call . 5 ) pc ( 7 : 0 ) is loaded with the value of the register pointed to by bits 4 : 0 of the interrupt control register f 01 ( 01h ) and the rom / ram selection bit pc ( 8 ) is set to the value specified by bit 5 of the interrupt control register f 01 ( 01h ). 6 ) the cpu interrupt enable bit , bit 6 of the interrupt control register f 01 ( 01h ), is cleared . prior to returning from an irq service routine the following must be done to allow further interrupts to occur : 1 ) read irq status word f 17 ( 11h ); this will clear both irq flags . if this is not done another interrupt will occur as soon as interrupts are re - enabled . 2 ) re - enable the cpu interrupt by setting bit 6 of the interrupt control register f 01 ( 01h ). after an interrupt has been serviced a retlw is issued and the following actions are taken as part of the retlw execution : 1 ) the current status , w and fsr registers are restored to their pre - interrupt values . 2 ) the current pc ( 8 : 0 ) is loaded with stackn ( 8 : 0 ). 3 ) the stack level pointer is decremented by one . 4 ) program execution continues from where it left off prior to the interrupt . the cpu interrupt is asserted whenever either the rtc or ext interrupt occurs . the rtc interrupt occurs when the rtc times out from its preset value . the ext interrupt occurs when a signal on pin irq of the ica0000035 asic transitions . this can be configured to occur on the rising or falling edge of the irq input pin . this is accomplished by writing bit 2 of the rtc / irq control register ( f 17 { 11h }); a ‘ 1 ’ in this bit position configures the circuit for rising edge trigger and a ‘ 0 ’ configures it for falling edge . the enables for the rtc and external interrupts are controlled separately by writing to the rtc / irq control register ( f 17 { 11h }). setting bit 0 of this register enables the rtc interrupt and setting bit 1 enables the external interrupt . the rtc may be separately enabled and disabled independent of the state of the rtc_irq enable . this is accomplished by writing bit 3 of the rtc / irq control register ( f 17 { 11h }). disabling the rtc and re - enabling will cause the rtc to be reloaded with the preset value stored in file register f 16 . this architecture would thus allow a software watch dog timer to operate simply by having the main program disable and re - enable the rtc at a rate faster than that which is set into the rtc register . ( conditions dvdd =+ 2 . 7 to + 5 . 5 volts ; avdd = 4 . 5 to 5 . 5 volts ; avss = dvss = 0 . 0 volts ; t a = min to t max ; parameter notes symbol min typ max units analog character - istics accuracy gain error 1 error gain − 10 ± 2 + 10 % gain drift − 50 ± 10 + 50 ppm /° c . offset error v offset − 15 ± 5 + 15 mv offset drift − 50 ± 10 + 50 μv /° c . output noise 2 1 μv √ hz − 1 / 2 i dd analog 3 — 1 . 5 2 ma notes : 1 even though this specification specifies all gains in db the error specification is absolute . specifically it is the expected gain minus the actual gain expressed as a percentage of the expected gain . 2 output noise is expressed as noise density ( rms ) as should be at 100 hz or below . 3 i dd analog measured with a vdd = 5 . 5 volts dc . note that specified current is over temperature . ( conditions dvdd =+ 2 . 7 to + 5 . 5 volts ; avdd = 4 . 5 to 5 . 5 volts ; avss = dvss = 0 . 0 volts ; t a = min to t max ; c load = 50 pf , unless otherwise noted ) parameter notes symbol min typ max units digital characteristics digital inputs input low voltage 1 v il 0 . 3 0 . 5 0 . 4 vdd threshold input high voltage 1 v ih 0 . 6 0 . 5 0 . 7 vdd threshold input current 2 i il & amp ; h — ± 1 ± 10 μa input capacitance c in — ± 5 ± 10 pf i dd digital 3 — 100 200 μa notes : 1 input threshold levels are expressed as a multiple of dvdd to account for the wide range of allowable supply voltage . 2 these current levels are for valid input levels only . 3 i dd digital measured with d vdd = 5 . 5 volts dc . note that specified current is over temperature . current measurement is made with input clock frequency = 500 khz . it will be understood by those skilled in the art that various modifications and changes may be made in the design of the integrated circuit configurations and methods described above without departing from the spirit and scope of the present invention . for example , a number of register map and pic microcode configurations will be generally known to those skilled in the art . however , specific formats are disclosed in appendix a and d , respectively , in the above - identified provisional application , which are incorporated herein by reference . further , to the extent that the skilled artisan is interested in determining differences between the particular pic configuration of the present invention with other commercially available designs , such information may be found at appendix b to the above - identified provisional patent application ; likewise , appendix c of the provisional application contains a description of a one - wire protocol . both appendix b and c are also incorporated herein by reference . there is of course significant additional information which will be readily available to those skilled in the art in practicing these inventions , which is not incorporated herein for purposes of brevity . | 7 |
the compounds of formulae i and ii are prepared according to procedures described in belgian pat . no . 854 , 655 . a suitable process begins with appropriately substituted anilines , e . g ., 3 - hydroxy - 5 -( z - w - substituted ) anilines , ( iii ) or derivatives thereof in which the 3 - hydroxy group is protected by a group ( y 1 ) easily removable to regenerate the hydroxy group ; e . g . methyl , ethyl , benzyl , substituted benzyl wherein the substituent is , for example , alkyl having from 1 to 4 carbon atoms , halo ( cl , br , f , i ), and alkoxy having from one to four carbon atoms . when z is --( alk 1 ) m -- x --( alk 2 ) n --, y 1 is preferably benzyl or a substituted benzyl group since it can subsequently be removed without detriment to the z group . the protected aniline derivative ( iii ) is then converted to a compound of formula iv by known technology as described below . an abbreviated reaction sequence ( flow sheet a ) for preparing representative compounds of formula via - c beginning with a 3 -( protected hydroxy )- 5 -( z - w - substituted ) aniline ( iii ) wherein -- z -- w is och 3 is given below . ## str8 ## r ° in the above flow sheet represents alkyl having from one to six carbon atoms . ( r 5 , for the purpose of illustration in the overall flow sheet , is represented as hydrogen . however , in the sequence iii → iv or iii → vi - b , r 5 can be hydrogen , methyl or ethyl .) the 5 - substituent of formula iii compounds can be group -- z -- w desired in compounds of formulae ii or i , or a group readily convertible to said group . when the z moiety of group -- z -- w is --( alk 1 ) m -- x --( alk 2 ) n -- wherein x is o or s and each of m and n is 0 , the 5 - substituent , when w is hydrogen , is -- xh ( i . e ., oh or sh ) or a protected -- xh group of the formula -- x -- y 1 wherein y 1 is as defined above . when , of course , -- z -- w is --( alk 1 ) m -- x --( alk 2 ) n -- w wherein m is 1 , n is 0 and w is hydrogen , the 5 - substituent becomes --( alk 1 ) m -- x -- h . the -- xh group is advantageously protected in the manner described below . the appropriate 3 -( protected hydroxy )- 5 - substituted anilines are reacted with an alkyl β - ketoester in the presence of acetic acid in a reaction - inert solvent such as benzene or toluene at temperatures of from about 50 ° c . to the reflux temperature of the solvent under conditions which result in removal of by - product water to provide the corresponding β -[( 3 - protected hydroxy )- 5 - substituted anilino ]- β -( r 4 )- acrylate ( iv ). the alkyl β - anilino - β -( r 4 )- acrylate ( iv ) is then reduced to the corresponding alkyl - 3 -[( 3 - protected hydroxy )- 5 - substituted anilino ]- 3 -( r 4 )- propionate ( v ) by , for example , sodium borohydride - acetic acid or catalytic hydrogenation ( heterogeneous or homogeneous ). of course , when the protecting group or groups are benzyl or substituted benzyl , catalytic hydrogenation will result in their removal . for this reason , methyl or ethyl groups are preferred as protecting groups for the 3 - and / or 5 - hydroxy groups of formula iii reactants . alternatively , compounds of formula v can be prepared directly from compounds of formula iii by reaction of formula iii compounds with an alkyl 3 , 3 - r 4 r 5 - acrylate in acetic acid at temperatures ranging from 0 ° c . to the reflux temperature . alternatively , compounds of formula vi - b can be prepared directly by condensation of equimolar quantities of iii with the appropriate substituted acrylic acid ( r 4 r 5 c ═ ch -- cooh ) in pyridine hydrochloride at 150 °- 200 ° c . in addition , when the r 4 , r 5 groups are both alkyl , treatment of iii and the alkyl r 4 , r 5 acrylate in a reaction - inert solvent , e . g . tetrahydrofuran , with mercuric acetate followed by reduction with sodium borohydride gives v . direct conversion of compounds of formula iii to compounds of formula v is also conveniently achieved by treating a 3 , 5 -( diprotected hydroxy ) aniline hydrochloride with an excess of an alkyl acetoacetate , e . g . ethyl acetoacetate , in the presence of sodium cyanoborohydride in a solvent such as methanol . the alkyl 3 - anilino - 3 -( r 4 )- propionate ( v ) is then cyclized to the corresponding 2 -( r 4 )- quinolin - 4 - one ( formula vi - a or - b ) by means of a suitable cyclizing agent such as polyphosphoric acid ( ppa ), hydrogen bromide - acetic acid , sulfuric acid , and others known to those skilled in the art . the ether protecting , or blocking , groups on the 3 -( and 5 -) hydroxy groups can be removed at the time of cyclization through the use of 48 % hydrobromic acid in acetic acid as cyclizing agent and deblocking agent . however , when z is --( alk 1 ) m -- x --( alk 2 ) n -- cyclization agents such as polyphosphoric acid or trifluoroacetic acid must be used to avoid cleavage of the ether or thioether linkage . alternatively , the protecting group ( or groups ) can be removed subsequent to the cyclization reaction . when the protecting groups are benzyl or substituted benzyl groups , they can be removed by catalytic hydrogenolysis using palladium or platinum supported on carbon or by solvolysis using trifluoroacetic acid . of course , when group -- z -- w contains sulfur , acid debenzylation rather than catalytic debenzylation is used . group r 6 , if not already present in compounds of formula vi - a - c , can be introduced into said compounds by reaction with the appropriate cl - r 6 or br - r 6 reactant according to known procedures . of course , when an acyl , e . g . acetyl , group r 6 is desired in products of formulae i or ii , such groups are generally introduced at that point in the reaction sequence ( flow sheet b ) following formation of formula ii compounds wherein r 6 is hydrogen , e . g ., by acylation with the appropriate acyl halide according to known procedures . compounds of formula vi and , of course , of formula vi - a - c , are converted by the following illustrative sequence ( flow sheet b ) to representative compounds of formulae ii and i ( r 5 and r 6 = h in the illustration ). ## str9 ## the quinolines of formula vi are converted to hydroxymethylene derivatives of formula vii by reaction with ethyl formate and sodium hydride . the bis - formylated derivative thus produced is treated with methyl vinyl ketone to give a mixture of the corresponding mono - n - formylated michael adduct ( viii ) and 1 , 3 - bis - formylated michael adduct . the two products are conveniently separated by column chromatography on silica gel . aldol condensation of the mono - n - formyl compound of formula viii affords the enone ix . the enone ( ix ) is converted by birch reduction to a compound of formula ii . the birch reduction is favored because it offers stereoselectivity resulting in formation of the desired trans - ketone of formula ii as the major product . the hydroxy ketones of formula ii ( compounds wherein r 1 is hydrogen ) and the dihydroxy compounds of formula i ( r = or 1 = oh ) appear to be rather unstable to oxidation as evidenced by formation of purple to red colors upon standing . they can be stabilized by acylation , particularly acetylation , of the 1 - hydroxyl group ( or 1 ) with acetic anhydride in pyridine , and by formation of acid addition salts , e . g ., hydrochlorides . chemical ( sodium borohydride ) reduction of the 9 - oxo group of compounds of formula ii , and preferably , for reasons of stability mentioned above , of the acetylated derivative of formula ii , via metal hydride reduction affords compounds of formula i wherein the hydroxyl group at the 1 - position is present as its acetylated derivative . alternately , and more desirably , compounds of formula ix , especially those wherein the 1 - hydroxy group is protected as an ester or benzyl ether , are converted to compounds of formula i by catalytic ( pd / c ) hydrogenation . the acetylated derivatives of formula i thus produced are converted to the corresponding hydroxy derivatives by cleavage of the acetyl group by standard methods . esters of compounds of formula ii wherein r 1 is alkanoyl or -- co --( ch 2 ) p -- nr 2 r 3 are readily prepared by reacting formula ii compounds with the appropriate alkanoic acid or acid of formula hooc --( ch 2 ) p -- nr 2 r 3 in the presence of a condensing agent such as dicyclohexylcarbodiimide . alternatively , they are prepared by reaction of a formula ii compound with the appropriate alkanoic acid chloride or anhydride , e . g ., acetyl chloride or acetic anhydride , in the presence of a base such as pyridine . esters of formula i compounds in which each of the r and r 1 groups is esterified are prepared by acylation according to the above - described procedures . compounds in which only the 9 - hydroxy group is acylated are obtained by mild hydrolysis of the corresponding 1 , 9 - diacyl derivative , advantage being taken of the greater ease of hydrolysis of the phenolic acyl group . formula i compounds in which only the 1 - hydroxy groups is esterified are obtained by borohydride reduction of the corresponding formula ii ketone esterified at the 1 - position . the thus - produced formula i compounds bearing 1 - acyl - 9 - hydroxy substitution or 1 - hydroxy - 9 - acyl substitution can then be acylated further with a different acylating agent to produce a diesterified compound of formula i in which the ester groups at the 1 - and the 9 - positions are different . the presence of a basic group in the ester moiety ( or 1 ) in the compounds of this invention permits formation of acid - addition salts involving said basic group . when the herein described basic esters are prepared via condensation of the appropriate amino acid hydrochloride ( or other acid addition salt ) with the appropriate compound of formula i - ii in the presence of a condensing agent , the hydrochloride salt of the basic ester is produced . careful neutralization affords the free base . the free base form can then be converted to other acid addition salts by known procedures . acid addition salts can , of course , as those skilled in the art will recognize , be formed with the nitrogen of the benzo [ c ] quinoline system . such salts are prepared by standard procedures . the basic ester derivatives are , of course , able to form mono - or di - acid addition salts because of their dibasic functionality . the antiemetic properties of the compounds of formulae i and ii are determined in unanesthetized unrestrained cats according to the procedure described in proc . soc . exptl . biol . and med ., 160 , 437 - 440 ( 1979 ). the compounds of the present invention are active antiemetics via oral and parenteral administration and are conveniently administered in composition form . such compositions include a pharmaceutical carrier selected on the basis of the chosen route of administration and standard pharmaceutical practice . for example , they may be administered in the form of tablets , pills , powders or granules containing such excipients as starch , milk sugar , certain types of clay , etc . they may be administered in capsules , in admixtures with the same or equivalent excipients . they may also be administered in the form of oral suspensions , dispersions , solutions , emulsions , syrups and elixirs which may contain flavoring and coloring agents . for oral administration of the therapeutic agents of this invention , tablets or capsules containing from about 0 . 01 to about 100 mg . are suitable for most applications . the physician will determine the dosage which will be most suitable for an individual patient and it will vary with the age , weight and response of the particular patient and the route of administration . generally , however , the initial antiemetic dose of drug is administered in an amount effective to prevent nausea . such dosage in adults may range from 0 . 01 to 500 mg . per day in single or divided doses . in many instances , it is not necessary to exceed 100 mg . daily . the favored oral dosage range is from about 0 . 01 to about 300 mg ./ day ; the preferred range is from about 0 . 10 to about 50 mg ./ day . the favored parenteral dose is from about 0 . 01 to about 100 mg ./ day ; the preferred range from about 0 . 01 to about 20 mg ./ day . the compounds ( drugs ) described herein can be formulated for administration in solid or liquid form for oral or parenteral administration . capsules containing compounds of formulae i or ii are prepared by mixing one part by weight of drug with nine parts of excipient such as starch or milk sugar and then loading the mixture also telescoping gelatin capsules such that each capsule contains 100 parts of the mixture . tablets are prepared by compounding suitable mixtures of drug and standard ingredients used in preparing tablets , such as starch , binders and lubricants , such that each tablet contains from 0 . 01 to 100 mg . of drug per tablet . suspensions and solutions of these drugs , particularly those wherein r 1 ( formulae i and ii ) is hydroxy , are generally prepared just prior to use in order to avoid problems of stability of the drug ( e . g . oxidation ) or of suspensions or solution ( e . g . precipitation ) of the drug upon storage . compositions suitable for such are generally dry solid compositions which are reconstituted for injectable administration . the examples presented below illustrate the preparation of preferred compounds useful in the process of this invention . they are representative of procedures which can be used to synthesize compounds of formulae i and ii described herein . a mixture of 3 , 5 - dimethoxyaniline ( 4 . 6 g ., 0 . 03 mole ), crotonic acid ( 2 . 54 g ., 0 . 03 mole ) and pyridine hydrochloride ( 3 . 0 g ., 1 . 26 moles ) is heated at 185 °- 200 ° c . for 45 minutes . the cooled reaction mixture is suspended in water ( 500 ml .) ( ph ˜ 3 ) and the ph adjusted to 7 and the resultant mixture stirred for 10 minutes . the organic layer is separated , dried ( mgso 4 ) and concentrated to 3 . 2 g . of a yellow oil . a mixture of glacial acetic acid ( 110 ml . ), 48 % hydrobromic acid ( 110 ml .) and the yellow oil is refluxed for one hour and is then concentrated in vacuo to a dark oil . the oil is dissolved in water and the aqueous solution neutralized to ph 6 - 7 with 1 n sodium hydroxide . a saturated solution of salt water is added and the resulting mixture extracted with ethyl acetate . the extracts are combined , dried ( mgso 4 ) and concentrated under reduced pressure to a dark oil ( 2 . 8 g .). column chromatography of the crude residue on silica gel using benzene - ether ( 4 : 1 ) as eluant gives an additional 510 mg . of product , m . p . 168 °- 170 ° c . further purification is achieved by recrystallizing the product from ethyl acetate ; m . p . 173 °- 174 ° c . analysis : calc &# 39 ; d for c 10 h 11 o 3 n : c , 62 . 16 ; h , 5 . 74 ; n , 7 . 25 %; found : c , 62 . 00 ; h , 5 . 83 ; n , 7 . 14 %. a mixture of 5 - phenyl - 2 -( r , s )- pentanol ( 16 . 4 g ., 100 mmole ), triethylamine ( 28 ml ., 200 mmole ) and dry tetrahydrofuran ( 80 ml .) under a nitrogen atmosphere is cooled in an ice / water bath . methanesulfonyl chloride ( 8 . 5 ml ., 110 mm ) in dry tetrahydrofuran ( 20 ml .) is added dropwise at such a rate that the temperature holds essentially constant . the mixture is allowed to warm to room temperature and is then filtered to remove triethylamine hydrochloride . the filter cake is washed with dry tetrahydrofuran and the combined wash and filtrate evaporated under reduced pressure to give the product as an oil . the oil is dissolved in chloroform ( 100 ml .) and the solution washed with water ( 2 × 100 ml .) and then with saturated brine ( 1 × 20 ml .). evaporation of the solvent affords 21 . 7 g . ( 89 . 7 %) yield of the mesylate of d , l - 5 - phenyl - 2 - pentanol which is used in the next step without further purification . a mixture of d , l - 5 , 7 - dihydroxy - 2 - methyl - 4 - oxo - 1 , 2 , 3 , 4 - tetrahydroquinoline ( 114 . 8 g ., 0 . 594 mole ), potassium carbonate ( 174 . 8 g ., 1 . 265 moles ), n , n - dimethylformamide ( 612 ml .) and d , l - 5 - phenyl - 2 - pentanol mesylate ( 165 . 5 g ., 0 . 638 mmole ), under a nitrogen atmosphere , is heated to 80 °- 82 ° c . in an oil bath for 1 . 75 hours . the mixture is cooled to room temperature and then poured into ice / water ( 4 liters ). the aqueous solution is extracted with ethyl acetate ( 2 × 4 liters ) and the combined extracts washed successively with water ( 4 × 2 liters ) and saturated brine ( 1 × 2 liters ). the extract is then dried ( mgso 4 ), and evaporated to give the product ( 196 g .). it is used without further purification . 1 h nmr ( 60 mhz ) β cdcl . sbsb . 3 tms ( ppm ): 12 . 73 ( s , 1h , oh ), 7 . 22 ( s , 5h , aromatic ), 5 . 80 ( d , j = 3 h 3 , 1h , meta h ), 5 . 58 ( d , j = 3 h 3 , 1h , meta h ), 1 . 25 ( d , 6h , ch 3 -- ch -- n and ch 3 -- ch -- o --), 1 . 41 - 4 . 81 ( m , 11h , remaining protons ). a solution of d , l - 5 - hydroxy - 2 - methyl - 7 -( 5 - phenyl - 2 - pentyloxy )- 4 - oxo - 1 , 2 , 3 , 4 - tetrahydroquinoline ( 195 g ., ca . 0 . 58 mole ) in ethyl formate ( 1140 g ., 14 . 6 moles ) is added dropwise to sodium hydride ( 72 g ., 3 . 0 moles , obtained by washing 144 g . of 50 % sodium hydride with hexane , 3 × 500 ml . ), with good stirring . after about 1 . 5 hours when 2 / 3 of the ethyl formate solution is added , the addition is discontinued to allow the vigorous foaming to subside . diethyl ether ( 600 ml .) is added and the mixture stirred for 15 minutes before adding the remainder of the ethyl formate solution . when addition is complete , diethyl ether ( 600 ml .) is added , the reaction mixture stirred for an additional 10 minutes and then poured onto ice water ( 2 liters ). it is acidified to ph 1 with 10 % hcl and the phase separated and extracted with ethyl acetate ( 2 × 2 liters ), brine ( 1 × one liter ) and dried ( mgso 4 ). concentration gives 231 g . of red - brown oil which is used without further purification . r f = 0 . 1 - 0 . 5 ( stretched ) on thin layer chromatography , silica gel plates , benzene / ether ( 1 : 1 ). to a solution of d , l - 1 - formyl - 3 - hydroxymethylene - 5 - hydroxy - 2 - methyl - 7 -( 5 - phenyl - 2 - pentyloxy )- 4 - oxo - 1 , 2 , 3 , 4 - tetrahydroquinoline ( 229 g ., ca . 0 . 58 mole ) in methanol ( 880 ml .) under a nitrogen atmosphere is added triethylamine ( 27 . 2 ml .) with stirring . methyl vinyl ketone ( 97 . 0 ml .) is then added and the mixture stirred overnight at room temperature . the reaction is complete at this point and comprises a mixture of the title compound and d , l - 1 , 3 - diformyl - 5 - hydroxy - 2 - methyl - 7 -( 5 - phenyl - 2 - pentyloxy )- 4 - oxo - 3 -( 3 - oxobutyl )- 1 , 2 , 3 , 4 - tetrahydroquinoline . the following steps are required to convert the diformyl compound to the desired title compound . the reaction mixture is diluted with ether ( 6 liters ) and then washed successively with 10 % aqueous sodium carbonate ( 4 × 1700 ml . ), brine ( 1 × 2 liters ) and then dried ( mgso 4 ). concentration of the solution affords 238 g . of a red - brown oil . the oil is dissolved in methanol ( 1920 ml .) and the solution cooled to 0 ° c . potassium carbonate ( 21 . 2 g .) is added , the mixture stirred for 3 hours at 0 ° c . and then treated with acetic acid ( 18 . 7 g .). the methanol is removed under reduced pressure and the resultant oil stirred with water ( 2 liters ) and ethyl acetate ( 2 liters ) for 10 minutes . the aqueous phase is separated , extracted with ethyl acetate ( 1 × 2 liters ) and the combined ethyl acetate solutions washed with water ( 2 × 2 liters ), brine ( 1 × 2 liters ) and dried ( mgso 4 ). concentration under reduced pressure and chromatography of the concentrate on silica gel ( 1 . 8 kg .) gives 159 g . of the title product . 1 h nmr ( 60 mhz ) δ cdcl . sbsb . 3 tms ( ppm ): 12 . 7 ( s , 1h , oh ), 8 . 78 ( bs , 1h , -- cho ), 7 . 22 ( s , 5h , aromatic ), 6 . 22 ( bs , 2h , meta h &# 39 ; s ), 2 . 12 , 2 . 07 ( s , 3h , -- ch 3 -- co --), 1 . 31 ( d , 3h , -- ch 3 -- c -- o --), and 1 . 57 - 5 . 23 ( m , 13h , remaining protons ). similar treatment of 35 g . ( 0 . 09 mole ) of dl - 1 - formyl - 5 - hydroxy - 3 - hydroxymethylene - 2 - methyl - 7 -( 4 - phenylbutyloxy )- 4 - oxo - 1 , 2 , 3 , 4 - tetrahydroquinoline gives 22 . 7 g . ( 60 %) of dl - 1 - formyl - 5 - hydroxy - 2 - methyl - 7 -( 4 - phenylbutyloxy )- 4 - oxo - 3 -( 3 - oxobutyl )- 1 , 2 , 3 , 4 - tetrahydroquinoline , m . p . 101 °- 103 ° c . the analytical sample is obtained by recrystallization from methanol , m . p . 104 °- 105 ° c . calc &# 39 ; d . for c 25 h 29 o 5 n : c , 70 . 90 ; h , 6 . 90 ; n , 3 . 31 %; found : c , 70 . 77 ; h , 6 . 81 ; n , 3 . 46 %. 1 h nmr ( 60 mhz ) δ cdcl . sbsb . 3 tms ( ppm ): 12 . 88 ( s , 1h , -- oh ), 9 . 08 ( bs , 1h , -- cho ), 7 . 29 ( s , 5h , c 6 h 5 ), 6 . 25 ( bs , 2h , meta h &# 39 ; s ), 4 . 88 - 5 . 43 ( m , 1h , -- chn ), 3 . 86 - 4 . 21 ( m , 2h , -- ch 2 -- o --), ca . 2 . 49 - 3 . 02 [ m , 7h , arch 2 , --( ch 2 ) 2 -- c (═ o )--, -- ch -- c (═ o )], 2 . 18 [ s , 3h , ch 3 -- c (═ o )], 1 . 68 - 2 . 03 [ m , 4h , --( ch 2 ) 2 --], 1 . 13 ( d , 3h , ch 3 ). m / e - 423 ( m + ). a solution of d , l - 1 - formyl - 5 - hydroxy - 2 - methyl - 7 -( 5 - phenyl - 2 - pentyloxy )- 4 - oxo - 3 -( 3 - oxobutyl )- 1 , 2 , 3 , 4 - tetrahydroquinoline ( 174 g ., 0 . 398 mole ) in methanolic 2 n koh ( 5 . 9 liters ) and methanol ( 5 . 9 liters ) is stirred and heated at reflux overnight under a nitrogen atmosphere . to the cooled solution is added acetic acid ( 708 g .) dropwise with stirring over a 15 minute period . the resulting solution is concentrated by rotary evaporation ( in vacuo , water aspirator ) to a semisolid which is filtered and washed first with water to remove potassium acetate and then with ethyl acetate until all the black tar is removed . yield = 68 g . ( 44 %) yellow solids , m . p . 188 °- 190 ° c . recrystallization from hot ethyl acetate affords the pure product , m . p . 194 °- 195 ° c . analysis : calc &# 39 ; d . for c 25 h 29 o 3 n : c , 76 . 09 ; h , 7 . 47 ; n , 3 . 58 %; found : c , 76 . 43 ; h , 7 . 48 ; n , 3 . 58 %. 1 h nmr ( 60 mhz ) δ tms ( 100 mg . dissolved in 0 . 3 ml . cd 3 od and 0 . 3 ml . cd 3 s ( o ) cd 3 ) ( ppm ): 7 . 21 ( s , 5h , aromatic ), 5 . 80 ( s , 2h , meta h &# 39 ; s ), 1 . 20 ( d , 6h , ch 3 -- cho and ch 3 -- ch -- n ). from the mother liquors , a small amount of the corresponding axial methyl derivative is obtained upon evaporation . it is purified by column chromatography on silica gel using benzene / ether ( 1 : 1 ) as eluant . evaporation of the eluate and recrystallization of the residue from ether / hexane ( 1 : 1 ) affords analytically pure material , m . p . 225 °- 228 ° c . its r f value upon thin layer chromatography on silica gel using 2 . 5 % methanol in ether as eluant and visualization with fast blue is 0 . 34 . the 6β - methyl derivative exhibits r f = 0 . 41 . 1 h nmr ( 60 mhz ) δ tms ( 100 mg . dissolved in 0 . 3 ml . cd 3 od and 0 . 3 ml . cd 3 s ( o ) cd 3 ) ( ppm ): 7 . 19 ( s , 5h , aromatic ), 5 . 75 ( s , 2h , meta h &# 39 ; s ), 1 . 21 ( d , 3h , ch 3 -- cho --), and 0 . 95 ( d , 3h , ch 3 -- ch -- n ). ammonia ( 1150 ml .) is condensed directly into a flame - dried 3 liter / 3 neck flask ( under a nitrogen atmosphere ) equipped with mechanical stirrer , a 500 ml . dropping funnel and solid co 2 / acetone cooling (˜- 75 ° c .). lithium wire ( 2 . 2 g ., cut into 1 / 4 &# 34 ; pieces ) is added and a characteristic blue color forms immediately . to the stirred blue solution at - 78 ° c . is added d , l - 5 , 6 , 6a , 7 - tetrahydro - 1 - hydroxy - 6β - methyl - 3 -( 5 - phenyl - 2 - pentyloxy ) benzo [ c ] quinolin - 9 ( 8h )- one ( 21 . 5 g ., 0 . 055 mole ) dissolved in tetrahydrofuran ( 250 ml .) dropwise over a 10 minute period . after an additional 5 minutes of stirring at - 78 ° c ., the reaction mixture is quenched by the addition of dry ammonium chloride ( 20 g .). the cooling is then discontinued and the reaction mixture warmed slowly on a steam bath to evaporate the ammonia . when almost dry , ethyl acetate ( 2 liters ) and water ( 1 liter ) are added and the mixture stirred for 10 minutes . the layers are then separated and the aqueous phase is extracted once more with ethyl acetate ( 500 ml .). the combined organic extracts are washed once with water ( 1 liter ), dried ( mgso 4 ) and concentrated to a brown semi - solid (˜ 28 g .). this residue is immediately dissolved in methylene chloride ( 200 ml . ), 4 - dimethylaminopyridine ( 7 . 5 g ., 0 . 061 mole ) and triethylamine ( 6 . 1 g ., 0 . 061 mole ) added and the stirred solution cooled to 0 ° c . ( ice / water cooling ) under a nitrogen atmosphere . acetic anhydride ( 6 . 1 g ., 0 . 061 mole ) is then added dropwise over 5 minutes with good stirring . after an additional 30 minutes of stirring at 0 ° c ., the reaction mixture is diluted with ethyl acetate ( 2 liters ) and water ( 1 liter ) and stirred for 10 minutes . the aqueous is extracted once more with water and the combined organics washed successively with water ( 4 × 1 liter ), saturated sodium bicarbonate ( 1 × 1 liter ), brine ( 1 × 1 liter ), dried ( mgso 4 ) and concentrated to a light brown oil (˜ 27 g .). the residue is chromatographed on 1 . 8 kg . of silica gel using benzene 15 / ethyl acetate as the eluting solvent . one liter fractions are collected . after elution of less polar impurities , fractions 16 - 20 are combined and evaporated to a residue which is crystallized from ether / petroleum ether to yield 5 . 6 g . ( 23 . 4 %) of the trans - isomer of the title product . fractions 21 - 27 are combined to give 7 . 6 g . ( 31 . 8 %) of a mixture of the trans - and cis - isomers , and fractions 28 - 32 are combined to give 2 . 5 g . ( 10 . 4 %) of the cis - isomer of the title product . 1 h nmr ( 60 mhz ) δ cdcl . sbsb . 3 tms ( ppm ): 7 . 24 ( s , 5h , aromatic ), 5 . 97 ( s , 2h , meta h &# 39 ; s ), 2 . 28 ( s , 3h , ch 3 -- coo ), 1 . 23 ( d , 3h , ch 3 -- ch -- o --), 1 . 20 ( d , 3h , ch 3 -- ch -- n ), 1 . 3 - 4 . 5 ( m , 17h , remaining protons ). analysis : calc &# 39 ; d . for c 27 h 33 o 4 n : c , 74 . 45 ; h , 7 . 64 ; n , 3 . 22 %; found : c , 74 . 15 ; h , 7 . 68 ; n , 3 . 18 %. analysis : calc &# 39 ; d . for c 27 h 33 o 4 n . hcl : c , 68 . 71 ; h , 7 . 26 ; n , 2 . 97 %; found : c , 68 . 86 ; h , 7 . 16 ; n , 2 . 97 %. sodium borohydride ( 7 . 57 g ., 0 . 20 mole ) is added to methanol ( 200 ml .) under a nitrogen atmosphere and cooled in an acetone / dry ice bath to about - 75 ° c . the mixture is stirred for about 20 minutes to dissolve most , if not all , the sodium borohydride . a solution of d , l - trans - 5 , 6 , 6aβ , 7 , 10 , 10aα - hexahydro - 1 - acetoxy - 6β - methyl - 3 -( 5 - phenyl - 2 - pentyloxy ) benzo [ c ] quinolin - 9 ( 8h )- one ( 8 . 71 g ., 0 . 02 mole ) in tetrahydrofuran ( 88 ml .) is cooled to about - 50 ° c . and then added dropwise over a 5 - 10 minute period to the sodium borohydride solution . the reaction mixture is stirred at about - 70 ° c . for 30 minutes and is then poured onto a mixture of water ( 1000 ml .) containing ammonium chloride ( 45 g ., 0 . 80 mole ) crushed ice ( 250 ml .) and ethyl acetate ( 250 ml .). the layers are separated and the aqueous extracted with ethyl acetate ( 3 × 200 ml .). the combined extracts are washed with water ( 1 × 100 ml .) and dried ( mgso 4 ). the dried extract is cooled to about 5 ° c . a solution of ethyl acetate ( 15 ml . )/ hcl , 1 . 5 n ( 0 . 025 mole ) is then added dropwise over a 15 minute period . upon stirring the mixture at 0 °- 5 ° c ., the hydrochloride salt of the title product precipitates . the mixture is stirred for a half - hour , filtered and the salt dried at 25 ° c ./ 0 . 055 mm . to give 6 . 378 g . ( 67 . 3 %) of product , m . p . 195 °- 198 ° c . ( dec .). to a solution of d , l - cis - 5 , 6 , 6aβ , 7 , 10 , 10aβ - hexahydro - 1 - acetoxy - 6β - methyl - 3 -( 5 - phenyl - 2 - pentyloxy )- benzo [ c ] quinolin - 9 ( 8h )- one ( 1 . 0 g ., 2 . 296 mmole ) in dry tetrahydrofuran ( 100 ml .) at - 78 ° c . is added , with stirring , potassium tri - sec - butyl borohydride ( 4 . 6 ml ., of 0 . 5 m , 2 . 296 mmole ) dropwise over a period of five minutes . the reaction mixture is stirred an additional 30 minutes at - 78 ° c . and is then poured , with stirring , into a solution of 5 % acetic acid ( 250 ml .) and ether ( 500 ml .) pre - cooled to 0 ° c . the layers are separated and the aqueous layer extracted with additional ether ( 250 ml .). the combined ether extracts are washed successively with water ( 2 × 250 ml . ), saturated sodium bicarbonate solution ( 1 × 250 ml .) and brine ( 1 × 250 ml . ), dried ( mgso 4 ) and concentrated in vacuo to give a yellow oil ( 1 . 4 g .). the crude oil is chromatographed on silica gel ( 100 g .) using benzene / ether ( 3 : 1 ) as eluant . after elution of less polar impurities , the title compound is isolated as a clear oil ( 700 mg .). the oil is dissolved in ether ( 35 ml .) and treated with ether saturated with hcl gas to give the hydrochloride salt of the title compound ( 448 mg . ), m . p . 115 °- 124 ° c . after recrystallization from ether / chloroform . analysis : calc &# 39 ; d . for c 27 h 35 o 4 n . hcl : c , 68 . 41 ; h , 7 . 66 ; n , 2 . 96 %; found : c , 68 . 52 ; h , 7 . 91 ; n , 2 . 73 %. a solution of 145 mg . d , l - trans - 5 , 6 , 6aβ , 7 , 8 , 9 , 10 , 10aα - octahydro - 1 - acetoxy - 9 - hydroxy - 6β - methyl - 3 -( 5 - phenyl - 2 - pentyloxy ) benzo [ c ] quinoline and 46 mg . potassium carbonate in 35 ml . methanol is stirred at room temperature . after 30 minutes , the reaction mixture is neutralized with acetic acid and concentrated under reduced pressure . the residue is dissolved in ether ( 100 ml . ), washed successively with water ( 2 × 35 ml . ), saturated sodium bicarbonate ( 1 × 35 ml . ), brine ( 1 × 40 ml . ), dried ( mgso 4 ) and concentrated under reduced pressure to give d , l - trans - 5 , 6 , 6aβ , 7 , 8 , 9 , 10 , 10aα - octahydro - 1 , 9 - dihydroxy - 6β - methyl - 3 -( 5 - phenyl - 2 - pentyloxy ) benzo [ c ] quinoline . to a stirred solution of 436 mg . of d , l - trans - 5 , 6 , 6aβ , 7 , 10 , 10aα - hexahydro - 1 - acetoxy - 6β - methyl - 3 -( 5 - phenyl - 2 - pentyloxy ) benzo [ c ] quinolin - 9 ( 8h )- one in 3 ml . acetonitrile cooled to 15 ° c . is added 0 . 5 ml . 37 % aqueous formaldehyde followed by 100 mg . sodium cyanoborohydride . acetic acid is added to maintain a neutral ph until the reaction is complete as evidenced by no remaining starting material by thin layer chromatography . the product is isolated in the following manner . ice water and ether is added to the reaction mixture , the ether layer separated and the aqueous extracted once more with ether . the combined ether layers are combined , dried and evaporated to yield the desired d , l - trans - 5 , 6 , 6aβ , 7 , 10 , 10aα - hexahydro - 1 - acetoxy - 5 , 6β - dimethyl - 3 -( 5 - phenyl - 2 - pentyloxy ) benzo [ c ]- quinolin - 9 ( 8h )- one ; an oil . analysis of hydrochloride calc &# 39 ; d . for c 28 h 35 o 4 n . hcl : c , 69 . 19 ; h , 7 . 47 ; n , 2 . 88 %; found : c , 68 . 72 ; h , 7 . 18 ; n , 2 . 74 %. analysis : calc &# 39 ; d . for c 28 h 35 o 4 n : c , 74 . 80 ; h , 7 . 85 ; n , 3 . 12 %; found : c , 74 . 66 ; h , 8 . 05 ; n , 2 . 66 %. formaldehyde ( 1 . 1 ml . of 37 % aqueous ) is added to a solution of d , l - trans - 5 , 6 , 6aβ , 7 , 10 , 10aα - hexahydro - 1 - acetoxy - 6β - methyl - 3 -( 5 - phenyl - 2 - pentyloxy ) benzo [ c ]- quinoline - 9 ( 8h )- one in acetonitrile ( 15 ml .) at room temperature , followed by sodium cyanoborohydride ( 0 . 262 g .). the reaction mixture is stirred for one hour during which time the ph is maintained at neutral ph by addition of acetic acid as needed . additional sodium cyanoborohydride ( 0 . 262 g .) and methanol ( 15 ml .) are added to the reaction mixture , which is then acidified to ph 3 , stirred for two hours , and concentrated under reduced pressure to an oil . the oil is diluted with water ( 50 ml . ), the ph then adjusted to 9 - 10 by means of aqueous sodium hydroxide , and the alkaline mixture extracted with ether ( 3 × 200 ml .). the combined ether extracts are washed with brine , dried ( na 2 so 4 ) and concentrated under reduced pressure to a clear oil . the oil is then dissolved in 50 % ether - hexane and charged to a silica gel column . the column is eluted first with 50 % ether - hexane followed by 60 %, 70 % and 75 % etherhexane . the eluate is monitored by thin layer chromatography ( ether - 10 , hexane - 1 ). the first product collected is d , l - trans - 5 , 6 , 6a , 7 , 10 , 10a - hexahydro - 1 - acetoxy - 5 , 6β - dimethyl - 3 -( 5 - phenyl - 2 - pentyloxy ) benzo [ c ]- quinolin - 9 ( 8h )- one . d , l - trans - 5 , 6 , 6aβ , 7 , 8 , 9 , 10 , 10aα - octahydro - 1 - acetoxy - 5 , 6β - dimethyl - 9β - hydroxy - 3 -( 5 - phenyl - 2 - pentyloxy ) benzo [ c ] quinoline , which is isolated as the hydrochloride salt ; m . p . 163 °- 165 ° c . to a stirred solution of 1 . 0 g . ( 0 . 0021 moles ) ( 2 &# 39 ; r , 6s , 6ar , 9r , 10ar )-(-)- 1 - acetoxy - 5 , 6 , 6a , 7 , 8 , 9 , 10 , 10a - octahydro - 9 - hydroxy - 6 - methyl - 3 -( 5 - phenyl - 2 - pentyloxy )- benzo [ c ] quinoline hydrochloride in 30 ml . chcl 3 is added 30 ml . saturated nahco 3 solution , and the mixture stirred 5 minutes at room temperature . the layers are separated and the aqueous layer re - extracted with 20 ml . chcl 3 . the combined chloroform layers are dried ( mgso 4 ), filtered and the solvent removed in vacuo to yield the free base as a colorless foam . this foam is dissolved in 40 ml . tetrahydrofuran and combined with 1 . 0 g . 5 % pd / c , 1 . 05 ml . ( 0 . 018 moles = 8 . 7 equiv .) glacial acetic acid and 15 . 8 ml . ( 0 . 20 moles = 100 equiv .) 37 % aqueous formaldehyde . the mixture is placed in a parr apparatus at 50 p . s . i . and hydrogenated for 50 minutes . the catalyst is filtered through diatomaceous earth , washing well with ethyl acetate . the filtrate is diluted to 150 ml . with ethyl acetate then washed successively 3 × with 100 ml . saturated nahco 3 solution , 75 ml . h 2 o 3 ×, 75 ml . brine 1 ×, and dried over mgso 4 . the solvent is filtered and removed in vacuo yielding a yellow viscous oil which is chromatographed on 50 g . silica gel ( 0 . 04 - 0 . 63 mm .) and eluted with toluene / diethyl ether ( 1 : 1 ). similar fractions are combined and removed in vacuo to yield a colorless oil which is redissolved in 50 ml . diethyl ether and dry hcl bubbled in under a nitrogen atomsophere with stirring . the resulting white solid is filtered under a nitrogen atmosphere and dried in vacuo ( 0 . 1 mm .) for 24 hours at room temperature to yield 0 . 45 g . ( 44 %) of the title product , m . p . 90 °- 95 ° c . ( d ). nmr ( cdcl 3 ) - 2 . 73 ppm . singlet , 3h ( n -- ch 3 ). calc &# 39 ; d . for c 28 h 37 o 4 n . hcl : c , 68 . 90 ; h , 7 . 85 ; n , 2 . 87 %; found : c , 68 . 60 ; h , 7 . 92 ; n , 2 . 77 %. a stirred suspension of 47 . 4 g . ( 0 . 10 mol ) of dl - 5 , 6 , 6aβ , 7 , 8 , 9α , 10 , 10aα - octahydro - 1 - acetoxy - 9 - hydroxy - 6β - methyl - 3 -( 1 - methyl - 4 - phenylbutoxy ) benzo [ c ] quinoline , hydrochloride and 500 ml . of chcl 3 under a n 2 atmosphere is cooled to 0 ° c . and treated with 250 ml . pyridine followed by 58 ml . ( 0 . 50 mole ) benzoyl chloride in 500 ml . chloroform . the resultant homogeneous solution is then refluxed on a steam bath for one hour . the reaction mixture is poured onto crushed ice and extracted with chloroform . the organic extracts are combined , washed successively with water ( 2 × 500 ml . ), 10 % hydrochloric acid , saturated sodium bicarbonate solution ( 500 ml .) and saturated brine solution ( 500 ml . ), dried over mgso 4 , filtered and concentrated to give 119 g . of a light yellow oil . chromatography on 2000 g . silica gel ( 20 % etoac - cyclohexane ) affords 50 . 5 g . ( 78 %) of dl - 5 , 6 , 6aβ , 7 , 8 , 9α , 10 , 10aα - octahydro - 1 - acetoxy - 5 - benzoyl - 9 - benzoyloxy - 6β - methyl - 3 -( 1 - methyl - 4 - phenylbutoxy ) benzo [ c ] quinoline , m . p . 125 °- 30 ° c . anal . calc &# 39 ; d . for c 41 h 43 o 6 n : c , 76 . 24 ; h , 6 . 72 ; n , 2 . 17 %. found : c , 76 . 35 ; h , 6 . 92 ; n , 2 . 19 %. recrystallization of 50 . 5 g . dl - 5 , 6 , 6aβ , 7 , 8 , 9α , 10 , 10aα - octahydro - 1 - acetoxy - 5 - benzoyl - 9 - benzoyloxy - 6β - methyl - 3 -( 1 - methyl - 4 - phenylbutoxy ) benzo [ c ] quinoline from 2 l . 2 - propanol yielded 23 . 8 of white solids , m . p . 136 °- 8 °, which are recrystallized twice more from 2 - propanol and once from acetonitrile to yield 5 . 7 g . of dl - 5 , 6 , 6aβ , 7 , 8 , 9α , 10 , 10aα - octahydro - 1 - acetoxy - 5 - benzoyl - 9 - benzoyloxy - 6β - methyl - 3 -( 1β - methyl - 4 - phenylbutoxy ) benzo [ c ] quinoline , m . p . 148 °- 9 ° c . the filtrate from the original 2 - propanol recrystallization of dl - 5 , 6 , 6aβ , 7 , 8 , 9α , 10 , 10aα - octahydro - 1 - acetoxy - 5 - benzoyl - 9 - benzoyloxy - 6β - methyl - 3 -( 1 - methyl - 4 - phenylbutoxy ) benzo [ c ] quinoline is evaporated to a white foam and triturated with 500 ml . ether to yield 12 . 9 g . of white solids , m . p . 129 °- 132 °. these solids are triturated twice again with ether to yield 3 . 8 g . of dl - 5 , 6 , 6aβ , 7 , 8 , 9α , 10 , 10aα - octahydro - 1 - acetoxy - 5 - benzoyl - 9 - benzoyloxy - 6β - methyl - 3 -( 1α - methyl - 4 - phenylbutoxy ) benzo [ c ] quinoline , m . p . 139 °- 141 ° c . to a stirred solution of 2 . 0 g . lithium aluminum hydride in 150 ml . tetrahydrofuran under a nitrogen atmosphere is added a solution of 5 . 7 g . ( 8 . 8 mmole ) dl - 5 , 6 , 6aβ , 7 , 8 , 9α , 10 , 10aα - octahydro - 1 - acetoxy - 5 - benzoyl - 9 - benzoyloxy - 6β - methyl - 3 -( 1β - methyl - 4 - phenylbutoxy ) benzo [ c ] quinoline in 112 ml . tetrahydrofuran dropwise over a five minute period . the resultant mixture is heated at reflux for 45 minutes , cooled and poured carefully onto an ice cold mixture of 1125 ml . 5 % acetic acid in water and 2250 ml . ether . this biphasic mixture is stirred for ten minutes and the layers separated . the aqueous layer is extracted with an additional 500 ml . ether and the combined ether extracts ae washed successively with water ( 3 × 500 ml . ), saturated sodium bicarbonate solution ( 2 × 500 ml .) and saturated brine solution ( 1 × 500 ml . ), dried over mgso 4 , filtered and evaporated to yield 5 . 4 g . dl - 5 - benzyl - 5 , 6 , 6aβ , 7 , 8 , 9α , 10 , 10aα - octahydro - 1 , 9 - dihydroxy - 6β - methyl - 3 -( 1β - methyl - 4 - phenylbutoxy ) benzo [ c ] quinoline as a light purple oil . dl - 5 - benzyl - 5 , 6 , 6aβ , 7 , 8 , 9α , 10 , 10aα - octahydro - 1 , 9 - dihydroxy - 6β - methyl - 3 -( 1β - methyl - 4 - phenylbutoxy )- benzo [ c ] quinoline is immediately taken up in 450 ml . methanol and hydrogenated at atmospheric pressure over 4 . 27 g . pd / c for 3 hours to yield dl - 5 , 6 , 6aβ , 7 , 8 , 9α , 10 , 10aα - octahydro - 1 , 9 - dihydroxy - 6β - methyl - 3 -( 1β - methyl - 4 - phenylbutoxy ) benzo [ c ] quinoline after filtration of the catalyst and evaporation of the methanol . dl - 5 , 6 , 6aβ , 7 , 8 , 9α , 10 , 10aα - octahydro - 1 , 9 - dihydroxy - 6β - methyl - 3 -( 1β - methyl - 4 - phenylbutoxy ) benzo [ c ] quinoline is immediately dissolved in 210 ml . methylene chloride , cooled to 0 ° c . under a nitrogen atmosphere , and treated successively with 1 . 35 ml . triethylamine , 1 . 19 g . ( 9 . 7 mmol ) of 4 - dimethylaminopyridine and finally with 0 . 834 ml . ( 8 . 8 mmol ) of acetic anhydride . after stirring for 30 minutes , the reaction mixture is poured onto 250 ml . of water and the organic layer separated . the aqueous layer is extracted once more with methylene chloride and the combined methylene chloride layers washed successively with a saturated sodium bicarbonate solution ( 2 × 150 ml . ), wate ( 150 ml .) and a saturated brine solution , dried over mgso 4 , filtered , evaporated and chromatographed on 300 g . silica gel using 33 % ether - toluene as eluent to give 1 . 4 g . dl - 5 , 6 , 6aβ , 7 , 8 , 9α , 10 , 10aα - octahydro - 1 - acetoxy - 9 - hydroxy - 6β - methyl - 3 -( 1β - methyl - 4 - phenylbutoxy ) benzo [ c ] quinoline , as the free base . treatment of dl - 5 , 6 , 6aβ , 7 , 8 , 9α , 10 , 10aα - octahydro - 1 - acetoxy - 9 - hydroxy - 6β - methyl - 3 -( 1β - methyl - 4 - phenylbutoxy ) benzo [ c ] quinoline , in ether with hcl ( gas ) yields 795 mg . dl - 5 , 6 , 6aβ , 7 , 8 , 9α ,- 10 , 10aα - octahydro - 1 - acetoxy - 9 - hydroxy - 6β - methyl - 3 -( 1β - methyl - 4 - phenylbutoxy ) benzo [ c ] quinoline , hydrochloride , m . p . 213 °- 215 ° c . after filtration and trituration in acetone , m / e = 437 ( m + , 100 %). anal . calc &# 39 ; d . for c 27 h 35 o 4 n . hcl : c , 68 . 42 ; h , 7 . 66 ; n , 2 . 96 . found : c , 68 . 48 ; h , 7 . 63 ; n , 3 . 05 . similarly prepared from 3 . 8 g . dl - 5 , 6 , 6aβ , 7 , 8 , 9α , 10 , 10aα - octahydro - 1 - acetoxy - 5 - benzoyl - 9 - benzoyloxy - 6β - methyl - 3 -( 1α - methyl - 4 - phenylbutoxy ) benzo [ c ] quinoline is 1 . 1 g . dl - 5 , 6 , 6aβ , 7 , 8 , 9α , 10 , 10aα - octahydro - 1 - acetoxy - 9 - hydroxy - 6β - methyl - 3 -( 1α - methyl - 4 - phenylbutoxy ) benzo [ c ]- quinoline hydrochloride , m . p . 202 °- 205 ° ( d . ), m / e = 437 ( 100 %, m + ). anal . calc &# 39 ; d . for c 27 h 35 o 4 n . hcl : c , 68 . 42 ; h , 7 . 66 ; n , 2 . 96 . found : c , 68 . 20 ; h , 7 . 56 ; n , 3 . 04 . to a 25 ° c . solution of d , l - trans - 5 , 6 , 6aβ , 7 , 8 , 9 , 10 , 10aα - octahydro - 1 , 9 - dihydroxy - 6β - methyl - 3 -( 5 - phenyl - 2 - pentyloxy )- benzo [ c ] quinoline ( 1 . 0 g ., 2 . 53 mmoles ) in methylene chloride ( 20 ml .) is added 4 - n - piperidylbutyric acid hydrochloride ( 0 . 524 g ., 2 . 53 mmoles ) and dicyclohexylcarbodiimide ( 0 . 573 g ., 2 . 78 mmoles ). the reaction mixture is stirred at 25 ° c . for 6 hours and then cooled for 12 hours and filtered . evaporation of the filtrate and trituration of the residue with ether gives 1 . 3 g . of solid of the monohydrochloride salt . preparative layer chromatography of a portion of this solid on 0 . 5 mm . thick silica gel and elution with 10 % methanol - methylene dichloride affords the free base , d , l - trans - 5 , 6 , 6aβ , 7 , 8 , 9 , 10 , 10aα - octahydro - 1 -( 4 - n - piperidylbutyryloxy )- 9 - hydroxy - 6β - methyl - 3 -( 5 - phenyl - 2 - pentyloxy ) benzo [ c ] quinoline . 1 h nmr ( 60 mhz ) δ cdcl . sbsb . 3 tms ( ppm ): 1 . 12 ( d , j = 7 hz , c - 3 side - chain methyl ), 1 . 25 ( d , j = 6 hz , c - 6 methyl ), 5 . 84 ( s , two arh ) and 7 . 16 ( s , 5h ). treatment of this free base with excess hydrogen chloride in ether yield the dihydrochloride salt as a hygroscopic powder . to a 25 ° c . solution of d , l - 5 , 6 , 6a , 7 - tetrahydro - 1 - hydroxy - 6β - methyl - 3 -( 5 - phenyl - 2 - pentyloxy ) benzo [ c ]- quinoline - 9 ( 8h )- one ( 550 mg ., 1 . 41 mmole ) in methylene chloride ( 26 ml .) is added 4 - n - piperidylbutyric acid hydrochloride ( 291 mg ., 1 . 41 mmole ) and dicyclohexylcarbodiimide ( 319 mg ., 1 . 55 mmole ). this reaction mixture is stirred for 18 hours and is then cooled to 0 ° c . and filtered . evaporation of the filtrate and trituration of the residue with ether gives 800 mg . of d , l - 5 , 6 , 6a , 7 - tetrahydro - 1 -( 4 - n - piperidylbutyryloxy )- 6β - methyl - 3 -( 5 - phenyl - 2 - pentyloxy ) benzo [ c ] quinoline - 9 ( 8h )- one hydrochloride as a hygroscopic yellow powder . ir ( chcl 3 ): 2 . 92 , 4 . 14 ( hn . sup .⊕ =), 5 . 69 ( ester ), 6 . 00 , 6 . 20 and 6 . 40μ . in like manner , d , l - trans - 5 , 6 , 6aβ , 7 , 8 , 9 , 10 , 10aα - octahydro - 1 -( 4 - n - morpholinobutyryloxy )- 9 - hydroxy - 6β - methyl - 3 -( 5 - phenyl - 2 - pentyloxy ) benzo [ c ] quinoline hydrochloride is prepared from 4 - n - morpholinobutyric acid and d , l - trans - 5 , 6 , 6aβ , 7 , 8 , 9 , 10 , 10aα - octahydro - 1 , 9 - dihydroxy - 6β - methyl - 3 -( 5 - phenyl - 2 - pentyloxy ) benzo [ c ]- quinoline : excess hydrogen chloride is passed into a solution of the appropriate benzo [ c ] quinoline of formulae i and ii and the resulting precipitate separated and recrystallised from an appropriate solvent , e . g . methanol - ether ( 1 : 10 ). analysis : calc &# 39 ; d . for c 27 h 36 o 4 ncl : c , 68 . 48 ; h , 7 . 70 ; n , 2 . 89 %; found : c , 68 . 42 ; h , 7 . 66 ; n , 2 . 96 %. | 2 |
[ 0023 ] fig1 shows a flow chart as applied to apparatus used in implementing the present invention . the flow chart illustrates an embodiment according to the method and apparatus of the present invention . the shown embodiment applies the above described public key encryption method in combination with a signed public key and certificate , respectively . a typical exemplary scenario shall be described below to enlighten the virtue of the software protection method against unauthorized use . hardware devices and the corresponding software can be purchased via the internet using a web shop of the manufacturer or distributor or via a classical shop . if the purchase is performed via the internet contact information like mail address or e - mail address are submitted to the vendor . the hardware devices and the corresponding software are put together and sent to the purchaser . the respective hardware identification numbers can be obtained for example by the serial number of the hardware products . the unique hardware identification numbers and serial numbers are linked by a database system . to allow the use of the software also the license key has to be submitted to the purchaser . the hardware identification numbers are encrypted using a secret key according to a public key encryption method . in order to ensure a certain security of the secret key the encryption of the hardware identification numbers and the coding of the encrypted numbers in the license key should be performed by a single key authority to avoid a wide distribution of the secret key . the generated license key is submitted using preferably another way of submission . it is also possible that the license key has to be requested by the user . the user submits for example the serial number of the hardware devices in his property or the unique hardware identification numbers determined by a special software tool and a contact address to the key authority . the key authority has to be able to check the hardware numbers to ensure that the hardware device is authorized to be used in combination with the software . the user is now in possession of the hardware devices , the corresponding software and a personal license key . a public key according to the secret key has also to be provided . coding of the public key would be the simplest but also an unsafe way of providing . according to the currently preferred embodiment the public key is provided as a certificate or signed public key . the signed public key involves a third party key authority which encrypts the public key according to the secret key used for encrypting the hardware identification numbers contained in the license key . both the signed public key and the public key of the third party key authority can be submitted to the user via e - mail or can be accessed by the user using the internet . the software can now decrypt the hardware identification numbers of the license key in a two step decryption . in a first decryption step the signed public key or certificate , respectively , is decrypted using the public key of the third party key authority . this decryption results in the public key of the manufacturer or distributor . the following second decryption step involving the gained public key and the license key results in revelation of the hardware numbers contained in the license key . the contained hardware numbers are now compared with the hardware identification numbers read out by the software of the accessible hardware devices . if the numbers match access to the software and its execution is permitted to the user . in the other case it is for example possible to permit access to the software with limited functionality . due to the additional encryption of the public key used for decrypting the license key data the manipulation of the software and thereupon the unauthorized use of the software is made more difficult in comparison to using a coded public key for decryption . the certificate ensures that only the public key of the manufacturer or distributor is a legal public key . additionally , if the certificate and the corresponding public key of the third party key authority are submitted in any way parallel to the submission of the license key , the exchange of the keys is easier and once compromised keys can be exchanged against new secure ones . [ 0028 ] fig2 is a flow chart illustrating the steps and functions of the method and apparatus performed to activate repeatedly the protected software after the first activation . in the present embodiment according to fig2 the public key of the third party authority or certificate , respectively , the public key of the manufacturer or distributor and the license key are stored . each time the software is restarted the signed public key is decrypted using the public key of the manufacturer or distributor and subsequent the contained hardware identification numbers are decrypted and extracted for the license key and compared with the accessible hardware devices in order to ensure that the authorized hardware devices are used . this proceeding ensures that the public key of the manufacturer can not be exchanged against a public key of an authorized party . hereby , a complete protection against misuse of the software program is given . often software programs once installed on a computer system can not be copied and reinstalled on another one . in this case the protection against exchange of the public key of the manufacturer or distributor is not necessary any more . hence , it can be sufficient to check only once the public key to ensure the origin of the public key from an authorized source . only the decrypted certificate and the license key have to be stored which saves the execution of one decrypting process . the complete software protection is to be preferred , since the same decryption methods and algorithms are often used and the implementation of the complete staggered decryption process does not extend the software program to much . [ 0030 ] fig3 shows a possible arrangement of two computers 301 each equipped with a bluetooth ™ network interface 303 as an example of a hardware arrangement . the both bluetooth ™ network interfaces 303 each comprise a unique hardware identification address . both identification addresses can be read out by both software installed on one of the both computers 301 since bluetooth ™ network interfaces 303 are accessible from each other and all network interface cards have to comprise a unique hardware identification address to recognize them worldwide . software applying the protection method according to the present invention can be installed on one of the two computers and checking if at least two bluetooth ™ network interfaces 303 comprising certain hardware identification address are accessible . it is even possible to co - code additional license conditions . for example , it could be coded that one of the bluetooth ™ network interface 303 has to be connected electrically to the computer which executes the software and the other network interface 303 is accessed via radio frequency transmission 305 . obviously , the number of verified hardware devices comprising unique hardware identification addresses can vary according to the license conditions . [ 0031 ] fig4 shows a possible arrangement of a mobile terminal 401 and a mobile phone 403 each equipped with a bluetooth ™ network interface 303 , 405 as a further example of a hardware arrangement . this arrangement is similar to the arrangement shown in fig3 . a mobile phone 403 is used for linking a mobile terminal 401 to an access server to the internet . the data communication between mobile phone 403 and mobile terminal 401 is performed using bluetooth ™ network interfaces 303 , 405 . a special software is implemented on the mobile terminal 401 which use is only authorized in combination with a mobile phone 403 of a certain manufacturer . the manufacturer of the bluetooth ™ network interface 405 plugged on the mobile phone 403 distributes the necessary communication software which shall only be usable if this certain bluetooth ™ network interface 405 is connected . the software executed on the mobile terminal is protected against unauthorized use applying the method according to the present invention . the license key contains the bluetooth ™ hardware address of the bluetooth ™ network interface 405 . the corresponding bluetooth ™ network interface 303 connected to the mobile terminal 401 is not involved in the verification process so that a bluetooth ™ network interface of any manufacturer can be used . [ 0032 ] fig5 shows a further embodiment involving a controller unit like a mobile phone 403 or a personal computer 301 both equipped with a bluetooth ™ network interface 303 to control a home electronic device 501 like digital versatile disk player ( dvd ), video recorder ( vcr ), digital video recorder ( dvcr ). rising numbers of features included in home electronic devices requires just operable user interfaces . particularly , video processing devices comprising multiple features are suitable to be equipped with interface devices for remote controlling by another terminal device , e . g . personal computer , mobile phone or the similar devices able to execute controlling software . a bluetooth ™ network interface can be implemented as preferred interface device . related controlling software executed on the controlling devices has to be protected and shall only be usable in combination with the home electronic device of the certain manufacturer but executable on controlling devices of several manufacturer . therefore , the method of the present invention is suitable to prevent unauthorized use of the software for controlling unauthorized devices of a competitor which implement the same controlling interface . the forgoing description of the preferred embodiment of the invention has been presented for the purpose 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 . the method and apparatus to prevent unauthorized software use applies a unique hardware identification sequence of hardware devices accessed by the software . the identification sequence is compared with coded sequences in a special license key comprising hardware identification sequences . to protect the contained hardware identification sequences against unauthorized manipulation the sequences can be encrypted using different encryption methods according to the desired degree of protection . accordingly , software which use is bonded to certain hardware devices can be protected effectively and reasonably by employing the method of the present invention . | 6 |
digital video signals generally comprise a series of image frames , which include a large number of image pixels to formulate a desired image . these image frames are processed at a high rate of speed , typically on the order of several image frames per second ( e . g . 60 frames per second ). image frames have heretofore been processed according to a constant nonlinear transfer function defining light intensity output in terms of the applied voltage video signal . the principles of the present disclosure , however , seek to improve a resulting video image by allowing for frame - to - frame image adjustment . in one aspect , frame - to - frame image adjustment may be accomplished by altering the nonlinear transfer function ( graphically depicted as a gamma curve ) between video signal input and light intensity output . in other words , the nonlinear transfer function can be altered for each image frame , thus allowing each image frame to have a tailored gamma correction for optimal image quality . referring to fig3 , in one embodiment , frame - to - frame gamma correction may vary between a standard gamma curve 30 and an s - shaped gamma curve 32 . for example , image frames that have a large number of dark or light pixels will typically have better image quality when following the standard gamma curve 30 than when following the s - shaped gamma curve 32 . however , image frames that comprise a large number of pixels falling between the extremes of excessively dark and bright images generally have better image quality when following the s - shaped gamma curve 32 than when following the standard gamma curve 30 . accordingly , it is desirable to incorporate a process during conditioning of a video signal that allows for adjustment of gamma correction between the standard gamma curve 30 and the s - shaped gamma curve 32 for each individual frame of a video image . the standard gamma curve 30 and the s - shaped gamma curve 32 as discussed herein do not correspond to defined nonlinear transfer functions . rather , varying standard gamma curves and varying s - shaped gamma curves are contemplated as falling within the scope of this disclosure so long as varying standard gamma curves generally correspond in shape to the standard gamma curve 30 and varying s - shaped gamma curves generally correspond in shape to the s - shaped gamma curve 32 . fig4 illustrates an exemplary video signal path 40 for conditioning a video signal v to achieve frame - to - frame gamma correction adjustment . the video signal path 40 begins with transmission of a video signal v from a video signal generator 42 . the video signal generator 42 may be any device capable of transmitting an analog or digital video signal , such as a cable box , a digital videodisc player , or a videocassette recorder . the video signal v feeds into a digital video processor 44 , which conditions the video signal for digital output . the video signal v then feeds into a field programmable gate array ( fpga ) 46 , which includes various video - processing modules for manipulating the video signal as will be further described . after leaving the fpga 46 , the video signal v passes through an application specific integrated circuit ( asic ) 48 , which converts the video signal into displayable bit planes . a digital micro mirror device ( dmd ) 50 receives the bit planes from the asic 48 and displays an image defined by the bit planes on a digital display device 52 , such as a digital television . the term “ digital television ” is meant to include both television monitors and those digital televisions having built - in tuners . in practice , the digital video processor 44 , the fpga 46 , the asic 48 , and the dmd 50 may all be provided inside the digital display device 52 . more particularly , the fpga 46 and asic 48 may be implemented via a printed circuit board housed within the digital display device 52 . the foregoing video signal path 40 is only exemplary , and other hardware implementations are contemplated . for example , specific hardware implementations , such as the fpga 46 and the asic 48 , may be replaced or otherwise altered without departing from the scope of the disclosure . also , the dmd 50 may be replaced with some other optoelectronic device , such as an lcd device . still further , the digital display device 52 may be any digital video display device . for example , the digital display device 52 may be any digital display device other than a digital television , such as a plasma display or a cathode ray tube ( crt ). the digital display device 52 may also be utilized in front projection systems . in one embodiment , the fpga 46 may include processes for conditioning the video signal v for frame - to - frame gamma correction adjustment . referring to fig5 , the fpga 46 includes an rgb2hsv block 54 , which provides conventional color space conversion for the video signal v . the rgb2hsv block 54 generally converts color components r , g , b of the video signal v into hue , saturation , and value h , s , v components , which can be read and processed by subsequent conditioning modules . two video paths leave the rgb2hsv block 54 , with one path leading to a histogram block 56 and the other path leading to a gamma - shaping block 58 . a third path depicts the hue h and saturation s components being transferred to a back - end conditioning block as will be further described . the histogram block 56 generally conditions the video signal v by segregating pixels of an image frame and transmitting the resulting information v hist to the gamma - shaping block 58 . the gamma - shaping block 58 , in turn , performs additional conditioning processes on the video signal v received from the rgb2hsv block 54 using the information v hist received from the histogram block 56 . the resulting video signal output , v ″, along with the hue h and saturation s components are then passed into an hsv2rgb block 60 , which provides conventional color space conversion to r ′, g ′ and b ′ values . the r ′, g ′ and b ′ values are then passed to the asic 48 for further processing . as discussed previously , the video signal v is conditioned on a frame - to - frame basis . each frame comprises a predetermined amount of pixels depending on the input spatial resolution . in some embodiments , the number of pixels for any given frame can number in the millions . each pixel has an associated intensity value , which falls within a certain range depending on the defined intensity resolution . for example , an 8 - bit intensity resolution includes 256 different levels of intensity , which collectively form the image . accordingly , each pixel is assigned a value between 0 and 255 to indicate the level of intensity associated with the pixel , wherein 0 indicates the lowest level of intensity ( e . g . darkest pixel ) and 255 indicates the highest level of intensity ( e . g . brightest pixel ). an exemplary embodiment will be described with respect to the conditioning of a video signal having 8 - bit resolution images , but it is understood that the present disclosure equally applies to images of varying intensity resolutions . referring to fig6 , the histogram block 56 may be set up to divide the individual pixels of any given frame into three separate bins — hist 1 , hist 2 , hist 3 . in this example , hist 1 is categorized as receiving all pixels having an intensity value between 0 and 79 , hist 2 is categorized as receiving all pixels having an intensity value between 80 and 179 , and hist 3 is categorized as receiving all pixels having an intensity value between 180 and 255 . the demarcations between hist 1 and hist 2 and between hist 2 and hist 3 may be arbitrarily defined , and therefore are not limited to the exemplary values indicated in fig6 . separating pixels according to intensity gives a general idea as to the relative darkness or lightness of a particular frame . the v hist values ( i . e . v hist1 , v hist2 and v hist3 ) of the three bins hist 1 , hist 2 , and hist 3 are then transferred to the gamma - shaping block 58 ( fig5 ) for manipulation of the video signal v . referring again to fig5 , the video signal v is not only sent from the rgb2hsv block 54 to the histogram block 56 , but is also sent directly from the rgb2hsv block to the gamma - shaping block 58 . referring to fig7 , the gamma - shaping block 58 conditions the video signal v to undergo transfer functions to map the digital video signal to an output light intensity . in some embodiments , it may not be desirable to make sharp gamma correction adjustments , which may occur between frames having marked differences in intensity resolution . such gamma correction adjustments may lead to poor image quality . accordingly , in an effort to produce gradual and smooth frame - to - frame gamma correction adjustments , weighting calculations 70 may be determined according to the v hist values supplied by the histogram block 56 . these weighting calculations are then incorporated into the transfer functions to ensure smooth frame - to - frame gamma correction adjustments . the weighting calculations 70 generally produce two values — w b and w d , which when applied to first and second transfer functions 72 and 74 , respectively , dictate the amount of transfer function to apply to the input video signal v and v ′, respectively . the w b and w d values may be calculated according to different bit weights . in this example , the w b and w d values are calculated in 8 - bit weights . more particularly , the w b value is calculated by first multiplying the number of dark pixels ( v hist1 ) by a user - defined parameter , typically provided by an original equipment manufacturer of the digital display device 52 ( fig4 ). this value is then subtracted from 256 : the w d value may be calculated in a similar manner by first multiplying the number of light pixels ( v hist3 ) by a user - defined parameter , again , typically provided by an original equipment manufacturer of the digital display device 52 ( fig4 ). this value is then subtracted from 256 : the w b value is used in manipulating a v lut1 value returned from a first lookup table ( lut 1 ) 76 . the video signal v received by the first transfer function 72 is also 8 - bit weighted and has a defined value falling somewhere between 0 and 255 . the first transfer function 72 sends this value for the video signal v to the first lookup table 76 , which returns a lut 1 value ( v lut1 ) to the first transfer function . in practice , lut 1 values are programmable values that correspond to weighted input values . in one example , if v were to equal 55 , the lut 1 would return a value v lut1 corresponding to the 55 th entry in the lut 1 . the first transfer function 72 further processes the video signal v to arrive at an output video signal v ′ by multiplying v lut1 by the w b value and dividing the returned value by 256 . this value is then added to v to arrive at v ′. accordingly , v ′ may be calculated as follows : the v ′ value is then transferred into the second transfer function 74 , which sends the v ′ value to a second lookup table ( lut 2 ) 78 . as with the video signal v , the v ′ value is 8 - bit weighted and has a defined value falling somewhere between 0 and 255 . the second lookup table 78 returns a lut 2 value ( v lut2 ) to the second transfer function . from here , the second transfer function 74 further processes the video signal v ′ to arrive at an output video signal v ″ by multiplying v lut2 by the w d value and dividing the returned value by 256 . this value is then added to v ′ to arrive at v ″. accordingly , v ″ may be calculated as follows : therefore , each frame is processed to have an output video signal v ″ that has an optimal gamma correction for the particular image displayed by the frame . referring again to fig4 , the video signal v ″ leaves the fpga 46 and enters the asic 48 , which further conditions the video signal v ″ before transmitting the signal to the dmd 50 and ultimately the digital display device 52 . as discussed above , the weighting calculation values w b and w d are used in tailoring an appropriate gamma correction for a particular frame . however , a gamma correction for a subsequent frame may be substantially different than the preceding frame , thus leading to an undesirable resulting video image . accordingly , the weighting calculations 70 may be manipulated to ensure a smooth transition between gamma corrections for adjacent frames . referring to fig8 , an additional process 80 may be implemented into the gamma - shaping block 58 , and more particularly , into the weighting calculation 70 , for adjusting the weighting calculation values w b and w d for each subsequent frame . in one embodiment , the process 80 generally involves application of an algorithm for evaluating the weighting calculations values w b and w d for a current frame against the weighting calculation values w b and w d for the previous frame . for the sake of clarity , the current weighting calculation values are referred to as w bn and w dn and the previous weighting calculation values are referred to as w bo and w do . the process 80 begins with calculating the w bn and w dn values 82 for the current frame . each of the w bn and w dn values are then evaluated to determine the ultimate weighting calculations w b and w d , which will be applied in determining v ′, and ultimately , v ″. however , prior to evaluating the w bn and w dn values , a determination should be made as to whether adjustment of the w bn and w dn values is desired . for example , drastic changes in gamma correction may occur at a scene cut ( i . e . changing of one scene of a video to a different scene of the video ). in these instances , drastic changes in gamma correction will not adversely affect the quality of the resulting image because continuity of images will not be an issue . scene cuts generally correspond to large changes in the v hist values described above . accordingly , the v hist values for a current frame can be compared with the v hist values for the previous frame to determine if there has been a large enough change in any of the v hist values to merit a large gamma correction difference between frames . in one embodiment , if any of the v hist values ( i . e . for any one of the three bins ) is larger than a certain val new value 82 , 84 , then the weighting calculation will forego any further processing and the current weighting calculation w b , w d , respectively may be used in the transfer function 86 , 88 , respectively . the val new value may be any prescribed value , which represents a large enough change in v hist1 , v hist2 , or v hist3 values to indicate that a scene cut has taken place . if none of the changes in v hist values rise above the val new value , then further evaluation of the weighting calculation values takes place . assuming that none of the changes in v hist values rises above the val new value , the current w bn and w dn values are then evaluated against the previous w bo and w do values , respectively . for example , the current w bn and w dn values may be evaluated to determine if they are larger than the respective previous w bo and w do values 90 , 92 . if the current w bn and w dn values are greater than the respective w bo and w do values , then the weighting calculations to be introduced into the respective transfer functions may be calculated as w bo + 1 ( 94 ) and w do + 1 ( 96 ). similarly , the current w bn and w dn values may be compared against the previous w bo and w do values to evaluate whether the current w bn and w dn values are lesser than the respective w bo and w do values 98 , 100 . if the w bn and w dn values are lesser than the respective w bo and w do values , then the weighting calculations to be introduced into the respective transfer functions may be calculated as w bo − 1 ( 102 ) and w do − 1 ( 104 ). of course , should the current w bn and w dn values equal the previous w bo and w do values , the previous w bo and w do values 106 , 108 may be used in the respective transfer functions . in this manner , large changes in weighting calculations within continuous scenes will not translate into sharp changes in gamma corrections . also , in some instances , the w bn value may increase relative to the previous w bo value , while the w dn value decreases relative to the previous w do value . accordingly , an increase in one value does not necessarily correspond to an increase in the other value . rather , each weighting calculation w bn value is independent of the w dn value for the same frame . while various embodiments for making frame - to - frame gamma correction adjustments according to the principles disclosed herein have been described above , it should be understood that they have been presented by way of example only , and not limitation . for example , weighting calculation adjustments have been described with respect to certain finite adjustments . however , the precise frame - to - frame adjustments may vary beyond the described embodiments . thus , instead of adding or subtracting “ 1 ” to a determined weighting calculation , the weighting calculation may be modified in other manners without departing from the scope of this disclosure . still further , the equations described with respect to calculating the output voltage signal may vary and are not meant to limit this disclosure to any particular embodiment . for example , different image resolutions may account for changes to these equations . rather , the following claims should be construed broadly to cover any embodiment tailored to achieve frame - to - frame adjustment of gamma correction . thus , the breadth and scope of the invention ( s ) should not be limited by any of the above - described exemplary embodiments , but should be defined only in accordance with any claims and their equivalents issuing from this disclosure . furthermore , the above advantages and features are provided in described embodiments , but shall not limit the application of such issued claims to processes and structures accomplishing any or all of the above advantages . additionally , the section headings herein are provided for consistency with the suggestions under 37 cfr 1 . 77 or otherwise to provide organizational cues . these headings shall not limit or characterize the invention ( s ) set out in any claims that may issue from this disclosure . specifically and by way of example , although the headings refer to a “ technical field ,” such claims should not be limited by the language chosen under this heading to describe the so - called technical field . further , a description of a technology in the “ background ” is not to be construed as an admission that technology is prior art to any invention ( s ) in this disclosure . neither is the “ brief summary ” to be considered as a characterization of the invention ( s ) set forth in issued claims . furthermore , any reference in this disclosure to “ invention ” in the singular should not be used to argue that there is only a single point of novelty in this disclosure . multiple inventions may be set forth according to the limitations of the multiple claims issuing from this disclosure , and such claims accordingly define the invention ( s ), and their equivalents , that are protected thereby . in all instances , the scope of such claims shall be considered on their own merits in light of this disclosure , but should not be constrained by the headings set forth herein . | 7 |
this invention relates to compounds of formula i ## str1 ## having a monosubstituted ester or amide linked moiety -- coz ( r 1 ) n ( r 2 ) m wherein when z is o or nh , n is 0 , m is 1 and r 2 is a straight or branched c 16 . 50 alkyl , alkenyl or alkoxy and when z is n , n is 1 , m is 1 , and r 1 and r 2 are each a straight or branched alkyl , alkenyl or alkoxy and r 1 and r 2 together have a total 16 - 50 carbons , and the monosubstituted moiety may be at the 2 , 3 , or 4 position on the pyridine ring , y is a c 1 - 3 alkyl and x - is a water soluble anion . the term &# 34 ; water soluble &# 34 ; means that the cationic compounds of formula i remain dispersed throughout the laundry solution during the washing process . preferred compounds of formula iinclude those wherein when z is 0 or nh , r 2 is a straight or branched c 24 - 40 alkyl and when z is n , r 1 and r 2 are each a c 16 - 25 alkyl . the anion x - is preferably the anion of a strong acid such as , for example , chloride , bromide , iodide , sulfate and methyl sulfate . the anion may carry a double charge in which case x - represents half a group . preferred compounds of formula iinclude salts of a c 24 - 50 alkyl ester of n - methyl 3 - carboxypyridinium , c 24 - 50 alkyl ester of n - methyl 2 - carboxypyridinium , and c 24 - 50 alkyl ester of n - methyl 4 - carboxypyridium ; and n - methyl n , n dioctadecyl , 3 - carboxamide pyridinium and n - methyl n , n dioctadecyl , 4 - carboxamide pyridinium . the compounds of the invention are prepared from pyridine and quaternary sources which are naturally occurring and not synthetically produced . upon degradation , these compounds are reduced to their natural sources to form environmentally friendly compounds . pyridine carboxylic acid chloride hci salt is added to an alkanol or dialkyl amine in a suitable solvent , such as methylene chloride , toluene and xylene , and the mixture allowed to react at 0 ° to 160 ° c . for 10 - 24 hours . the mixture is treated with sodium carbonate solution , and the isolated pyridine ester or amide is reacted with a methylating agent such as dimethyl sulfate or methyl halide . optionally , a base such as pyridine may be added to neutralize the hci salt . the products may be isolated as waxy materials . useful alkanols include straight or branched chains up to c 50 such as dodecanol , octadecanol , and c 24 - 28 primary branched alcohols known as guerbet alcohols . long chain amines which can be used include dihexadecyl amine having up to two c 32 chains , and mixtures of chains . long chain esters such as n ( ch 2 ch 2 oco 2 c 17 h 35 ) 2 are also possible . the novel compounds may be formulated in a variety of physical forms to form a fabric conditioning composition . such a composition would comprise from about 1 to about 99 wt . % of a compound of formula i and from about 1 to about 99 wt . % water . such compositions may be prepared by any conventional method known in the art . it may be understood that the compounds of the invention may be combined with conventional fabric conditioning components to form a mixture of fabric conditioning actives useful in preparing fabric conditioning compositions . such conventional conditioning agents include acyclic quaternary ammonium salts such as ditallowdimethylammonium - methylsulfate , cyclic quaternary ammonium salts , particularly those of the imidazolinium type , diamido quaternary ammonium salts , tertiary fatty amines having at least 1 and preferably 2 c 8 to c 30 alkyl chains , carboxylic acids having 8 to 30 carbon atoms and one carboxylic group per molecule , esters of polyhydric alcohol such as sorbitan esters or glycerolstearate , fatty alcohols , ethoxylated fatty alcohols , ethoxylated fatty amines , mineral oils , polyols such as polyethyleneglycol , silicone oils and mixtures thereof . suitable conventional fabric conditioning compounds are described in taylor et al ., u . s . pat . no . 5 , 254 , 269 , herein incorporated by reference . additionally , one or more optional additives may be incorporated in the fabric conditioning composition selected from the group consisting of perfumes , dyes , pigments , opacifiers , germicides , optical brighteners , fluoresers , anti - corrosion agents and preservatives . the amount of each additive in the composition is up to about 0 . 5 % by weight . it has been found that the conditioning compositions of the present invention can be incorporated into both granular and liquid detergent formulations with little detrimental effect on cleaning . the compositions are typically used at levels up to about 30 % of the detergent composition , preferably from about 5 to 20 % of the composition . detergent surfactant included in the detergent formulations of the invention may vary from 1 % to about 98 % by weight of the composition depending on the particular surfactant ( s ) used and the cleaning effects desired . preferably , the surfactant is present in an amount of from about 10 to 60 % by weight of the composition . combinations of anionic , preferably alkyl sulfates , alkyl ethoxylated sulfates , linear alkyl benzene sulfonates , and nonionic , preferably alkyl polyethoxylated alcohol surfactants are preferred for optimum cleaning , softening and antistatic performance . it may be appreciated that other classes of surfactants such as ampholytic , zwitterionic or cationic surfactants may also be used as known in the art . as generally known , granular detergents incorporate the salt forms of the surfactants while liquid detergents incorporate the acid form where stable . examples of surfactants within the scope of the invention are described in u . s . pat . no . 4 , 913 , 828 issued to caswell et al ., herein incorporated by reference . builders , accumulating agents and soil release agents known in the art may also be used in the detergent formulations . examples of suitable such components are described in caswell et al ., u . s . pat . no . 4 , 91 3 , 828 , herein incorporated by reference . optional ingredients for the detergent compositions of the present invention other than those discussed above include hydrotropes , solubilizing agents , suds suppressers , soil suspending agents , corrosion inhibitors , dyes , fillers , optical brighteners , germicides , ph adjusting agents , enzyme stabilizing agents , bleaches , bleach activators , perfumes and the like . the following non - limiting examples illustrate the compounds , compositions and method of the present invention . all percentages , parts and ratios used herein are by weight unless otherwise specified . c 24 -- c 28 alkyl ester of n - methyl 3 - carboxypyridinium methyl sulfate was prepared as follows . 7 . 2 g ( 0 . 04 mole ) nicotinic acid chloride hydrochloride in 30 ml methylene chloride was reacted with 15 . 2 g ( 0 . 041 mole ) exxal 26 ( c 24 -- c 28 guerbet alcohol ). the mixture was refluxed for 24 hours , then a solution of 40 g sodium carbonate in 180 ml water was added and the mixture shaken in a separatory funnel . the layers were separated and the methylene chloride layer was dried over mgso 4 . after distilling off the solvent , 17 . 6 g ( 0 . 036 mole ) of nicotinic acid ester was obtained . this product was redissolved in 30 - 40 ml methylene chloride and 4 . 6 g ( 0 . 036 mole ) of dimethyl sulfate was added . the mixture was fluxed for 16 hours , 300 ml methylene chloride added and the solution extracted with water to remove impurities . 21 . 1 g of c 24 -- c 28 alkyl ester of n - methyl 3 - carboxypyridinium methyl sulfate was obtained . n - methyl , n , n dioctadecyl , 3 - carboxamide pyridinium methyl sulfate was prepared as follows : 17 . 8 g ( 0 . 1 mole ) of nicotinic acid chloride hydrochloride in 200 ml toluene was added to 54 . 7 g ( 0 . 105 mole ) dioctadecyl amine and 30 g pyridine . the solution was stirred at 50 ° c . for 30 hours , was cooled and filtered , to remove insolubles . the toluene solution was evaporated on a roto evaporator and the residue was dissolved in methylene chloride . the solution was allowed to sit and insolubles were filtered . the methylene chloride flitrate was evaporated to a liquid to afford 44 g ( 0 . 07 mole ) n , n dioctadecyl 3 - carboxy pyridine . this product was dissolved in 150 ml methylene chloride and reacted with 9 . 4 g ( 0 . 075 mole ) dimethyl sulfate for 24 hours . the solution was extracted with water to remove impurities and the methylene chloride layer was evaporated to afford 54 . 9 g of waxy n - methyl , n , n dioctadecyl , 3 - carboxamide pyridinium methyl sulfate . compounds of examples 1 and 2 are used to prepare fabric conditioning formulations as follows . sample a contains 50 % by weight of the compound of example 1 . the compound is heated to 60 ° c . to form a premelt which is then added to water of 60 ° c . under stirring to form a dispersion . a salt solution as necessary to obtain a desired viscosity is also added . sample b containing 30 % of the compound of example 2 is prepared as described above . to test softening performance , two grams of each of sample a and b are separately added to one liter of tap water of ambient temperature containing 0 . 001 % by weight of sodium alkyl benzene sulphonate to simulate the carry over of anionic detergent active from a wash . 800 ml of the obtained solution are put in a tergotometer pot and four pieces of terry towel ( 40 g total weight ) are added . the cloths are treated for 5 minutes at 60 rpm , spun dried and line dried . the dried fabrics are assessed for softeners by an expert panel . as a control , sample c is prepared as described in example 3 and contains 40 % by weight 1 , 2 ditallow oxy trimethyl ammonium propane chloride . | 2 |
with reference now to the figures , and in particular with reference to fig2 there is depicted one embodiment 10 of the polarized illumination system of the present invention . system 10 is particularly adapted for use with a liquid crystal display ( lcd ) projector , and the combination generally comprises a light source or lamp 12 , a collimator or parabolic reflector 14 , means 16 for separating p - and s - polarized light , taking the form of a polarizing beam splitter ( pbs ), mean 18 for redirecting one of the polarized beams ( in this case , the reflected beam ) parallel with the other polarized beam ( the transmitted beam ), taking the form of a right angle prism reflector , a half - wave retarder plate 20 , a spatial integrator cell 22 , an analyzer 26 , an lcd panel 24 , and a projection lens 28 . embodiment 10 is a single - panel , transmissive lcd projector , but those skilled in the art will appreciate that the general principle can be extended to color and pseudo - color transmissive lcd projectors using multiple panels , as well as reflective lcd light valve projectors . randomly polarized light from light source 12 is collimated by parabolic reflector 14 ( or some other means ) and enters pbs cube 16 . the p - polarized light is transmitted and the reflected s - polarized light is turned 90 ° by light angle reflecting prism 18 , where it is then converted to p - polarized light by half - wave ( λ / 2 ) retarder plate 20 . the adjacent and spatially separated collimated light beams enter the microprismatic spatial integrator cell 22 where they are spatially integrated and exit as a single collimated polarized beam . components 12 - 18 are individually known in the prior art and nearly any conventional components will suffice . therefore , in embodiment 10 , the primary novelty resides in spatial integrator 22 . fig3 shows spatial integrator cell 22 . each adjacent entrance beam is equally deviated by the first microprismatic element 32 , which consists of a series of 60 ° equilateral linear microprisms 34 ( see fig3 a ). half of the light passes directly to a second , oppositely disposed microprismatic element 36 . the other half of the light is reflected off side mirrors 38 and 40 , where it then passes to the opposite microprismatic element 36 . by controlling the length of cell 22 , both beams exit the cell as a spatially integrated and collimated beam . the spatial integrator cell length l = a tan ( π / 6 ), where a is the half - height of the cell ( see fig5 ), and light rays entering the center of cell 22 exit at the edge of the cell . fig3 a shows an enlarged section of first linear microprismatic element 32 , where all the prism angles α = 60 °, and the deviation angle δ = 60 °. there is no refraction , hence no chromatic dispersion , at either microprismatic element since all ray deviations occur by total internal reflection ( tir ), i . e ., the angle of incidence at the interface between air and the microprismatic element is zero . for slight deviations from perfect collimation , there is substantially no chromatic dispersion for rays which are refracted at either surface , and also reflected from the tir facets , since the microprisms are 60 ° equilateral triangles . since pbs cube 16 forms adjacent square beams , each having an aspect ratio ar = 1 : 1 , the polarization converted beam entering and exiting the spatial integrator cell has an ar = 2 : 1 . since most lcd panels have an ar = 4 : 3 = 1 . 33 , the ar should be adjusted for efficient illumination of the lcd panel . one standard method of aspect ratio conversion that preserves the direction of the light beam is by the use of positive and negative cylinder lenses 42 and 44 , respectively , as shown in fig4 . a novel variation of this method is used in the current invention by forming a positive cylinder fresnel lens 46 in the exit surface of the spatial integrator cell 48 , as shown in fig5 . the negative cylinder lens 50 can be continuous or of the fresnel type . another standard method of converting aspect ratio , or anamorphic beam compression , uses a pair of identical prisms as shown in fig6 . the chromatic dispersion of the first prism 52 is canceled by the opposite dispersion of the second prism 54 , and the direction of the collimated light is preserved . a similar effect may be achieved in the current invention by forming the first element as a series of linear microprisms on the exit element 56 of a spatial integrator cell 58 . a second linear microprismatic element 60 is then set at an oblique angle 6 equal to the ray deviation of the first element , as shown in fig7 . for example , for acrylic plastic ( n d = 1 . 492 ) with prism angles α = 40 . 52 °, and δ = 35 . 25 °, the aspect ratio of the beam is converted from 2 / 1 to 4 / 3 , with no chromatic dispersion . it is also possible to perform anamorphic beam compression in conjunction with the present invention with a 90 ° beam deviation , by using two prisms as shown in fig8 . here the first refracting prism 62 is followed by a second prism 64 that deviates the beam by refraction and total internal reflection . by specifying the vertex angles and tilt angles as shown , the chromatic dispersion of the first prism is canceled out by the dispersion of the second prism . for example , using optical crown glass ( n d = 1 . 523 ) for both prisms , and φ 1 = 30 °, φ 2 = 8 °, α 1 = 18 . 6 °, α 2 = 68 °, α 3 = 38 . 2 °, then the beam is converted from an ar = 2 : 1 to an ar = 4 : 3 with negligble chromatic dispersion . if a beam deviation of 90 ° is introduced between the spatial integrator and the lcd panel , there are several other methods of achieving the desired aspect ratio conversion . one method is shown in fig9 which utilizes a reflective wedge prism 66 . the incident beam , having an ar = 2 : 1 is converted to an output beam with an ar = 4 : 3 by specifying the tilt angle φ and the prism wedge angle α . here the φ value shown is an approximation . in practice , it is necessary to account for the varying prism thickness and its effect on the compression of the exit beam . thus φ and α are iteratively adjusted until the exit beam is compressed to achieve the desired aspect ratio . for a reflecting wedge prism 66 of optical crown glass ( n d = 1 . 523 ), φ ≈ 17 . 0 °, and α ≈ 13 . 9 °, a beam compression ratio a &# 39 ;/ a = 0 . 375 can be obtained . fig1 shows a spatial integrator 70 where anamorphic beam compression and spatial integration of dual incoming beams has been performed using reflecting wedge prisms 72 and 74 , and auxiliary planar side mirrors 76 and 78 . the prism deviation angle δ is 60 °, and the entrance angle for the 60 ° linear microprismatic elements 80 and 82 is 60 °. for the figure shown : θ = angle of incidence of exiting reflected ray at refracting surface of wedge prism , θ &# 39 ;= angle of refraction of entrance ray at refracting surface of wedge prism , and for c = 2 / 3 , two adjacent collimated entrance beams of the same polarization , each of cross - section a × a , are combined into an integrated , collimated and polarized exit beam of cross - section 4a / 3 × a , having an aspect ratio ar = 4 : 3 , each reflecting wedge prism has refractive index n d = 1 . 523 , φ = 26 . 0 °, and α = 15 . 2 °. in the system of fig1 , the reflecting surfaces of the wedge prisms are generally opposed , but not parallel . fig1 shows a compact lcd illumination and projection system 84 using this combined spatial integrator and anamorphic beam compressor . fig1 shows a polarization converter 86 that uses two reflecting prisms 88 and 90 and a single 60 ° microprismatic element 92 to spatially integrate the two beams and convert the aspect ratio . collimated light enters a polarization beam splitter 94 where the p - polarized light is transmitted and s - polarized light is reflected and converted to p - polarized light by the half - wave retarder 96 . the two beams enter reflecting prisms at a 45 ° entrance angle , are compressed by a factor c , and exit the prisms at an angle of 60 °. there is a 75 ° deviation angle δ between the input and exit beams of the reflecting prism . the compressed beams are then spatially integrated into a single collimated polarized beam by the 60 ° microprismatic element . an incoming beam having an aspect ratio ar = 1 can be converted to an outgoing beam having an aspect ratio ar = 4 : 3 by the use of reflecting prisms having a refractive index n d = 1 . 523 , a vertex angle α = 10 . 3 °, a tilt angle φ = 26 °, and an anamorphic compression factor c = 2 / 3 . a single panel lcd projection system was constructed as an optical breadboard to evaluate components of the current invention . a 24 volt , 250 watt tungsten - halogen lamp ( ehj type ) having a spherical back reflector , produced a beam of collimated light of ≈ 50 mm diameter by means of a pair of glass condensing lenses . the beam was masked down to a 32 mm by 32 mm square aperture , and a piece of heat reflecting glass was positioned near this square aperture . a broadband 450 - 680 nm pbs cube ( melles griot # 03 pbb 007 ) produced a transmitted p - polarized beam and a reflected s - polarized beam . a 45 ° uncoated prism ( edmund scientific # 32531 ) deviated the reflected beam 90 ° by total internal reflection to be adjacent to the transmitted beam . the s - polarized beam was converted to a p - polarized beam by a half - wave retarder sheet ( polaroid # 605208 ). a spatial integrator cell was constructed using two linear 60 ° microprism elements , each element 32 mm wide by 64 mm high , of 2 mm thick acrylic , with each microprism width = 0 . 25 mm . the separation of the microprism elements was l = 18 . 5 mm . spatial integration and common polarization of the two beams was verified by examining the output from the spatial integrator cell . an anamorphic beam - compressing reflecting wedge prism was constructed from acrylic plastic ( n d = 1 . 492 ), having a length of 100 mm , a width of 38 mm , and a wedge angle = 14 . 3 °. the reflecting wedge prism changed the beam dimension exiting the spatial integrator from 64 mm by 32 mm ( ar = 2 : 1 ) to 32 mm by 24 mm ( ar = 4 : 3 ). a vga compatible 1 . 3 &# 34 ; diagonal monochrome lcd module ( seiko epson # p13vm115 / 125 ), with an analyzer on the exit side , was illuminated by the collimated and polarized light beam exiting the wedge prism . a piano - convex field lens focused the light from the lcd module into a 3 &# 34 ; focal length , f / 2 . 5 coated anastigmat projection lens ( jml optical industries ). using a spectra - physics brightness spot meter , measured brightness increase of the projected screen image was ≈ 70 %, when the output of the converted polarized light was added to the primary beam . although the invention has been described with reference to specific embodiments , this description is not meant to be construed in a limiting sense . various modifications of the disclosed embodiment , as well as alternative embodiments of the invention , will become apparent to persons skilled in the art upon reference to the description of the invention . it is therefore contemplated that such modifications can be made without departing from the spirit or scope of the present invention as defined in the appended claims . | 6 |
with reference to fig1 , a flow diagram of a plant - system for the manufacture of melamine from urea in a high - pressure process is shown . in this melamine plant , which is indicated in its entirely with reference number 1 , block 2 indicates a high - pressure reactor for melamine synthesis , block 3 indicates a quenching section for a melamine melt obtained in the reactor 2 , block 4 indicates a melamine crystallisation section , block 5 indicates a liquid / solid separator for recovering melamine crystals of high purity and block 6 indicates a mother liquor treatment section for ammeline conversion . generally , in the present description and in the enclosed claims , and where it is not differently indicated , by the terms : “ feeding or connecting means or flow line ”, it is intended to mean pipelines , connecting lines or ducts , pumps , compressor , ejectors or other devices of known type , which are used for transporting a liquid or gaseous flow from a location to another one in the plant . flow line 7 indicates a flow of liquid urea fed to the reactor 2 in which it is converted into melamine by pyrolysis . the reactor 2 usually operates at a pressure in the range of 70 bar to 200 bar and at a temperature in the range of 360 - 420 ° c . the reacted mass is discharged by the reactor as two separate outputs , namely a gas flow 8 comprising ammonia and carbon dioxide and melamine vapours , and a flow 9 of raw melamine in liquid phase or melt which also contains some impurities such as oat and polycondensates . the gaseous flow 8 is normally recycled to the urea synthesis plant after separation of the melamine vapours ( which are in turn returned to the reactor 2 ) in a conventional gas scrubbing unit ( not shown ). on the contrary , the flow 9 of raw melamine is fed to the quenching section 3 where it is brought into intimate contact with a flow 10 of mother liquor , the latter coming from the treatment section 6 for ammeline conversion , in the manner that will be better disclosed in the following description , obtaining a melamine solution in concentrated ammonia - water where the polycondensates present are substantially fully converted into melamine . the quenching section 3 is kept at a temperature of 150 - 190 ° c ., under autogenously pressure , and is crossed by a small flow of gaseous ammonia , injected through line 11 , while the excess is relieved through line 12 . the melamine solution discharged from the quenching section 3 is fed , through the flow line 13 , to the crystallisation section 4 where the temperature is lowered to 30 ° c .- 60 ° c ., under autogenously pressure , causing the precipitation of crystals of very high - purity melamine , while the residual impurities and residual melamine remain into the solution . the liquid stream containing the residual impurities and residual melamine ( so - called mother liquor ), and the crystallized melamine are discharged from the crystallisation section 4 and fed , through the flow line 14 , to the liquid / solid separation section 5 where crystallized melamine is separated from the mother liquor . melamine crystals , as discharged by the flow line 15 , are wet of mother liquor , which is removed by the usual technique of washing the crystals cake with water , obtaining a filtrate ( containing dissolved melamine ), which is returned to the mother liquor loop . crystals are dried and delivered to the final packing . from the separation section 5 the mother liquor is transferred , through the flow line 16 , to the treatment section 6 , where the liquid flow is heated up to 150 - 190 ° c ., under autogenously pressure , and is kept in that condition for a time of 1 to 4 hours , depending on the operating temperature ( the higher the temperature , the shorter the residence time ). in this way , the ammeline in solution converts mainly into melamine , and to a lesser extent into ammelide . finally , the treated mother liquor is closing the loop by recycling , through the flow line 10 , to the quenching section 3 . a very minor part of the mother liquor from section 6 is purged off through the flow line 17 , to avoid an excessive build up of ammelide inside the mother liquor loop , and therefore risking the precipitation of ammelide during melamine crystallization . this stream is de - ammoniated and possibly neutralised in a ammelide removal section 18 obtaining the precipitation of ammelide , which is separated by filtration and discharged through the flow line 19 , while the filtrate , containing melamine , is returned to the mother liquor loop through the flow line 20 . fig2 shows an apparatus according to an embodiment of the present invention for melamine quenching suitable to be used in the quenching section 3 of the melamine plant of fig1 . this quenching apparatus is indicated , in its entirety , with reference number 20 . the apparatus 20 comprises a vessel 21 , of cylindrical , vertical type , which is designed and constructed so as to be effectively operated at a pressure substantially equal or below the operating pressure of the reactor 2 , for example a pressure of 20 - 100 bar , preferably 30 - 70 bar and at an operating temperature of the melamine quenching preferably in the range of 150 - 190 ° c . the vessel 21 is internally provided with a mechanical agitator indicated in its entirety with 26 and baffles 23 extending vertically from the shell of the vessel 21 for transferring to the liquid under agitation a significant deal of power . the agitator 26 includes a vertical shaft 27 extended along the vertical axis of the vessel 1 from its top to the lower portion of the vessel 21 , and an impeller 22 at the lower end of the shaft 27 . the agitator impeller 22 may be of turbine , or of propeller type and preferably it is a flat - blades turbine . the agitator 26 is controlled by a suitable motor 28 situated external to the vessel 21 . the vessel 21 is also internally provided with heat transfer coils 24 which may be realised as pipes internally crossed by a heat transfer fluid , as for instance by a stream of diathermic oil or pressurised boiling water . in particular , the heat transfer fluid enters the vessel 21 and the coils through a inlet pipe 29 and is discharged from them through a outlet pipe 30 . the vessel 21 also comprises suitable openings ( not shown ) for the inlet of the mother liquor coming from the treatment section 6 , for the inlet of melamine melt coming from the reactor 2 , for the inlet and the outlet of gaseous ammonia and for the outlet of melamine solution . in particular , according to the present invention , the mother liquor is introduced in the vessel 21 through the pipe 10 . melamine melt is admitted through pipe 9 , which preferably extends inside the vessel 21 from its top to the proximity of a upper part of the agitator impeller 22 . in this way , advantageously , as soon as the melt arrives to the upper part of the agitator impeller 22 , it is immediately dispersed inside the liquid phase present in the vessel 21 . gaseous ammonia is fed to the vessel by pipe 11 , which is advantageously extended inside the vessel 21 from its bottom to a lower part of the agitator impeller 22 . in this way , as soon as ammonia arrives to the lower part of the agitator impeller 22 , it is immediately subdivided into very fine droplets , and dispersed inside the liquid phase present in the vessel 21 . surplus ammonia is relieved through pipe 12 according to the invention , in the vessel 21 , melamine melt is contacted with mother liquor and quenched at a temperature from 150 ° c . to 190 ° c ., preferably 160 ° c .- 180 ° c ., while the resulting solution is kept into intimate contact with gaseous ammonia , for a time in the range from 15 minutes to 90 minutes . in this way , melamine passes into solution at a concentration preferably from 8 % to 16 % by weight while , at the same time , some of the impurities such as polycondensates , as formed in the reactor 2 , are converted to melamine by reaction with ammonia , obtaining the practical disappearing of polycondensate content in the resulting melamine solution . in this regard , according to the invention , ammonia present in the mother liquor and gaseous ammonia are preferably introduced into the vessel 21 so as to keep a concentration in said solution in the range from 20 % to 35 % by weight , in the stated range of temperatures , at the equilibrium pressure reached by the quench vessel . in addition , gaseous ammonia is advantageously highly dispersed and distributed in the liquid mass thanks to the agitator impeller 22 which realizes a high efficient gas - liquid contacting system . in the vessel 21 , the temperature conditions are controlled by the heat exchanging fluid flowing in the coils 24 which removes heat from the vessel 21 to keep the total liquid mass at the desired temperature . the liquid phase discharged out from the vessel 21 is transferred to the successive crystallisation section 4 of the plant 1 , where it is immediately cooled down to the final crystallisation temperature , in the range of 30 to 60 ° c . under autogenously pressure . the transfer may be simply done under the pressure differential through pipe 13 by means of a level control device or by a pump . fig3 shows an apparatus according to another embodiment of the present invention for melamine quenching suitable to be used in the quenching section 3 of the melamine plant of fig1 . this quenching apparatus is indicated in its entirety with reference number 40 . to the elements of the apparatus 40 of fig3 which are structurally or functionally equivalent to corresponding elements of the apparatus 20 of fig2 the same reference numbers of the latter elements are assigned . the apparatus 40 includes a vessel 41 and closed loop , indicated in its entirety with reference number 42 , external to the vessel 41 . the closed loop 42 includes a suction pump 44 , a heat exchanger 45 , a pipe 43 connecting the bottom of the vessel 41 to the pump 44 , a pipe 46 connecting the pump 44 to the heat exchanger 45 and a pipe 47 connecting the heat exchanger 45 to the vessel 41 . in this embodiment , all fluids to be intimately mixed together , namely mother liquor coming from the flow line ( pipe ) 10 , melamine melt coming from the flow line ( pipe ) 9 and gaseous ammonia coming from the flow line ( pipe ) 11 are mixed in the pipe 43 and the resulting liquid / gaseous phase is allowed to circulate continuously in the closed loop 42 and in the vessel 41 through the pump 44 . this allows ammonia to be finely distributed in the liquid mass . the control of the liquid temperature is performed by the heat exchanger 45 crossed at the process side by the liquid / gaseous phase from which heat is removed as necessary by a heat exchanging fluid . a flow of melamine solution is continuously discharged out from the vessel 41 through pipe 13 and sent to the crystallisation step in the section 4 as indicated above . fig4 shows an apparatus according to an embodiment of the present invention for treating crystallization melamine mother liquor in order to convert ammeline into ammelide and melammine . this apparatus is indicated , in its entirety , with reference number 60 and is suitable to be used in the treatment section 6 of the melamine plant of fig1 . the apparatus 60 comprises single pressure vessel 61 of total volume sufficient to allow the mother liquid flow the desired residence time at the selected temperature . the pressure vessel 61 is internally provided with a mechanical agitator 66 and baffles 63 extending vertically , helping the liquid under agitation to have heat transferred from the coil 64 , internally crossed by a heating fluid , as for instance condensing steam . in particular , the heat transfer fluid enters the vessel 61 and the coils 64 through a inlet pipe 69 and is discharged from them through a outlet pipe 65 . the agitator 66 includes a vertical shaft 67 extended along the vertical axis of the vessel 61 from its top to the lower portion of the vessel 61 , and an impeller 62 at the lower end of the shaft 67 . the agitator impeller 62 may be of turbine , or of propeller type and preferably it is a flat - blades turbine . the agitator 66 is controlled by a suitable motor 68 situated external to the vessel 61 . the vessel 61 is also internally provided with heat transfer coils 24 which may be realised as pipes internally crossed by a heat transfer fluid , as for instance by a stream of diathermic oil or steam . in particular , the heat transfer fluid enters the vessel 21 and the coils 24 through a inlet pipe 29 and is discharged from them through a outlet pipe 30 . the mother liquor is introduced in the vessel 61 through the pipe 16 , while the treated liquid exits through the pipe 10 . fig5 shows an apparatus according to another embodiment of the present invention for treating crystallization melamine mother liquor in order to convert ammeline into ammelide and melammine . this apparatus is indicated , in its entirety , with reference number 70 and is suitable to be used in the treatment section 6 of the melamine plant of fig1 . the apparatus 70 comprises two pressure vessels 71 a and 71 b , of the same configuration as for vessel 61 described above , set in series on the liquid flow . this configuration has the advantage of using much smaller vessels , i . e having a volume lower than in case of single vessel 61 . according to another embodiment of the invention ( not shown ), the mother liquor coming from the solid / liquid separation section 5 may be pre - heated at the desired temperature in an appropriate exchanger upstream the vessel 61 of apparatus 60 or the vessel 71 a of apparatus 70 . in this case , the heat transfer coils 64 in vessel 61 or vessels 71 a and 71 b are not required anymore . in the vessel 61 of apparatus 60 and in the vessels 71 a and 71 b of apparatus 70 , due to the temperature increase , the ammonia solution constituting the mother liquor rises in pressure up to 15 - 80 bar pressure , depending on the ammonia concentration used . the treated mother liquor , depleted in ammeline , and enriched in melamine ( and some ammelide ) is transferred to the quenching section 3 , which operates at approximately the same temperature and pressure of the ammeline conversion section 6 . the following examples are intended to better show as the invention may be practiced , and the advantages thereof , but they are not to be interpreted as limiting its scope . a sample of 100 g of melamine melt , as delivered by a high - pressure technology after separation of the off gas , and kept in liquid phase at 390 ° c ., 80 bar pressure , had the following composition ( percentages by weight ): the sample has been quickly transferred into a stirred tank reactor , kept at 170 ° c ., where 800 g of aqueous solution of ammonia at 31 % strength had been previously placed . the vessel reached an internal pressure of 41 bar . after 10 minutes under stirring , the reactor content was quickly transferred in a further , agitated vessel , equipped for cooling down rapidly to about 40 ° c . the obtained melamine solution . after reaching the desired temperature , the vessel internal pressure was about 1 bar . a sample of liquid phase , submitted to analysis , showed a melamine concentration of 0 . 67 %, ammeline 0 . 08 %, which is less than its solubility limit in ammonia 31 % strength , ammelide 0 . 02 %, very far from its solubility limit ( 2 %). poly - condensates were not detectable . urea resulted to be partially hydrolysed . separated melamine crystals were of very high purity . similar to the one recovered in example 1 from the melamine crystallization step , has been fed in continuous , at the rate of 800 g / h , into a 1 - liter stirred tank reactor heated to maintain the temperature constant to 180 ° c . gaseous ammonia has been injected in the same reactor to raise the pressure up to 66 bar . by keeping constant the internal liquid level , the product was discharged , cooled and analysed . ammeline was substantially disappeared , and converted by approx 80 % into melamine , the balance into ammelide . the same experiment has been repeated in milder conditions , by halving the ammonia concentration and operating at 170 ° c ., bar pressure . in order to observe a substantial conversion of ammeline the flow rate had to be reduced down to 250 g / h . meanwhile the main product of the reaction was ammelide . the process according to the invention for obtaining melamine at high purity was carried out in a pilot plant according to fig1 . a melamine melt having the same composition described in example 1 was delivered by the high - pressure urea reactor 2 . this melamine melt was fed , at a rate of 100 kg / h , to the quenching section 3 in a stirred tank - type reactor ( vessel 21 ) equipped as described above with reference to fig2 , the reactor 21 accommodating 150 liters of liquid volume and the quenching and dilution process taking place in the reactor 21 at 170 ° c . the same reactor 21 received in continuous 810 kg / h of recycled , aqueous ammonia solution containing 250 kg / h of ammonia , and about 550 kg / h of water , the balance being mainly dissolved melamine and ammelide ( recycled mother liquor ). said aqueous ammonia solution came from the ammeline conversion section 6 , operating also at 170 ° c . and the quenching reactor 21 and the ammeline conversion section 6 operated at approximately the same , autogenously internal pressure of 44 bar . the temperature of the quenching reactor 21 , receiving the melamine melt at 380 - 390 ° c . and the ammonia solution at 170 ° c ., was temperature - controlled at 170 ° c . by adequate cooling . the liquid overflowing in continuous from the quenching reactor was a 10 . 7 - 10 . 9 % strength solution of melamine , practically free of melamine poly - condensates . it was de - pressurized and fed in continuous to the crystallization section 4 in a cooler - crystallizer of about 1 m 3 volume , wherein the temperature of the process matter was kept at 45 ° c . the pressure of the crystallizer stabilized at 1 . 2 bar . melamine crystals precipitated , forming with the mother liquor a slurry , which was gradually extracted from the crystallizer , and fed to a centrifuge , which provided the crystals separation , and washed with demineralised water , while the filtrate mother liquor was collected in a tank , at atmospheric pressure . the mother liquor , which was saturated by 0 . 84 % melamine , and contained 0 . 12 % ammeline and 0 . 17 % ammelide , was fed in continuous , at a rate of about 940 liters / h , to the ammeline conversion section 6 in a stirred tank reactor ( vessel 60 ), provided by an internal steam coil , heating the liquid and keeping it at 170 ° c . as described above with reference to fig4 . a small flow of gaseous ammonia was also introduced , to compensate for the losses at the crystals separation in the reactor 60 , up to reach an internal pressure of 44 bar . the reactor volume was 2 m 3 , providing then a liquid phase residence time of about 2 hours . thanks to this operation , the poorly soluble ammeline was converted into melamine and ammelide , allowing to re - circulating the aqueous ammonia solution ( mother liquor ) without the risk of ammeline precipitation during the melamine crystallization step . in addition , some urea ( 0 . 45 %) left in solution as residual from the melamine melt , was effectively hydrolysed in this reactor 60 . the 80 % of the treated mother liquor stream was re - sent directly to the quench section 3 while the remaining 20 % of the treated mother liquid stream was purged off to remove ammelide , in the average about 0 . 4 kg / h , to avoid its excessive build - up in the process loop . the removal was done in ammelide removal section 18 by stripping away the dissolved ammonia , which makes ammelide insoluble in the residual water and separating ammelide by filtration . then , the mother liquid stream substantially deprived of ammelide and still containing some melamine , was recovered from the treatment section 18 and returned to the process loop in the mother liquid stream to be recycled to the quench section 3 . in this way , the concentration of oat in the process loop never reached the solubility limit , above which it could precipitate and contaminate the produced melamine . in addition , the process yield was very high , namely more than 98 % of melamine having high purity ( more than 99 . 8 %) was recovered from the original melt containing melamine as such , or under form of poly - condensates and oat . a study was been carried out with the aim of reducing as much as possible the fraction of mother liquor to be purged off for the elimination of ammelide , after its generation from ammeline , as shown in the preceding examples , avoiding at the same time the risk of ammeline or ammelide precitation in the aqueous ammonia solution at the melamine crystallization step in the crystallization section 4 . according to this study , it was found that operating the plant of the preceding example 3 in the same conditions , but by reducing the purging from 20 % to 10 % of the re - circulating aqueous ammonia solution ( recycled mother liquid ), the risk of oat precipitation at melamine crystallization is avoided by 5 % increase of the ratio between aqueous ammonia solution and melamine melt at the quenching section 3 . furthermore , purge reduction to 5 % of the recycled mother mother was possible by increasing of 20 % the aqueous ammonia solution / melamine melt ratio at the quenching section 3 . | 1 |
referring now to the figures of the drawing in detail and first , particularly , to fig1 a thereof , there is shown a memory element se with magnetoresistive effect that is arranged between a first line l 1 , for example made of alcu , and a second line l 2 , for example made from alcu . the memory element se is electrically connected both to the first line l 1 and to the second line l 2 . the first line l 1 and the second line l 2 run perpendicularly to one another . the memory element se is arranged at the point of intersection between the first line l 1 and the second line l 2 . the second line l 2 is partially surrounded by a yoke j ( see fig1 a ). the yoke j includes an upper part j 1 , two lateral parts j 2 and two lower parts j 3 . the upper part j 1 adjoins that surface of the second line l 2 which faces away from the memory element se . the lateral parts j 2 adjoin the upper part j 1 and the side walls of the second line l 2 . the lower parts j 3 adjoin the lateral parts j 2 and the part of the surface of the second line l 2 which is adjacent to the memory element se . the yoke j is formed from iron . furthermore , all the soft ferromagnetic elements such as fe , feni , ni , co or similar are suitable . the thickness d of the upper part j 1 perpendicular to the plane extending through the first line l 1 and the second line l 2 , and the comparable thickness of the lateral parts j 2 parallel to the plane extending from l 1 and l 2 are approximately 20 percent of the width of the line l 2 . the thickness d of the lower parts j 3 perpendicular to the plane extending from the first line l 1 and the second line l 2 is at least equal to the thickness of the memory element se , at maximum approximately 20 percent of the width of the conductor track l 2 ( see fig1 b ). if a current flows through the second line l 2 , a magnetic field h is generated outside the line l 2 . this magnetic field generates in the yoke j a magnetic flux φ = μ o μ r which is approximately constant in the magnetic circuit . in the upper part j 1 of the yoke , the magnetic flux φ = μ o μ r f h , f = d b being the cross sectional face of the yoke parts j 1 and j 2 , and b the extent of the yoke j perpendicular to the plane of the drawing . in the lower parts j 3 of the yoke j the magnetic flux ( φ = μ o μ r f h , f = d b being the cross sectional face of the parts j 3 . the lower parts j 3 of the yoke j have magnetic poles on the end faces which face one another . a magnetic field ha for which the following approximately applies owing to the constancy of the magnetic flux : h a = μ r f / f h is generated between the magnetic poles p . because , on the other hand , the maximum achievable magnetic field strength in soft - magnetic material is determined , in the case of saturation , by the saturation magnetization m s of the pole shoe material , the following applies : h a = f / f ( h + m s )≈( f / f ) m s . in comparison with the saturation magnetization m s , the magnetic field h , which is of the order of the magnitude of 10 to 100 a / cm , is usually negligible . iron has a saturation induction of μ o m s ( m s : saturation magnetization )= 2 . 1 t . the maximum achievable magnetic field strength h a is thus 1 . 67 × 10 6 a / m ( 21 koe ) if f / f equals 1 . in this statement it has been assumed that the leakage field losses between the lower parts j 3 of the yoke j and the memory element se are negligible . a memory element se ′ with magnetoresistive effect is switched between a first line l 1 ′ and a second line l 2 ′ ( see fig2 a ). the first line l 1 ′ is partially surrounded by a yoke j ′. the yoke j ′ has a lower part j 1 ′ and two lateral parts j 2 ′. perpendicular to the plane extending through the first line l 1 ′ and the second line l 2 ′, the lower part j 1 ′ of the yoke j ′ has a thickness d of approximately 20 percent of the width of the line l 1 ′ ( see fig2 b ). the thickness of the memory element se ′ perpendicular to the plane passing through the first line l 1 ′ and the second line l 2 ′ is d = 20 nm to approximately 100 nm . if a current flows through the first line l 1 ′, a magnetic field h is produced which brings about a magnetic flux φ in the yoke j ′ and the memory element se ′. as a result the memory element can be switched as a function of the sign of the current . in the same way as in the exemplary embodiment explained with reference to fig1 a and 1 b , in this exemplary embodiment which is to be preferred in terms of production , a comparable reinforcement and concentration of the magnetic field generated by the conductor current is produced at the location of the memory element se ′. this concentrated variant results in inhomogeneous magnetization distributions in the memory element in the edge areas which adjoin the yoke j 2 ′. these do not adversely affect the switching effect , but must be taken into account during reading out . the manufacture of a memory cell array for a 0 . 18 μm technology will be described below with reference to fig3 to 8 . a first insulating layer 2 made of sio 2 is applied to a carrier wafer 1 made of monocrystalline silicon . the first insulating layer 2 has a thickness of 300 to 400 nm . a first trench 3 is produced in the first insulating layer 2 using photolithographic process steps . the first trench 3 has a depth of 200 to 300 nm , a width of 250 to 300 nm and a length , dependent on the cell field , of 50 μm to 400 μm . subsequently , a first soft - magnetic layer 4 made of fe or permalloy ( ni 80 fe 20 ) is deposited to a layer thickness of 20 to 60 nm . the thickness of the first soft - magnetic layer 4 is approximately 10 to 20 percent of the width of the first trench 3 . the deposition can be carried out by sputtering , vapor deposition , cvd , electroplating or the like ( see fig3 ). the first soft - magnetic layer 4 is structured transversely to the direction of the first trench 3 using photolithographic process steps and anisotropic etching , so that it has a strip intersecting the first trench 3 . by depositing a metalization layer which contains alcu and fills up the region of the first trench 3 completely , and by subsequent chemical - mechanical polishing a first line 5 is formed , and a first yoke 4 ′ is formed by structuring the first soft - magnetic layer 4 . the extent of the first yoke 4 ′ perpendicular to the plane of the drawing is determined by the proceeding structuring and is 200 to 300 nm . the chemical - mechanical polishing stops as soon as the surface of the first insulating layer 2 is exposed ( see fig4 ). a thin insulation layer 6 made of sio 2 is deposited over the entire surface to a layer thickness of 20 to 60 nm and is structured using photolithographic process steps in such a way that the surface of the first line 5 is partially exposed . a first ferromagnetic layer 7 is subsequently generated by deposition and chemical - mechanical polishing . the first ferromagnetic layer 7 fills up the opening in the insulation layer 6 . the first ferromagnetic layer 7 is electrically connected to the first line 5 ( see fig5 ). the thickness of the ferromagnetic layer 7 is 20 to 40 nm , the width is 180 to 200 nm and the depth perpendicular to the plane of the drawing is 180 to 200 nm ( see fig5 ). the first ferromagnetic layer 7 is insulated from the first yoke 4 ′. a tunnel barrier layer 8 made of al 2 o 3 is formed on the surface of the first ferromagnetic layer 7 by reactive sputtering a 2 to 4 nm thick aluminum oxide layer ( al 2 o 3 ) ( not shown on drawing ). the first ferromagnetic layer 7 is formed from co ( or another ferromagnetic material ). a second ferromagnetic layer 9 is formed on the surface of the tunnel layer by deposition and photolithographic structuring . the second ferromagnetic layer 9 is formed from co . it has a thickness of 20 to 60 nm , a width of 180 to 200 nm and a depth transversely to the path of the first line 5 of 200 to 300 nm ( see fig6 a and fig6 b ). a second insulating layer 10 made of sio 2 is deposited to a layer thickness of 200 to 300 nm . a second trench 11 is produced in the second insulating layer 10 using photolithographic process steps . the surface of the second ferromagnetic layer 9 is at least partially exposed on the bottom of the second trench 11 . the second trench 11 has a width of 200 to 300 nm , a depth of 200 to 300 nm and a length perpendicular to the routing of the first line 5 of 50 to 400 μm . spacers 12 are formed on the edges of the second trench 11 by depositing a second soft - magnetic layer made of fe or ni 80 fe 20 and anisotropic etching back . the width of the spacers 12 is 20 to 60 nm . it is determined by the thickness of the deposited second low - reactivity layer . a second line 13 is formed in the second trench 11 by depositing a metalization layer which has alcu and a thickness of 200 to 400 nm , and subsequent chemical - mechanical polishing which stops at the surface of the second insulating layer 10 made of sio 2 . the second line 13 fills the second trench 11 completely ( see fig7 ). a yoke part 14 whose cross section corresponds essentially to the cross section of the second ferromagnetic layer 9 is formed on the surface of the second line 13 by depositing a third soft - magnetic layer of 20 to 60 nm and structuring using photolithographic process steps . the yoke part 14 and the spacers 12 together form a second yoke which partially surrounds the second line 13 . the second yoke reinforces the magnetic field generated by the second line 13 through which current flows , at the location of the second ferromagnetic layer 9 . the first yoke 4 ′ reinforces the magnetic field which is generated by the first line 5 through which current flows . the first line 5 and the second line 13 are connected by means of a memory element which is formed from the first ferromagnetic layer 7 , the tunnel layer 8 and the second ferromagnetic layer 9 and which exhibits a magnetoresistive effect . the resistance of the memory element can be measured by appropriately driving the first line 5 and the second line 13 . in this way , the information stored in the various magnetization states is read out . to write information , the first line 5 and the second line 13 are driven in such a way that the magnetic field at the location of the second ferromagnetic layer 9 , resulting from the current flow , is sufficient to change the magnetization state of the second ferromagnetic layer 9 . because of the different material properties , the magnitude and / or the ferromagnetic layer 7 , 9 , the magnetization state of the first ferromagnetic layer 7 remains unchanged here . to form a memory cell array which has magnetoresistive elements and memory cells s , the memory elements s are arranged in a grid ( see fig9 ). each memory element s is switched here between a first line le 1 and a second line le 2 . the first lines le 1 run parallel to one another and intersect the second lines le 2 which also run parallel to one another . | 6 |
with reference now to the drawings , and particularly to fig1 and 10 , there is shown a cut - away perspective view of a metal building 100 . with reference to fig1 , 11 , the metal building 100 preferably includes a heat collection air gap layer 10 , 12 , air vent spacers 36 , 38 , an insulation retaining sheet material 14 , 30 , a material insulation layer 16 , 32 , 34 and a plurality of ducts 40 , 42 , 44 , 48 , 50 . the metal building 100 is shown , but other types of buildings may also be used . the metal building 100 includes a plurality of rafter columns 102 , a plurality of end columns 104 , a plurality of wall girts 106 , a plurality of rafters 108 , a plurality of purlins 110 , 128 , 134 , a plurality roof exterior sheeting panels 112 , a plurality of wall exterior sheeting panels 114 and a peripheral base channel 116 . the plurality of rafter columns 102 and the plurality of end columns 104 are attached to the peripheral base foundation 118 . the peripheral base channel 116 is attached to a foundation 118 to form a perimeter of the metal building 100 . the plurality of girts 106 are retained between horizontally extended girt clips 111 , off the exterior surfaces of the plurality of rafter columns 102 and end columns 104 . the plurality of rafters 108 are attached to a top of the plurality of rafter columns 102 . the plurality of purlins 110 , 128 , 134 are retained between vertically extended purlin clips 113 above the exterior faces the plurality of rafters 108 . with reference to fig1 and 16 , the heat collecting air gap layers include a roof heat collecting ceiling air gap layer 10 and a wall heat collecting air gap layer 12 , which communicate with each other on demand through duct damper holes 56 to increase the total heat collector surface area available to absorb solar heat . the solar heat from the east , west , south or north walls can be individually directed through ducts 40 , 42 , 48 through damper holes 56 to the solar exposed roof 120 , to melt snow and ice , thereby maximizing the total heat absorption surface area to achieve greatest volume and heat energy concentration . with reference to fig2 - 8 , the composite roof assembly preferably includes at least one ceiling sheet material 14 , a ceiling material insulation layer 16 , at least two intermediate ceiling support struts 18 , at least two ridge ceiling support struts 20 and at least two eave inside corner ceiling support struts 22 . each intermediate ceiling support strut 18 and eave inside corner ceiling support strut 22 are attached between two adjacent rafters 108 . each ridge ceiling support strut 20 is attached to two adjacent rafters 108 adjacent a ridge 122 of the roof 120 and vertically aligned below the roof 120 ridge purlins 128 . each eave inside corner ceiling sheet material support strut 22 is attached to define an inside corner between a roof 120 and a side wall 124 sheet materials 14 , 30 of the metal building 100 . one end of the ceiling sheet material 14 is inserted behind the eave inside corner ceiling sheet material support strut 22 , above the intermediate ceiling sheet material support struts 18 , above the ridge ceiling sheet material support strut 20 adjacent a ridge 122 of the roof 120 and securely attached to the nearest ridge ceiling support strut 20 with fasteners or the like . the other end of the ceiling sheet material 14 is attached to either a foundation 118 or a floor 126 of the metal building 100 with adhesive , a tensioning device 24 or any other suitable means . with reference to fig1 a - 10 h , a variety of tensioning devices include a turnbuckle tensioning device 202 , a right angle take - up tensioning device 204 , a hook and threaded rod tensioning device 206 , a ratchet strap tensioning device 208 , a turning shaft tensioning device 210 , a single adjustable strut tensioning device 212 , a bi - directional adjustable strut tensioning device 214 and a strap winch tensioning device 216 . alternatively , one end of the sheet material 14 is secured to the foundation 118 or the floor 126 on one side of the metal building 100 and the other end of the sheet material 14 is inserted around the exterior side of one eave inside corner ceiling support strut 22 , inserted over the intermediate ceiling sheet material support strut ( s ) 18 , inserted over the two ridge ceiling sheet material support struts 20 , inserted over the opposite side intermediate ceiling sheet material support strut ( s ) 18 , inserted over the opposite side eave inside corner , ceiling sheet material support strut 22 and finally secured with a tensioning device 24 or any other suitable means to the foundation 118 or floor 126 on an opposing side of the metal building 100 . significant tension is typically required to limit deflection when supporting the load of the material insulation layer without the intermediate fasteners and the resultant thermal bridging common to all known prior art . the ceiling insulation layer 16 is laid on the at least one ceiling sheet material 14 and includes an insulation thickness that extends upward to near the bottom of the plurality of purlins 110 . although not required , an air flow path is desired between the material insulation layer 16 and the bottom of the plurality of purlins 110 to allow cooler , more dense air to flow toward the eave purlin 134 to more efficiently complete the movement of the heat energy up over the purlins 110 to the ridge 122 and allow the cooler , more dense air is allowed to flow back down toward the eave purlin 134 . open web purlins and joists are not shown , but allow the heat energy , humidity and air to flow in all directions without this efficiency concern . fig1 - 13 show a plurality of inner vent spacers 38 that include air vent holes 39 which would be installed on the under side of the bottom flange 132 of the plurality of solid web purlins 110 , 128 to ensure an air circulation path from ridge to eave . the ceiling heat collecting air gap layer 10 is created between a top of the ceiling material insulation layer 16 and a bottom of the roof panel 112 . preferably the roof sheeting panels 112 are connected to the tops of the purlins 110 with a plurality of thermal conductive fasteners 26 to maximize thermal conduction from the plurality of thermally conductive roof sheeting panels 112 into the plurality of conductive , radiative roof purlins 110 , 128 , 134 . with reference to fig1 , maximizing conduction will enhance the heat transfer , enhance the heat collection in the air gap layer 10 , enhance the heat concentration at the highest point of the air gap layer 10 closest the ridge 122 and enhance overall efficiency of heat energy collection at the heat collection fins 94 of the heat transfer pipe 92 of the metal building building 100 . heat transfer fluid 93 circulates inside the heat transfer pipe 92 powered by either a pump or compressor ( not shown ). fig1 - 20 illustrate a preferred alternative multi - vent 74 to a typical metal roof ridge cap 77 , 79 of fig2 - 22 . the ridge mounted multi - vent 74 extends through the ridge 122 of the roof 120 and preferably extends a length of the roof ridge 122 . the ridge mounted multi - vent 74 is located between two ridge purlins 128 and between the two ridge ceiling support struts 20 . fig2 illustrates a plurality of multi - vent box side panel extensions 154 and a plurality of multi - vent box end panel extensions 152 which attach to the bottoms of the plurality of multi - vents modules 74 to fill the open space to the bottoms of the two ridge ceiling support struts 20 shown in fig4 . if the preferred multi - vent is not used and a typical ridge cap 77 , 79 is used . a single ridge ceiling support strut centered below the ridge line is sufficient to support the ceiling sheet material and the overlying material insulation layer . with reference to fig1 - 13 , each metal building 100 composite wall structure includes an exterior metal wall sheeting panel 114 , an optional exterior girt mounted vent spacer 36 , a girt 106 in the air gap 12 , the interior mounted girt vent spacer 38 , an exterior side wall sheet material which may typically be an extension of the ceiling sheet material 14 , or may be an independent exterior wall sheet material 30 , a material insulation layer 32 , 34 , and an interior wall material 28 , 31 . a plurality of optional girt exterior flange mounted vent spacers 36 include a plurality of through air flow openings 37 , if desired to increase the heat flow area upward around the girts . the interior girt flange mounted vent spacers 38 are attached to an interior flange 132 of the girt 106 . the interior girt spacers 38 include a plurality of through air flow openings 39 , if desired to increase the heat flow area around the interior girt flanges . an exterior surface of the wall sheet material 14 , 30 abuts the plurality of interior flange mounted girt spacers 38 . with reference to fig2 - 26 , a wall material insulation layer 32 , 34 is secured to a vertical portion of the wall sheet material 14 , 30 with bi - directional impaling hangers 156 by first impaling the sheet material impaling arrows 160 through the sheet material 14 , 30 for support and then impaling the insulation layer 32 , 34 on the opposite side hanger insulation impaling arrows 162 with any suitable method or device . a top edge of each side wall interior insulation covering sheet material 28 is preferably attached to the ceiling sheet material 14 with adhesive , fasteners or other suitable attachment means , such that the exterior surface of insulation covering wall sheet material 28 contacts an interior surface of the wall insulation layer 32 which is typically fiber glass blanket or batt insulation . a bottom edge of each interior insulation covering wall sheet material 28 is attached at its base with a tensioning device 24 , adhesive , fasteners or any other suitable attachment method . a plurality of wall heat collecting air gap layers 12 are created between an interior facing surfaces of the exterior wall sheeting panels 114 and the exterior facing surfaces of the side wall sheet material layer 14 which are typically extensions of the ceiling sheet layer 14 . the outer end wall sheet material 30 abuts to the plurality of inner girt flange vent spacers 38 . a top end of first installed exterior end wall sheet material 30 is preferably attached to the ceiling sheet material 14 with adhesive , fasteners or other suitable attachment means , but may alternatively be attached to the end wall rafter 108 or to end wall girts 106 as limited by accessibility of an individual application . a bottom end of each first installed , exterior end wall sheet material 30 is attached to the foundation 118 or floor 126 with the tensioning device 24 , adhesive or any other suitable attachment device and methods . fig1 a - 10 h illustrate various styles of tensioning devices which may be used to apply tension to the ceiling or wall sheet material 28 , 31 . wall material insulation layers 32 , 34 preferably are suspended from the interior surfaces of the first installed , exterior wall sheet material 14 , 30 . the plurality of bi - directional impaling suspension hangers 156 are used to suspend the wall material insulation layers 32 , 34 without any conductive thermal bridges to the wall girts 106 . the exterior facing impaling arrows 160 impale the exterior wall sheet material for support . the insulation layer 32 , 34 is impaled on the opposing impaling arrows 162 to support the insulation in suspension without any thermal bridging to the exterior wall girts and panels . a top end of each second installed , interior wall sheet material 28 , 31 is preferably attached to the ceiling sheet material 14 with adhesive , fasteners or other suitable attachment means , such that its exterior surface contacts an interior surface of the wall insulation layer 32 , 34 . a bottom end of each second installed , interior wall sheet material 28 , 31 is attached at its base with a tensioning device 24 or any other suitable attachment device and method . the end wall heat collecting air gap layer 12 is created between an interior facing surface of the exterior end wall sheeting panels 114 and the exterior facing surface of the first installed , exterior end wall sheet material 30 . the side wall heat collecting air gap layer 12 is created between an interior facing surface of the exterior wall sheeting panels 114 and the exterior facing surface of the first installed , exterior side wall sheet material 14 , 30 . with reference to fig1 a , 10 - 11 , 16 - 17 and 23 - 24 the plurality of wall ducts include side wall ducts and end wall ducts . the ducts are joined in series with a plurality of connection couplings 57 . the plurality of side wall ducts 40 , 42 , 44 generally have a horizontal orientation . the plurality of side wall ducts preferably include two side wall eave roof ducts 40 , two sidewall upper wall ducts 42 , two sidewall base ducts 44 . the side wall eave roof ducts 40 provide an independent air flow path from the exterior air to the roof air gap layer . the upper side wall air flow duct provides and independent air flow path which communicates with the exterior air and the air gap layer 12 . the plurality of end wall ducts include upper wall ducts 48 with an orientation generally matching the roof slope along the top of the end wall air gap layer 12 . the plurality of the end wall base ducts 50 have a horizontal orientation along the base of the air gap layer 12 . the plurality of end wall ducts preferably include two upper wall ducts 48 and two end wall base ducts 50 . two subterranean air ducts 46 and subterranean tube ducts 72 connected between the two opposite wall subterranean air ducts 46 also may be installed to pre - condition air used for ventilation , heating , cooling and dehumidification . each duct 40 - 50 is preferably fabricated from an extruded rectangular ( preferably square ) tube 54 illustrated in fig1 . the tube 54 preferably includes a plurality of air flow holes 56 formed through one or more sides thereof . with reference to fig1 , a damper strip slot 58 is formed in at least one sides side of the tube 54 to receive a damper strip 60 . the damper strip 60 includes a plurality of holes 62 , which may be aligned with the plurality of air flow holes 56 to allow air flow into the tube 54 or to prevent air flow into the tube 54 . any suitable duct actuation device 64 may be used to slide the damper strip 60 in the damper strip slot 58 . fig1 illustrates a cut - away perspective view of the general spacial locations of the wall duct and eave line roof duct communicating with the air gap layers 10 , 12 of the metal building 100 . the ducts need not be installed continuously , nor the full lengths of the building walls but only as desired to provide a useful function . each sidewall eave roof duct 40 is located below a lengthwise eave purlin 134 . the side wall eave roof duct 40 may be constructed of any suitable material and used to replace the eave purlin 134 and provide the intended combined functions of both the eave line roof duct 40 and the eave purlin 134 . each end wall upper wall duct 48 is located below an end wall eave channel 136 or below the ends of the roof purlins 110 , 128 , 134 if there is no end wall eave channel 136 . the side wall , end wall , and subterranean ducts 40 , 42 , 44 , 46 , 48 , 50 are capable of receiving outside air or interior space air through either air flow holes 56 or through branch ducts 63 . typically there would be an operable damper strip 60 or an operable louver 67 to open or close the air flow holes 56 or branch ducts 63 to air flows . the side wall upper wall duct 42 is located below the sidewall eave roof ducts 40 . the upper wall ducts 42 , 48 and base wall ducts 44 , 50 communicate with the air gap layers 12 of the walls . the upper side wall ducts 42 allow heat and air in the wall air gap layers 12 to communicate with the roof air gap layers 10 directly or through eave line roof duct 40 . with reference to fig1 , a heat collection coil / dehumidifier 66 is preferably retained inside the sidewall upper wall air gap layer 12 or inside the upper wall ducts 42 at this same general location . an coil bracket 68 is secured to one edge of the side wall heat collection / dehumidifier coil 66 and a lower mounting bracket 70 is secured to the other edge of the heat collection / dehumidifier coil 66 . with reference to fig1 , a blower 65 may be used to transfer heat and air from the wall heat collection air gap layer 12 to an interior space of the metal building 100 . the side wall base ducts 44 and the end wall base duct 50 are located adjacent the wall panel 114 and above the floor 126 . ends of the side wall ducts 40 , 42 , 44 and ends of the end ducts 48 , 50 are preferably closed with a duct end cap 59 illustrated in fig1 . the base ducts 44 , 50 may be made of a suitable material and used to replace a base support channel ( not shown ) and provide the intended functions of both the base ducting 44 , 50 and of the base structural support channel 116 . with reference to fig9 , the two opposing side wall subterranean air ducts 46 are located at a base perimeter of the metal building 100 , preferably at or below floor level and which extends the side wall length of the metal building 100 . one side wall subterranean air duct 46 communicates with the interior air space of the metal building 100 through at least one branch duct 63 or the plurality of duct modules tubes 54 air flow holes 56 . the opposing side wall subterranean duct communicates with the exterior air through at least one opposing branch duct 63 to the exterior air . a plurality of subterranean tubing 72 is located below the floor 126 of the building at a depth of about 6 to 9 feet , which run parallel to each other in the earth with the opposing subterranean tubing 72 ends connected to the two opposing subterranean ducts 46 . air flowed through the subterranean ducts 46 flows through the subterranean tubing 72 under the building floor 126 will be cooled by a reduced temperature of the earth in contact with the subterranean tubing 72 . one end of the plurality of subterranean tubing 72 is connected to one of the two lengthwise subterranean air tubing ducts 46 and the other end of the plurality of foundation tubing 72 is connected to a second of the two lengthwise subterranean air tubing ducts 46 . it is preferable that the plurality of foundation tubing 72 be oriented either parallel to the end walls of the building or parallel to the side walls of the building . it is preferred that the plurality of subterranean tubing 72 be connected to either the opposing sidewall subterranean ducts 46 or to opposing end wall subterranean tubing ducts ( not shown ). it is possible to use more than one subterranean duct and tubing system under the floor 126 of the metal building 100 at different depths to condition additional volumes of ventilation air flowing through them . the subterranean tubes 72 should be sloped to a low point and connected to a liquid water drain pipe 71 which connects to a liquid water reservoir 73 from which the condensation water can be stored and recycled for other uses . with reference to fig9 , 18 - 20 , the ridge mounted multi - vent 69 includes a plurality of vent modules 74 attached to each other end to end in series . the plurality of vent modules 74 are secured in series to each other with bolts or any suitable attachment device or method . each vent module 74 includes a box unit 76 and a cover 78 . the box unit 76 includes a vent base 80 , two end walls 82 , two side walls 84 and two box side flanges 86 . the two end walls 82 extend upward from opposing ends of the vent base 80 and two side walls 84 extend upward from opposing sides of the vent base 80 . a single flange 86 extends outward from a top of each box side wall 84 . at least one air opening 88 may be formed through each end wall 82 to allow the flow of air between the vent modules 74 . with reference to fig1 , a heat transfer pipe hole 90 may also be formed through each end wall 82 to receive a heat transfer pipe 92 . a plurality of heat fins 94 are attached along a length of the heat transfer pipe 92 . a trough 96 is placed under the heat transfer pipe 92 to catch and channel condensation to a drain ( not shown ) along its length . the cover 78 includes a cover portion 98 and a pair of cover side flanges 99 disposed on opposing side edges thereof . the cover portion 98 preferably includes a curved cross section . the cover side flange 99 extends from each side of the cover portion 98 . a first sealing material ( not shown ) may be placed between the cover side flanges 99 and the box side flanges 86 . a second sealing material ( not shown ) may be placed between the cover portion ends 98 and the box end wall 82 top edges . the cover 78 is preferably fabricated from a material , which is light translucent , light collecting , light diffusing or opaque . a damper slot 150 may be formed into each side wall 84 to slidably retain the damper strip 60 . a plurality of air flow holes are formed through the side walls 84 in the damper slot 150 . the damper strip 60 of fig1 may be shifted in the damper slot 150 with an actuation device to allow air to flow through air flow holes 62 and 95 . with reference to fig2 - 22 , the covers 78 of the plurality of vent modules 74 are secured through their flanges 99 to ridge roof sheeting panel closures 75 or to the roof ridge purlins 128 structures with fasteners 26 or any suitable attachment device or method . with reference to fig1 - 20 , the box unit 76 may have two end wall extension panels 152 which attach to base of the end walls 82 , and two side wall extension panels 154 which attach to the base of the side wall panels 84 . these extension panels fill any gap between the ridge support struts 20 and the base 80 of the multi - vent box unit side walls 84 and end walls 82 . a cover 78 with two opposing side flanges 99 may be attached to the side wall extensions from the interior side . the cover 78 is preferably fabricated from a material , which is light translucent , light collecting , light diffusing or opaque . while particular embodiments of the invention have been shown and described , it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects , and therefore , the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of the invention . | 8 |
most of the commercially available sulfonic acid contains a residual amount of sulfuric acid and sulfur trioxide from its sulfonation reaction of sulfur trioxide with the representative organic compound . pilot chemical produces dodecylbenzene sulfonic acid for use in detergent industry . in section 2 of the material safety data sheet ( msds ), it listed the amounts of sulfuric acid and sulfur trioxide presence in the product . when the sulfonic acid is formulated with other solvents for the use in photoresist stripping and cleaning processes during the manufacturing of semiconductor devices , the presence of the minute amount of the sulfuric acid and sulfur trioxide will cause damage to the metal substrate surface . for example , the dodecylbenzene sulfonic acid product specification from pilot chemical shows the product to contain 1 . 0 % sulfuric and 1 % sulfur trioxide . mixing dodecylbenzene sulfonic acid with solvent system illustrated by the prior art , without allowing sufficient time to reduce the sulfuric acid in the stripper solution , will cause higher attack of the aluminum . alkanolamine in the present invention serves the purpose of neutralizing the acids to reduce the acid in the stripper solution and simultaneously work as an anionic surface active agent . the heat generated from the neutralization of alkanolamine with the organic sulfonic acid during the mixing of the stripper solution also aids the dissolution of corrosion inhibitor , such as catechol , gallic acid etc . to the stripper solution forming a homogenous blend . the following examples of stripping compositions and preparation are provided to further illustrate the present invention and are not intended to limit the scope of the present invention for removing a resist from a substrate are set forth in table i below . in another embodiment of the present invention discloses the method of preparation of the photoresist stripper . a mixture of organic sulfonic acid and organic solvent is mixed with mechanical agitation in a mixing tank to a homogenous solution . alkanolamine is gradually added to the mixture with continuous agitation . the temperature of the solution rises slowly to about 70 ° c . the temperature rise is moderated with the rate of addition of the alkanolamine . the corrosion inhibitor , 1 , 2 dihydroxybenzene ( catechool ) is dispersed in a mixture of exxon aromatic a - 150 solvent and dodecylbenzene sulfonic acid . triethanolamine is gradually added to the mixtures with continuous agitation . the temperature of the solution rises slowly to about 70 ° c . the dispersion becomes a homogenous solution . solutions a to j are non - limiting examples represent preferred forms and best modes contemplated by the inventor for practice of his invention , as well as illustrating the results obtained through its use . examples illustrating the removal of a resist from a substrate under varying conditions using the stripping compositions of the present invention are described further below . thereafter , examples illustrating the removal of etching residue from a substrate are set forth . the following examples are provided to further illustrate the present invention and are not intended to limit the scope of the present invention . these results show that the photoresist stripper composition produced by the invention is suitable for use under production conditions encountered in the manufacture of integrated circuits without damage the substrate metal surface . substitution of other solvents and organic sulfonic acids as described above in the above examples gives similar advantageous results . it should now be apparent to those skilled in the art that a novel method of manufacturing photoresist stripping composition and method capable of achieving the stated objects of this invention has been provided . at least equivalent results are obtained with the composition and method of this invention as compared with results achieved utilizing the sulfonic acid , phenol and chlorinated organic solvent photoresist stripping composition in general use in the manufacture of integrated circuits . no attack on aluminum metallurgy or silicon dioxide insulators on silicon wafers is observed with the present invention . it should further be apparent to those skilled in the art that various changes in form and details of the invention as described may be made . it is intended that such changes be included within the spirit and scope of the claims appended hereto . all references , patents , patent applications referred to in this application are herein being incorporated by reference in their entirety . | 6 |
referring now to the drawings in which like reference numerals indicate like or corresponding elements over the several views , fig1 shows an overview of the satellite communications system consisting of subsystems 12 , 10 , 16 . original signal 22 feeds subchannel divider 24 which separates the signal into a plurality of numbered subsignals . the exemplary system of fig1 shows the number of subsignals to be four , but the present invention is not so limited . subchannel divider 24 creates the subsignals by dividing original signal 22 employing one of two methods . a first method divides the signal on the basis of power . in this first method all the subchannel signals emerging from subchannel divider 24 are identical . a second method divides the signal on the basis of content . in this second method , each subchannel signal carries at least some information that is not carried by the other subchannels . the information content may be mutually exclusive or may overlap between subchannels , but in any case the subchannel signals under the second divider method are not identical as in the first method . each subchannel signal feeds an uplink transmitter 26 a - 26 d , each of which uplink transmitters feeds a separate antenna 28 a - 28 d , directing radio frequency energy toward a plurality of orbiting satellites 14 a - 14 d via propagation paths 18 a - 18 d . uplink transmitters 26 a - 26 d add timing signal 23 to the signal to be transmitted either on a separate frequency allocation or in the bandwidth of the information - bearing carrier . the exemplary system of fig1 shows the number of satellites used by the system to be four , but the instant invention is not so limited . each satellite 14 a - 14 d receives a band of frequencies , amplifies the signals received in that band , and retransmits the band at a different location in the spectrum . each of said satellites has a transmitting antenna pattern that includes receiving terminal system 16 . propagation paths 20 a - 20 d from each satellite 14 a - 14 d to representative receiving terminal 16 carry radio frequency energy from satellites 14 a - 14 d to the receiving terminal system 16 . it should be understood that although fig1 depicts each uplink signal being carried by a different satellite , the present invention is not so limited . for example , transponders of satellites 14 a , 14 b could be collocated on the same satellite . in this case , uplink transmitters 26 a , 26 b and uplink antenna systems 28 a , 28 b could be combined , in addition to satellites 14 a , 14 b representing the same satellite . propagation paths 18 a , 20 a , 18 b , 20 b in this case would be combined into single uplink and downlink propagation paths . receiving terminal system 16 incorporates one of two antenna methods . a first method includes a plurality of antenna components to receive the plurality of satellite signals 20 a - 20 d . a second method incorporates a multiple beam antenna . the exemplary system of fig1 uses multiple beam antenna 30 , but the present invention is not so limited . in either of the aforementioned receiving terminal antenna methods , the antenna subsystem produces a plurality of output signals corresponding to the subchannel signals emerging from subchannel divider 24 in uplink system 12 . in the exemplary system of fig1 each of the numbered signals emerging from multiple beam antenna 30 correspond to similarly numbered signals emitted by subchannel divider 24 . this signal identity remains true whether satellites 14 a , 14 b of fig1 are distinct or represent the same satellite as indicated in the foregoing description . the subchannel signals emitted by multiple beam antenna 30 feed a plurality of tuners 32 which then drive a plurality of demodulators 34 . a signal emerging from one of the demodulators 34 then represents a version of the corresponding output of subchannel divider 24 , but delayed in time in proportion to the sum of the lengths of the corresponding uplink and downlink propagation paths 18 and 20 . in receiving terminal 16 , delay component 36 further delays first - arriving signals such that all the subchannel components arrive at subchannel combiner 38 at nearly the same time . said combiner 38 produces a reconstruction 40 of original signal 22 . the method used in subchannel combiner 38 is consistent with and corresponds to the method used to divide original signal 22 in subchannel divider 24 . the instant invention uses one of four methods to perform the dividing and combining operations of subchannel divider 24 and subchannel combiner 40 . in each of said methods , subchannel divider 24 of fig1 feeds a plurality of uplink transmitters 26 a - 26 d , but the signals emerging from subchannel divider 24 are different in nature depending of the dividing and combining method used . in a first dividing and combining method , original signal 22 is digital . in said first method , subchannel divider 24 divides said digital signal into lower data rate subchannel signals with binary content that contains at least some mutually exclusive information . the division could be on a sequential bit - by - bit basis , could be on a sequential frame - by - frame basis , and may or may not relate to possible framing in the original digital signal ( e . g . dvb transport ). the exemplary receiving terminal 16 of fig2 depicts a two - subchannel digital receiving system where the radio frequency carriers feeding the demodulators 36 a and 36 b are quaternary phase shift keying ( qpsk ) modulated signals , but the present invention is not so limited . said figure further indicates the use of a multiple beam antenna 30 , but the present invention is not so limited . referring again to fig2 multiple beam antenna 30 emits first and second signals into first and second tuners 32 a and 32 b . each tuner shifts a band of higher frequencies to a band of lower frequencies of equal bandwidth such that receiver controller 42 sets the center frequency of the higher band , but the lower band is fixed . tuners 32 a , 32 b emit qpsk modulated signals at a frequency that the qpsk demodulators 36 a , 36 b expect to receive . as there are two subchannels in the example of fig2 the data rate of the binary information contained in these qpsk signals is approximately half the data rate of original signal 22 . the respective outputs of qpsk demodulators 36 a , 36 b emit signals to bit detectors 38 a , 38 b which in turn produce streams of binary data corresponding to the subchannel division in uplink system 12 . delay operators synchronize the data streams by introducing delay in the first - arriving binary stream such that there is a minimum of relative delay between the respective delay operator outputs . digital content combiner 48 reverses the content division process of subchannel divider 24 so as to produce at its output a faithful delayed replica 50 of original digital signal 22 . receiver controller 42 of fig2 responds to user input ( not depicted ) to select the transponders 14 to combine , subsequently emitting control signals to multiple beam antenna 30 to direct its antenna patterns toward the satellites containing selected transponders 14 . receiver controller 42 also selects each tuner frequency consistent with the signals emitted from the selected transponder . receiver controller 42 further processes information from timing signal correlator 44 to determine the correct setting of delays 40 a , 40 b . timing signal correlator 44 receives and time correlates tuner outputs 34 . for a system with more than two subchannels , correlator 44 processes tuner outputs in pairs to determine relative delay between subchannels . nonvolatile memory 46 contains parameters regarding the user - selected transponders to enable the correct setting of multiple beam antenna 30 and tuners 32 . the instant invention can use a second method for transporting a digital signal across a virtual satellite channel . referring to fig3 which depicts an example of said second method which combines delayed demodulator outputs from identical subchannels as described previously as power combining . under the direction of receiver controller 42 , multiple beam antenna 30 emits signals to tuners 32 a , 32 b which translate variable transponder bands into a fixed band of frequencies expected by the qpsk demodulators 54 . fig3 depicts a receiving terminal using a multiple beam antenna , but the present invention is not so limited . fig3 further depicts a receiving terminal with two subchannels , but the instant invention is not limited to two subchannels . the figure in addition shows the use of a qpsk modulation scheme , but the instant invention is not so limited . subchannel signals 52 emitted by tuners 32 contain identical digital information transmitted at the full rate of original signal 22 . qpsk demodulators 54 produce soft decision outputs i a and q a for each subchannel . since the total propagation delay for each subchannel is in general different , first arriving soft decisions must be delayed in time by an amount such that soft decisions emitted by delays 56 emerge with nearly zero relative delay between subchannels . delays 56 digitize the analog soft decisions produced by demodulators 54 , placing digitized results in a first - in first - out ( fifo ) buffer . receiver controller 42 controls the amount of time delay in delays 56 with input from timing signal processor 44 and digital correlator 58 . timing signal processor 44 analyzes input from tuner outputs 52 to determine the relative time delay between subchannels . for systems using more than two subchannels , the timing signal processor would process subchannel tuner outputs in pairs . since the subchannels of fig3 result from use of an uplink system 12 using power division , delay outputs ib and qb from delays 56 a , 56 b are correlated . this enables digital correlator 58 to compare digitized soft decisions between subchannels and provide additional information to receiver controller 42 about relative subchannel delay at the bit level . digital power combiner 66 processes synchronized i and q soft decisions from all subchannels to produce a single i and q decision 68 for every set of soft decisions presented . for the case of qpsk modulation , each final decision from combiner 66 produces two bits in digital output 68 . a third method for dividing and combining the original signal address the case that original signal 22 is analog in nature . referring to fig4 receiver controller 42 directs multiple beam antenna 30 to point to selected transponder signals and directs tuners 32 a , 32 b to translate said transponder frequencies to a fixed band of frequencies expected by demodulators 70 a , 70 b . the exemplary system of fig4 divides the signal into two subchannels , but the instant invention is not so limited . demodulators 70 a , 70 b produce analog outputs signals which are faithful replicas of the subchannel signals produced by subchannel divider 24 in the uplink system 12 . said analog signal outputs in general experience relative delay due to differing lengths of total propagation paths when using transponders on different satellites . under direction of receiver controller 42 , analog delays 72 add delay to first - arriving subchannel signals so as to create outputs of analog delays 72 which arrive at analog combiner 80 with near zero relative delay . analog delays 72 consist of a high quality analog - to - digital converter ( a / d ), a fifo buffer , and a digital - to - analog ( d / a ) converter . each of delays 72 creates a time delay in proportion the instant size of the fifo buffer contained therein . delays 72 present output signals to analog combiner 80 which represent faithful replicas of the subchannel signals produced by subchannel divider 24 in the uplink system 12 . these signals differ from outputs of demodulators 70 in that they are now time synchronized . fig4 represents both signal division strategies , power division and content - division . in the first case of power - divided subchannel signals , inputs to analog combiner 80 represent identical signals , differing only in distortion and noise added by satellite transport . in a second case , time - synchronized content - divided subchannel signals arrive at analog combiner 80 . analog combiner 80 creates output 82 most likely by a simple addition process , but is not so limited . in addition to producing combined output signal 82 , analog combiner 80 optionally provides a measure of time synchronization to receiver controller 42 to improve the accuracy of time alignment by controller 42 . as in first and second digital divider - combiner methods , timing signal correlator 44 provides relative subchannel delay information to receiver controller 42 , which together with further optional delay information from analog combiner 80 provides receiver controller 80 with a basis to create estimates of relative delay between subchannels ; which in turn affects the setting of delays 72 . a fourth method for dividing the original signal applies specifically to digital signals wherein the signal to be divided consists of a combination of a plurality of individual program streams as in a dvb multiplex ( mux ). as in the three previously described methods , subchannel divider 24 of fig1 represents the signal dividing process . in this method , subchannel divider 24 splits the multiple signal into subsignals , placing information bits associated with any particular program stream entirely in the same subchannel . this requires a remultiplexing operation at the uplink facility but eliminates the need to recombine multiple substreams at the receiving terminal . the required receiver is shown in fig5 which depicts a single tuner and demodulator but requires multiple beam antenna 30 , or multiple antennas , as the totality of signals in the service provided may necessarily pass through a plurality of satellites since the division process substantially increases the total satellite bandwidth requirement . the receiver block diagram is simplified since there is no requirement to recombine subchannels in this method . [ 0026 ] fig6 provides more details of an exemplary multiple beam antenna 30 a for receiving internet data . the multiple beam antenna 30 a is preferably a single ellipsoidal dish antenna with a major axis of approximately 24 to 30 inches . this allows simultaneous reception from up to five different satellites that are within a 30 - degree arc . exemplary signals that may be communicated include a 43 watt pas 3r signal , a 45 watt pas 1 signal , a 74 watt sbs 6 signal , an 81 watt satcom k2 signal , an 87 watt ge 3 signal , and a 123 watt sbs 5 signal . these signals are processed by a synchronization , timing , compression and decoding circuit block 90 . a personal computer 92 may then be the source and / or destination of the internet data . the embodiment of fig6 enables a reduced size and cost of the multiple beam antenna 30 a and the related processing circuitry 90 by reducing the size of the amplifier by approximately one - third , at the expense of increasing the bandwidth required by approximately three times . assume the multiple beam antenna 30 a transmits to up to three satellites , and assume the three uplink signals are processed in such a manner as to make them identical after they have been transponded through the satellite transponders and received at a downlink antenna . at the downlink antenna , which may be located at an internet gateway , the signals are reconstituted into a signal whose signal - to - noise ratio ( snr ) is approximately 4 . 77 db greater than any one of the received signals . consequently , the eirp of each of the channels transmitted from the multiple beam antenna 30 a ( also referred to as a virtual antenna ) can be 4 . 77 db less than would be required should a single channel be employed to receive the same signal power at the gateway antenna . specifically , assume n signals , which are exactly identical and perfectly synchronized , are to be perfectly combined . the n identical signals of amplitude x add to form a signal with amplitude n * x . the n uncorrelated , random signals with identical statistical properties and equal root - mean - squared ( rms ) amplitude y add to form a random signal with rms amplitude equal to y * sqrt ( n ). this process increases the snr from x / y to [ n * x ]/[ y * sqrt ( n )], yielding an improvement of sqrt ( n ) in the amplitude domain . in the db domain , the improvement is 20 * log 10 ( sqrt ( n )) or 10 * log 10 ( n ). for n = 3 , the improvement is 4 . 77 db . in first , second , and third divider - combiner methods , tuners 32 provide information to timing signal correlator 44 using one of two timing methods . in a first timing method , receiver controller 42 adjusts tuners 32 to receive timing signal 23 placed on all satellites with transponders used by the virtual satellite system . in this first method , tuner adjustment is necessary as the timing signals are placed at a frequency assignment separate form the information - bearing transponder signal . this out - of - band timing signal may be narrow - band in nature so as to conserve limited bandwidth on the satellite and reduce system cost . in general , timing signal 23 is unrelated to the information - bearing transponder signal in either information content , modulation strategy , or data rate or frame rate in the case of digital transmission , but the present invention is not so limited . the timing signal utilizes allocated bandwidth to enhance the resolution of relative subchannel delay estimation . possibilities for the timing signals include pseudorandom noise , tone ranging , and time - dispersed pulse , but the instant invention is not so limited . a good timing signal must have a strong sharp cross - correlation with a time - shifted version of itself and have minimum spurious correlations . the instant invention includes two timing signal processor methods . in a first timing processor method , timing signal correlator 44 correlates output signals from tuners 32 at various relative delays until an acceptable correlation occurs indicating that the relative delay between the subchannels has been reproduced in timing correlator 44 . receiver controller 42 then sets analog delays 72 in accord with this measured relative delay to synchronize inputs to analog combiner 80 . in the case that there are more than two subchannels in the virtual satellite channel , timing signal processor 44 compares subchannel signals pair - wise . in a second timing processor method , timing signal correlator 44 correlates the output from each tuner 32 with a stored version of the known timing signal , or by processing the recovered timing signal through a process that will produce a periodic output in response to the timing signal . one example of such a process is a matched filter , but the present invention is not so limited . once the delays 40 , 56 , 72 are adjusted to remove relative subchannel delay , tuners 32 are set to conduct the selected information - bearing transponder signals to the respective demodulators in fig1 fig2 fig3 . in a second timing method , the timing signal is as wide in bandwidth as the information - bearing transponder and resides in exactly the same bandwidth . in order to prevent distortion of the information signal , the timing signal is greatly attenuated . in order to recover the attenuated timing signal , timing signal correlator 44 first processes the tuner outputs through a linear system that creates a large processing gain to amplify the expected timing signal above the output created by the presence of the uncorrelated information - bearing carrier . the instant invention may use one of three exemplary processes to recover a low - level in - band timing signal , but the present invention is not so limited . in a first exemplary process the timing signal is a time - dispersed pulse with precise time dispersion introduced by a surface acoustic wave ( saw ) filter in timing signal generator 23 . a matching saw filter in receiving terminal 16 performs the inverse of the dispersion process , thus recovering the primary timing signal which is a periodic narrow - time pulse . in a second exemplary process , the timing signal is pseudorandom noise . timing signal processor 44 then applies spread spectrum techniques to recover the timing of the low - level in - band timing signal . upon timing signal acquisition , the correlated timing signal will experience a large process gain , but the uncorrelated information carrier will remain at the same relative level . this enables timing signal processor 44 to establish relative delay between subchannels , reporting results to receiver controller 42 . a third exemplary timing process uses a multiple tone signal to establish timing . the sine waves selected are harmonically related in such a way as to create a signal with a relatively long period , but giving good time resolution with the presence of some high frequencies . a linear filter at the selected frequencies recovers the timing signal in favor of the information carrier . timing signal processor 44 then analyzes filtered timing signals to establish relative time delay between subchannels . in the case of the digital content - division receiver of fig2 there is typically no correlation between the subchannels to provide feedback as to the accuracy of the delay settings of delays 40 . this is a feed forward control system . feedback is possible however in the exemplary systems of fig3 and 4 . outputs from delays 56 in the digital power - division receiver of fig3 are highly correlated . if the delay setting is slightly in error , a local digital correlation reveals the necessary small correction . outputs from delays 72 in the analog receiver of fig4 are correlated to some extent depending on the nature of the analog division and the instant properties of the analog content . this provides optional feedback to receiver controller 42 to affect local timing corrections . while several particular forms and variations thereof have been illustrated and described , it will be apparent that various modifications can be made without departing from the spirit and scope of the invention . accordingly it is not intended that the invention be limited , except by the appended claims . | 7 |
the optically active fluoroalkane derivative represented by the above formula ( i ) may be synthesized from optically active intermediates such as 2 - fluoro - 1 - alkanols , 2 - fluoroalkyl , p - hydroxybenzoates , 2 - fluoroalkyl p - hydroxybiphenylcarboxylates , hydroquinone 2 - fluoroalkyl ethers , and 4 -[ 4 &# 39 ;-( 2 - fluoroalkyl ) oxyphenyl ] phenol . for example , the mesomorphic compound represented by the formula ( i ) may be synthesized from these optically active intermediates through reaction paths as shown below . ## str11 ## ( in the above , the symbols r , r 1 ## str12 ## p , q , r , l , m and n have the meanings as defined above .) in the following table 1 are shown some examples of the fluoralkane derivatives produced in the manner as shown above together with their optical rotations and phase transition characteristics . the details of production will be explained in the examples appearing hereinafter . in the table and the description appearing hereinafter , the symbols used for describing phase - transition respectively denote the following phases . the liquid crystal composition according to the present invention contains at least one species of the fluoroalkane derivative represented by the formula ( i ). for example , the fluoroalkane derivative represented by the formula ( i ) may be mixed with a ferroelectric liquid crystal selected from those of the formulas ( 1 )-( 13 ) shown below to increase the spontaneous polarization and increase the response speed . in this case , it is preferred to use the fluoroalkane derivative represent by the formula ( i ) in an amount constituting 0 . 1 - 99 wt . %, particularly 1 - 90 wt . % of the resulting liquid crystal composition . ## str87 ## the fluoroalkane derivative represented by the formula ( i ) may also be mixed with a smectic liquid crystal such as those of the formula ( 1 )-( 5 ) below which per se are not chiral to provide a composition which may be used as a ferroelectric liquid crystal . in this case , the fluoroalkane derivative represented by the formula ( i ) may preferably be used in an amount of 0 . 1 - 99 wt . %, particularly 1 - 90 wt . %. the resultant composition may be provided with an increased spontaneous polarization corresponding to the content of a fluoroalkane derivative according to the present invention . ## str88 ## the present invention will be explained more specifically with reference tosome examples . 2 - fluorooctyl p - octyloxybiphenylcarboxylate represented by the above formula was produced through the following reaction scheme : ## str90 ## more specifically , 0 . 74 g ( 2 . 3 mmol ) of p - octyloxybiphenylcarboxylic acid and 5 ml of thionyl chloride were subjected to heat - refluxing for 2 . 5 hours , followed by removal of unreacted thionyl chloride by distillation to obtain a corresponding acid chloride . separately , 0 . 50 g ( 4 . 5 mmol ) of triethylenediamine was dissolved in 5 ml of dry benzene , and potassium chloride was added thereto for drying for about 30 min . the solution was charged in a vessel containing 0 . 40 g ( 2 . 7 mmol ) of (-)- 2 - fluorooctanol , followed by stirring under vibration . the solution was added dropwise into the above acid chloride under stirring , and the mixture was then further stirred at 50 ° c . for 2 hours . after the completion of the reaction , 1n - hydrochloric acid and water were added thereto , followed by extraction with benzene . into the benzene layer , a 1n - sodium carbonate aqueous solution was added , and further benzene - extraction was conducted . the resultant benzene solution was charged with anhydrous sodium sulfate for drying overnight . after distilling - off of the benzene , the residue was separated by silica gel column chromatography with the use of a benzene / hexane ( 1 / 1 ) mixture as an eluent to obtain 0 . 53 g ( yield : 50 %) of 2 - fluorooctyl p - octyloxybiphenylcarboxylate . the following optical rotation and ir ( infrared absorption ) data were obtained . optical rotation : [ α ] d 26 . 4 + 13 . 1 ° ( c = 2 , benzene ). ir ( cm - 1 ): 2900 1715 , 1605 , 1300 , 1200 , 1120 , 830 , 770 . example 1 was repeated except that p &# 39 ;- octyloxybiphenylcarboxylic acid and 2 - fluoro - 1 - octanol were replaced by a carboxylic acid providing groups r 1 , ## str91 ## l , m and n and a 2 - fluoro - 1 - alkanol providing a group r , respectively indicated in the above mentioned table 1 , whereby fluoroalkane derivativesshown in the table 1 according to the present invention were respectively obtained . the optical rotations and phase - transition temperature data of the obtainedproducts were also shown in table 1 together with those obtained in example 5 - octyloxy - 2 -[ 4 -( 2 - fluoroheptyloxy ) phenyl ]- pyrimidine shown above was produced according to the following scheme : ## str93 ## into a sufficiently nitrogen - substituted vessel , 0 . 40 g ( 3 . 0 mmol ) of (-)- 2 - fluoroheptanol and 1 . 00 g ( 13 mmol ) of dry pyridine were charged andstirred under cooling with ice for 30 min . the solution was charged with 0 . 69 g ( 3 . 6 mmol ) of p - toluenesulfonic acid chloride and further stirred for 5 hours . after the reaction , 10 ml of 1n - hcl was added , followed by two times of extraction with 10 ml of methylene chloride . then , the extract liquid was once washed with 10 ml of distilled water . the resultant methylene chloride solution was dried with anhydrous sodium sulfate added in an appropriate amount , and the solvent was distilled off to obtain 0 . 59 g ( 2 . 0 mmol ) of (+)- 2 - fluoroheptyl p - toluenesulfonate at a yield of 66 %. the optical rotation and ir data of the product were as follows : optical rotation [ α ] d 26 . 4 + 2 . 59 ° ( c = 1 , chcl 3 ). optical rotation [ α ] 435 23 . 6 + 0 . 58 ° ( c = 1 , chcl 3 ). ir ( cm - 1 ): 2900 , 2850 , 1600 , 1450 , 1350 , 1170 , 1090 , 980 , 810 , 660 , 550 . to 0 . 43 g ( 1 . 5 mmol ) of the (+)- 2 - fluoroheptyl p - toluenesulfonate obtained above and 0 . 28 g ( 1 . 0 mmol ) of 5 - octyl - 2 -( 4 - hydroxyphenyl ) pyrimidine , 0 . 2 ml of 1 - butanol was added , and they were sufficiently stirred . to the resultant solution was quickly added an alkalline solution which was prepared in advance by dissolving 0 . 048 g ( 1 . 2 mmol ) of sodium hydroxide in 1 . 0 ml of 1 - butanol , and the mixture was heat - refluxed for 5 . 5 hours . after the reaction , 10 ml of distilled water was added , followed by one time each of extraction with 10 ml and 5 ml of benzene . the extract liquidwas dried with an appropriate amount of anhydrous sodium sulfate . after thedrying , the solvent was distilled off , and the residue was subjected to silica gel column chromatography with chloroform , thereby to obtain 0 . 17 g ( 0 . 43 mmol ) of (+)- 5 - octyl - 2 [ 4 -( 2 - fluoroheptyloxy ) phenyl ] pyrimidine at a yield of 43 %. optical rotation [ α ] d 25 . 6 + 0 . 44 ° ( c = 1 , chcl 3 ). optical rotation [ α ] 435 22 . 4 + 4 . 19 ° ( c = 1 , chcl 3 ). ir ( cm - 1 ): 2900 , 2850 , 1600 , 1580 , 1420 , 1250 , 1160 , 800 , 720 , 650 , 550 . example 3 was repeated except that 2 - fluoroheptanol and 5 - octyl - 2 -( 4 - hydroxyphenyl ) pyrimidine were replaced by a 2 - fluoro - 1 - alkanol providing a r and a 4 - substituted phenol derivative providing groups r 1 , ## str94 ## l , m and n , respectively indicated in the above mentioned table 1 , whereby fluoroalkane derivatives shown in the table 1 according to the present invention were respectively obtained . p &# 34 ;-( 2 - fluorooctyloxycarbonyl ) phenyl p &# 39 ;- octyloxybiphenylcarboxylate shown above was produced through the following reaction steps ( 1 ), ( 2 ) and ( 3 ). 0 . 68 g ( 3 . 7 mmol ) of p - acetoxybenzoic acid ( the above 1 ) was heat - refluxed together with 7 ml of thionyl chloride for 2 . 5 hours , followed by removal of unreacted thionyl chloride to obtain a corresponding acid chloride . separately , 0 . 83 g ( 7 . 4 mmol ) of triethylenediamine was dissolved in 5 ml of dry benzene , and potassium chloride was added thereto to effect drying for about 30 min . the solution was charged in a vessel containing 0 . 66 g ( 4 . 5 mmol ) of (-)- 2 - fluoro - 1 - octanol , followed by stirring under vibration . the solution was added dropwise into the above acid chloride under stirring , and the mixture was further stirred at 50 ° c . for 2hours . after the reaction , 8 ml of 1n - hcl and 30 ml of water were added , followed by extraction with benzene . the aqueous layer was further subjected to twotimes of extraction with 8 ml of benzene . to the benzene layer , 15 ml of 1n - sodium carbonate was added , and further subjected to extraction with water similarly as above , followed by two times of extraction of the waterlayer with 8 ml of benzene . the benzene layer was charged with anhydrous sodium sulfate for drying overnight . by distilling off the benzene , a crude product was obtained , which was thensubjected to separation by silica gel column chromatography with a benzene : hexane ( 1 : 1 ) mixture , thereby to obtain 0 . 80 g ( yield : 69 %) of 2 - fluorooctyl p - acetyloxybenzoate . 0 . 750 g ( 2 . 5 mmol ) of the purified product ( 3 ) obtained in the above step ( 1 ) was dissolved in 1 . 5 ml of ether . into the solution , a solution of 0 . 27 g ( 2 . 5 mmol ) of benzyl amine in 1 . 5 ml of ether was added , followed by standing overnight at room temperature . thereafter , the ether was distilled off to obtain a mixture of 2 - fluorooctyl p - hydroxybenzoate ( 4 ) and n - acetylbenzylamine ( 5 ). the mixture was separated by silica gel column chromatography with a mixture liquid of ethyl acetate : methylene chloride (= 1 : 9 ), thereby to obtain 0 . 53 g of 4 in purified form ( yield : 78 %). the optical rotation and ir data ofthe product were as follows : 0 . 65 g ( 2 mmol ) of p &# 39 ;- octyloxybiphenylcarboxylic acid was heat - refluxed together with 4 ml of thionyl chloride for 2 . 5 hours , followed by removal of unreacted thionyl chloride to obtain a corresponding acid chloride . separately , 0 . 44 g ( 4 mmol ) of triethylenediamine was dissolved in 5 ml of dry benzene , and potassium hydroxide was added thereto to effect drying for about 30 min . the resultant solution was charged in a vessel containing 0 . 53 g ( 2 mmol ) of the 2 - fluorooctyl p - hydroxybenzoate , followed by stirring under vibration . the solution was added dropwise intothe above acid chloride under stirring , and the mixture was further stirredat 50 ° c . for 2 hours . after the reaction , 1n - hcl and water were added , followed by extraction with benzene , addition of 1n - sodium carbonate aqueous solution and extraction with benzene . the benzene solution was charged with anhydrous sodium sulfate for drying overnight . after distilling off the benzene , the residual product was separated by silica gel chromatography with benzene as an eluent , thereby to obtain 0 . 58 g of p &# 34 ;-( 2 - fluorooctyloxycarbonyl ) phenyl p &# 39 ;- octyloxybiphenylcarboxylate . the optical rotation and ir data of the product were as follows : ir ( cm - 1 ): 2950 - 2850 , 1740 , 1730 , 1610 , 1295 , 1285 , 1120 , 1080 , 830 , 760 . example 7 was repeated except that p - acetoxybenzoic acid , 2 - fluoro - 1 - octanol and p &# 39 ;- octyloxybiphenylcarboxylic acid were replaced bya carboxylic acid providing groups p , q and r , a 2 - fluoro - 1 - alkanol providing a group r , and a carboxylic acid providing groups r 1 , ## str99 ## l , m and n , respectively indicated in the above mentioned table 1 , whereby fluoroalkane derivatives shown in the table 1 according to the present invention were respectively obtained . the optical rotations and phase - transition temperature data of the obtained products were also shownin table 1 together with those obtained in example 7 . p &# 39 ;- 2 - fluorodecyloxyphenyl p - octyloxybenzoate was produced through the following reaction steps ( 1 ) and ( 2 ). 3 . 15 g ( 18 mmol ) of 2 - fluorodecanol ( 6 ) and 4 . 25 g ( 54 mmol ) of dry pyridine together charged in a vessel with a nitrogen atmosphere and stirred . the vessel was then cooled with ice , and 3 . 75 ( 20 mmol ) of p - toluenesulfonyl chloride was added thereto half by half in two times , followed by stirring for 3 hours . after the reaction , the reaction productwas neutralized with hydrochloric acid and subjected to extraction with 10 ml of methylene chloride . the water layer was further extracted two times with 5 ml of methylene chloride . water was added to the methylene chloride , followed further by extraction with methylene chloride . the resultant methylene chloride solution was charged with anhydrous sodium sulfate and dried overnight . by distilling off the methylene chloride , 5 . 60 g ( yield : 94 %) of 2 - fluorodecyl p - toluenesulfonate ( 7 ) was obtained . the optical rotation and ir data were as follows : optical rotation [ α ] d 22 . 0 + 4 . 2 ° ( c = 2 , chcl 2 ). ir ( cm - 1 ): 2850 - 2900 , 1600 , 1350 , 1170 , 1100 , 660 , 550 . 5 . 60 g ( 17 mmol ) of the above product 7 , 3 . 74 g ( 34 mmol ) of hydroquinone and 5 ml of 1 - butanol were mixed under stirring . into the mixture , a solution of 1 . 02 g ( 25 mmol ) of sodium hydroxide in 13 ml of 1 - butanol wasgradually added , followed by reaction at 130 ° c . for 7 hours . after the reaction , 40 ml of water was added , followed by extraction with ether . the resultant ether solution was charged with anhydrous sodium sulfate and dried overnight . after distilling off the solvent , the residue was subjected to separation by silica gel column chromatography with methylenechloride , thereby to obtain 2 . 57 g ( yield : 56 %) of purified p - hydroquinone mono ( 2 - fluorodecyl ) ether ( 8 ). the optical rotation and ir data of the product were as follows . optical rotation [ α ] d 24 . 0 + 1 . 8 ° ( c = 2 , chcl 2 ). ir ( cm - 1 ): 3600 - 3200 , 2900 , 1680 , 1590 , 1280 , 1160 , 700 . 0 . 93 g ( 3 . 7 mmol ) of p - octyloxybenzoic acid was heat - refluxed together with8 ml of thionyl chloride for 2 hours , followed by distilling - off of unreacted thionyl chloride to obtain a corresponding acid chloride . separately , 0 . 81 g ( 7 , 4 mmol ) of triethylenediamine was dissolved in dry benzene , and potassium hydroxide was added thereto to effect drying for about 30 min . the resultant solution was charged in a vessel containing 1 . 0 g ( 3 . 7 mmol ) of p - hydroquinone mono ( 2 - fluorodecyl ) ether obtained in the above step ( 1 ), followed by stirring under vibration . the solution wasadded dropwise into the above acid chloride under stirring , and the mixturewas further heated at 50 ° c . for 2 hours . after the reaction , 1n - hcl and water were added , followed by extraction with benzene , addition of 1n - sodium carbonate aqueous solution and extraction with benzene . the benzene solution was charged with anhydrous sodium sulfate for drying overnight . after distilling off the benzene , the residual product was separated by silica gel chromatography with benzene as an eluent , thereby to obtain 1 . 49 g ( yield : 81 %) of p &# 39 ;-( 2 - fluorodecyloxy ) phenyl p - octyloxybenzoate . theoptical rotation and ir data of the product were as follows : ir ( cm - 1 ): 2900 , 1 , 40 , 1610 , 1520 , 1280 , 1250 , 1210 , 1170 , 1130 , 760 , 690 . examples 8 , 9 , 10 , 14 , 17 , 18 , 19 , 20 , 21 , 22 , 23 28 , 29 , 30 and 31 example 11 was repeated except that 2 - fluorodecanol , p - hydroquinone and p - octyloxybenzoic acid were replaced by a 2 - fluoro - 1 - alkanol providing r , p - hydroquinone or p , p &# 39 ;- dihydroxybiphenyl , and a carboxylic acid providing groups r 1 , ## str103 ## l , m and n , respectively indicated in the above mentioned table 1 , whereby fluoroalkane derivatives shown in the table 1 according to the present invention were respectively obtained . the optical rotations and phase - transition temperature data of the obtainedproducts were also shown in table 1 together with those obtained in example a liquid crystal composition containing a mesomorphic compound ( 2 - fluorooctyl p - octyloxybiphenylcarboxylate ) was prepared as shown below together with the phase transition temperatures . ## str104 ## the composition showed a spontaneous polarization of 8 . 8 nc / cm 2 which is about 8 times 0 . 45 nc / cm 2 , the spontaneous polarization of mora 8 alone . a liquid crystal device was prepared by using a mesomorphic compound prepared in example 11 . a 1000 å - thick ito film was applied to form electrodes onto a highly polished glass substrate of 10 × 20 mm in size , and an about 1000 å - thick sio 2 layer was deposited thereon by the ion beam process . on one of the thus tread pair of glass substrates , the mesomorphic compound ( p &# 39 ;-( 2 - fluorodecyloxy ) phenyl p - octyloxybenzoate ) prepared in example 11 wasdropped , and the other substrate was superposed thereon . the substrates were held at 80 ° c . and mutually slided in a parallel movement while maintaining a spacing therebetween at 1 . 2 μm and observed througha polarizing microscope , whereby a homogeneously aligned monodomain having lost spiral structure was observed to be formed . in this state , pulses of ± 10 volts with a duration of 200μsec were applied at 65 ° c ., whereby satisfactory switching was effected with a contrast of 18 . | 2 |
fig1 is a cross - sectional diagram showing materials used in a completed borehole to achieve hydraulic isolation . a borehole 111 is cased with a first material 115 , typically steel pipe . outside and adjacent to first material 115 lies a second material . second material is usually a fill material , commonly referred to as cement , which is pumped into the annulus 119 between casing 115 and earth formation 117 . the cement hydrates to retain casing 115 rigidly in position . more importantly , it fills the annulus 119 between casing 115 and earth formation 117 sealing off the hydrocarbon strata from the other layers so that when casing 115 and the cement are subsequently perforated , the hydrocarbons enter directly into casing 115 and migration of fluids between adjacent formation layers is prevented . fluid 121 , usually in the form of mud , fills casing 115 and annulus 119 before cement placement . in accordance with the above description of borehole 111 , a number of interfaces are formed between the various materials . a first interface 123 exists along the juncture between fluid 121 ( usually mud ) and casing 115 . ideally , second material in the form of cement completely fills the annulus 119 between casing 115 and earth formation 117 . such a situation is shown along radial line r g . a second interface 125 is formed between casing 115 and cement . a third interface 127 emphasized by the bold line , exists at the juncture of cement and earth formation 117 . unfortunately , fill material or cement does not always completely fill the space between casing 115 and earth formation 117 . when cement does not completely fill the space , three possible conditions arise . the first condition is shown along radial line r 1 . a near channel 129 exists between casing 115 and cement . instead of second interface 125 existing between casing 115 and cement , it is formed between casing 115 and the fluid of near channel 129 . in such a situation , the fluid of near channel 129 is the second material . additionally , instead of third interface 127 existing between cement and earth formation 117 , it is formed at the juncture of a fluid and cement . a full channel 133 is shown along radial line r 2 . full channel 133 extends completely across the annulus to earth formation 117 . as in the case of near channel 129 , full channel 133 also has a second interface between first material 115 and a fluid . however , the third interface for full channel 133 is between a fluid and earth formation 117 . the third condition occurs when a channel is formed in the space 119 between second material and earth formation 117 . in this case , the channel does not contact first material 115 . this condition is shown along radial line r 3 and is referred to as a buried channel 131 . for such a channel , second interface 125 is formed between casing 115 and second material ( cement ), and third interface 127 is formed at the juncture of second material and the fluid of buried channel 131 . fig2 is a schematic diagram of a logging operation . tool or sonde 210 for acquiring acoustic data is located in borehole 111 penetrating earth formation 117 . sonde 210 is preferably lowered in the borehole by armored multiconductor cable 214 and slowly raised by surface equipment 215 over sheave wheel 216 while data measurements are recorded in azimuthal intervals by rotating transducer 212 . the depth of the tool is measured by depth gauge 217 which measures cable displacement . sonde 210 acquires acoustic data by emitting an acoustic pulse and detecting its return waveform . the sonde comprises at least one transducer . the transducer produces a pulse upon excitation . the pulse is directed into casing 115 and a transducer receives a resulting signal . the pulse interacts with all of the interfaces it encounters . this includes both inner and outer surfaces of the casing , both rear and far edges of the cement annulus , any fluid channel contained within the cement , and the formation surface . due to the typical acoustic impedances and dimensions of these materials , the return signal will largely represent interaction with the casing interfaces . representation of more distant structures such as formation or channeling , is typically of significantly lesser amplitude . in a preferred embodiment of the tool of the present invention , the transducers 212 are mounted to rotate azimuthally and transmit and receive acoustic energy at locations around the circumference of casing 115 as they rotate and at various depths as the tool is raised or lowered in the well . the depth can be analyzed by the sonde in situ , analyzed by data processor 218 at the surface , or stored , either in the sonde or at the site for analysis at a remote location . fig3 a is a waveform v , obtained from an ultrasonic cement - evaluation measurement taken , for example with the apparatus shown in fig2 . v is divided into two main portions . one portion , cv shown in fig3 b , represents the reflected energy which has interacted with a first interface 123 formed between casing 115 and fluid 121 and a second interface 125 formed between casing 115 and second material . the other portion , tiv shown in fig3 c , represents echoes which have interacted once with third interface 127 located between second material and third material 117 . multiple interactions with third interface 127 and interactions with more distant interfaces are neglected . all of the waveforms are functions of time ( t ) and the location at which they are collected . the location is specified in terms of azimuth ( θ ) and depth ( z ). mathematically : previous approaches to cement evaluation have concentrated on cv , because it is generally more energetic than tiv . however , this limits the techniques to measuring essentially the bonding condition at second interface 125 . it is desirable to extract the &# 34 ; buried &# 34 ; tiv under certain conditions , so that more information about the annulus itself can be gained . the first step of this method is to express tiv in mathematical form as : if a casing waveform is not negligible , subtracting it from the total waveform to obtain the third - interface waveform , provides information about the annulus beyond the casing . if the casing is perfect , i . e ., its inner and outer surfaces are perfect coaxial cylinders , and the exterior bonding condition is uniform ( either well bonded or free - pipe ), then cvs will be the same at all locations in the well . in other words , cvs are spatially invariant . also , if the third interface is not a cylinder coaxial with the casing , then the reflection from the third interface will vary spatially . in this case the spatial average of all the waveforms over θ and z , av ( t ), will be an approximation to cv ( t ): where the sums are over θ and z , and n is the number of points in the sum . there will be n identical cvs added together , and then divided by n , so one component of the average is cv itself . if tiv is different at every location , then the value of each location will appear with a factor of 1 / n in the final average . if n is large , and the different tivs do not add coherently , then the contribution of the tivs to the average will be small enough to neglect . an approximation to the desired third interface echo is obtained by subtracting the average from the original : however , casings are not perfect , so the casing waveform does vary spatially ( cv is cv ( t , θ , z )). in this case , a locally averaged waveform ( over θ and z ) must be calculated : ## equ1 ## where the sums are over θ and z , w is a spatial averaging window of finite extent whose sum is aw = σ [ w ( θ , z )], and cv ( t , θ , z ) is the waveform due to casing reverberations at the point ( θ , z ). w is not equal to zero only for some range in the θ and z directions . w does not need to be uniform , in which case it will have an effective range which is less than its full range . for the approximation to be good , the effective range must be chosen large enough such that tiv ( t , θ , z ) varies considerably in that range and nearly cancels itself out in the average . further , it must be small enough that cv ( t , θ , z ) is nearly constant over the effective range , so that the averaging does not effect it . if the casing signal were of interest , av could be regarded as the final product of spatial filtering . if the reflection from the third interface is of primary interest , subtracting the locally averaged signal from the original signal yields an appropriately spatially filtered signal : ## equ2 ## where δ ( θ , z ) is a kronecker delta function . this operation , which can be viewed as subtraction of a local average from the data , or as convolution (*) with the kernel sf , is one example of a spatial filter to select for tiv which has strong spatial variations over a cv which does not . this convolutional filter is a linear filter ; its output consists of weighted sums of its inputs , where the weights are predetermined and do not depend on the input . it is also possible to use nonlinear filters . for example , the weights may depend on the input , or the inputs may be raised to a power , or may appear as arguments of some transcendental function , etc ., as one skilled in the art will recognize . while the window - design criteria contain potentially conflicting requirements , they can be fulfilled . the geometry of the casing can be controlled much better than the geometry of the borehole or the position of the casing within the borehole . this is especially true in new casings , before corrosion has had time to occur , and in deviated holes where centralization and cementing is problematic . therefore , the casing waveform varies spatially less than the third - interface waveform under many practical conditions . practical problems exist for the application of spatial filtering . for example : some casing waveforms having fast spatial variations ; and some third - interface reflections have slow spatial variations . the invention seeks to overcome these problems by applying the choice of the domain for the spatial - averaging window , w . in other words , determining whether the average includes waveforms from far away from the position of interest , or only nearby . choosing a small window of interest , a large window of interest , or some window in between , requires the consideration of counter balancing interests . these counter balancing interests are summarized below in table i . table i______________________________________counter - balancing interests of small andlarge spatial averaging windows . large window small window______________________________________advantage &# 34 ; sees &# 34 ; slow variation removes fast variations in in the third - interface casing reflections reflectiondisadvantage does not remove fast does not &# 34 ; see &# 34 ; slowly variations in the varying casing reflections casing reflections______________________________________ there are other factors which also bear on the effectiveness of a particular window . these include the shape , as well as the width of the window . the shape determines whether all waveforms in the window receive the same weight , or whether more distant waveforms have more or less effect than nearer waveforms on the average . fig4 is a top view of a cased borehole 111 . casing 115 varies in thickness about its circumference . a spherically focused transducer 212 is mounted in sonde 210 ( fig2 ) and is situated in fluid 121 in borehole 111 . transducer 212 rotates azimuthally around the circumference of casing 115 generating and receiving signals , such as that of fig3 a as it rotates . fig5 illustrates a signal set . each signal is measured in terms of voltage as a function of time , from an individual azimuthal position obtained upon generating and receiving acoustic energy in accordance with the configuration of fig4 . each individual signal is similar to the one shown in fig3 a . fig5 permits identification of echoes from the various interfaces present in borehole 111 . the region between line 511 , whose endpoints are 511a and 511b , and line 513 , whose endpoints are 513a and 513b , is dominated by echoes from first interface 123 ( fig1 ). each signal has been aligned in time by shifting so that the echoes from first interface 123 occur at the same time . specifically , the zero crossing between the peak positive voltage and peak negative voltage has been shifted to approximately 7 μs . this removes any time shifts existing due to either minor errors in tool eccentering in the casing or non - roundness of the inside surface of the casing . the region to the left of line 513 contains energy which has reverberated in casing 115 . the frequency of reverberation is indicative of the thickness of casing 115 . the region between line 513 and sinusoidally - shaped line 515 , whose endpoints are 515a and 515b , is dominated by this energy which has reverberated in casing 115 without propagating beyond casing 115 . the region to the right of ( later than ) line 515 , is a mixture of energy which has reverberated in casing 115 , but not propagated beyond the casing , and energy which has reflected from third interface 125 ( fig1 ), and representing tiv . the energy to the left of line 515 is all from cv , while the energy to the right of line 515 is a mixture of cv and tiv . echoes between lines 511 and 513 ( from first interface 123 ) are substantially lined up vertically because the signals have been aligned . echoes between lines 513 and 515 ( second interface 125 ) line up with a slight curvature as a function of azimuth indicating that thickness of casing 115 changes as a function of azimuth . casing 115 is thinnest at about 67 °, and is thickest at about 247 ° ( 180 ° away ). finally , line 515 oscillates between about 15 μsec and 38 μsec indicating a great range of distances between transducer 212 and third interface 127 formed between second material and third material 117 . although the casing thickness is relatively constant around the circumference at a particular depth , casing 115 is eccentered within the cement . this causes a sinusoidal shaped onset ( beginning ) of energy received from third interface 127 between the cement and earth formation 117 . fig6 represents the same signals shown in fig5 after spatial filtering has been performed . the spatial filtering operation greatly increases the clarity of the reflections from third interface 127 ( tiv ). in fig6 this is represented by the region to the right of line 615 , formed between points 615a and 615b , which substantially retains the third interface echoes while substantially removing casing reflections ( cv ). the sinusoidally shaped onset of echoes from the third interface between annulus 119 and earth formation 117 accurately indicates the distance between the casing and formation . the spatial filter applied to signals in fig5 to obtain the result in fig6 consists of subtracting the locally averaged signal av ( t , θ , z ) from eq . ( 4 ): ## equ3 ## where m is the azimuthal incremental index and n the depth incremental index . δ ( n ) is a kronecker delta function . there is no averaging in the depth direction for this example so n does not appear in the equation . the total width of the window , m , is 20 azimuthal scan positions . fig7 a and 7b show a borehole configuration ( 7a ) and a corresponding aligned and spatially filtered signal set representing casing 115 centered and cemented in borehole 111 , with two buried channels 721a and 721b . two types of third interface conditions exist in fig7 a . the first type is the cement / formation bond , at azimuths where there is no channel . the onsets of the echoes from this interface condition occur along straight line 715 between points 715a and 715b ( fig7 b ). these echoes appear only weakly because they are nearly constant in azimuth , and the filter removes azimuthally invariant echoes . the second type of third interface condition is a cement / channel interface . echo 717 from a first channel is centered at approximately 90 ° and is about 35 ° wide . echo 719 from a second channel is centered at approximately 180 ° and is about 50 ° wide . at their edges , these channels are nearly the same distance from the casing as the cement / formation interface . however , as points closer to their centers are considered , third interface 127 moves closer to the casing as is seen in fig7 a . the echoes from the cement / channel interfaces appear strong in fig7 b because they are strong functions of azimuth , and thus not removed by the spatial filter . the onsets of echoes from the cement / channel interfaces accurately indicate their geometry , being simultaneous with the onsets from the cement / formation echoes at their edges , and earlier toward the centers . thus the onsets of the cement / channel interfaces 717 and 719 form an &# 34 ; image &# 34 ; of the channels , and are important in evaluating the quality of the cement job . a very simple deconvolution filter is shown in fig8 . when this filter is convolved with the signals in fig3 a and 3c , it yields the desirable results in fig9 and 10 , respectively . the filter has the form : c c is its compressional acoustic velocity of the casing ; and t 0 , can be found in a number of ways , either from previously known information about casing thickness and the acoustic impedances of materials in the borehole , or from the data itself . r is approximately the decay ratio of a signal reverberating in the casing after one reverberation . there are many approaches to the latter method , one of which is to use casing thickness and second - material impedance as calculated for example , by the processing algorithm of the usi ™ tool . many different forms of a deconvolution filter are possible , and there are many ways of determining their parameters ( see peacock , k . l . and treitel , s ., productive convolution theory and practice , geophysics , 1969 , vol . 34 , no . 2 .). in practice , the dirac impulse , δ , which is a function of continuous time , must be approximated by some function of discrete time . the quality of the results depends on the quality of the approximation . the total signal v ( t , θ , z ) of fig3 a is composed of three contributions which overlap in time but are affected differently by deconvolution : civ ( t , θ , z ) is the echo from the inner surface of the casing , which is essentially the high amplitude portion of cv ( t , θ , z ) in fig3 b . crv ( t , θ , z ) is the casing resonance , which is essentially the later , low - amplitude portion of cv ( t , θ , z ) in fig3 b . the sum of civ ( t , θ , z ) and crv ( t , θ , z ) is cv ( t , θ , z ), the casing echo discussed above . tiv ( t , θ , z ) is the third - interface echo . deconvolution with the filter in eq . ( 6 ) subtracts a scaled and shifted copy of the original signal from itself . the most important effect of deconvolution is to reduce the amplitude of crv ( t , θ , z ) as seen by comparing fig3 a and 9 . reducing the amplitude of the casing resonance generally improves the ability to examine the filtered version of tiv ( t , θ , z ). another important effect of deconvolution is to cause the peak of the filtered version of tiv ( t , θ , z ) to occur near its onset , around 42 μs in fig1 , rather than growing in amplitude as it does in fig3 c . detection of the onset is the easiest means of measuring the thickness of the second material , and peak detection or related algorithms tend to be more robust than threshold detection algorithms . fig1 a shows a spatially filtered set of signals from an unfocused transducer in a borehole configured like that of fig4 . fig1 b shows the same signal set after deconvolution . in fig1 a , there is remnant of the casing resonance between line 1111 and sinusoidally - shaped line 1113 than between line 1115 and sinusoidally - shaped line 1117 in fig1 b . while the echoes immediately after ( to the right of ) lines 1113 and 1117 are patterned similarly , the echoes in fig1 a grow in amplitude at later times . in contrast , echoes in fig1 b generally decrease in amplitude . the remnant of the reflection from the inner surface of the casing , to the left of line 1115 lasts longer due to deconvolution , than it does to the left of line 1111 . another aspect of the invention is its applicability to borehole measurements before hydration of fill material in the annulus between the casing and the earth formation . such information may be useful for a number of applications including quality control of casing centralization before cement placement and / or after cement is placed but before hydration occurs . it should be understood that although the figures show aligned signal sets , it is not a requirement of the invention that the signals be aligned . in addition , the results of spatial filtering may be dependent on the spatial sampling rates and on the dynamic range of the digitized signals in the signal set . therefore , the above description should not be taken as limiting the scope of the invention which is defined by the appended claims . | 6 |
example embodiments will now be described more fully with reference to the accompanying drawings . although the apparatus for producing centrifugal force can take many forms , in one presently preferred embodiment , a turntable 10 serves as a vehicle for supporting and rotating one or a plurality of sand molds about a rotation axis 12 , as illustrated in fig1 and 2 . in the exemplary embodiment illustrated , the turntable 10 supports 4 sand mold structures 14 a - 14 d at the 12 o &# 39 ; clock , 3 o &# 39 ; clock , 6 o &# 39 ; clock and 9 o &# 39 ; clock positions . of course , a greater or smaller number of molds can be implemented based on the needs of the particular application . at the center of turntable 10 is the ingate structure having a pouring basin 16 that defines an inlet 18 through which the molten metal is poured . molten metal poured into inlet 18 flows downwardly under force of gravity and then laterally through passageways 19 to each of the respective mold structures . as will be more fully explained , the molten metal is introduced into inlet 18 while the turntable is gradually ramped up in speed , causing the molten metal to flow in a controlled fashion into the mold cavity 20 by combined gravity feed and centrifugal force feed . referring to fig3 , further details of the mold structure and ingate system may be seen . a steel base 20 , steel side wall 24 and steel lid 26 define the casting flask that house the sand mold 28 . a riser 30 and sprue 32 couple the passageways 19 of pouring basin 16 with the mold cavity 20 so that molten metal introduced into orifice 18 will flow initially by gravity feed through the sprue 32 , into the riser 30 and then finally into the cavity 20 . if desired , a filter 34 may be introduced in the flow path to filter out impurities . note that the sprue and riser system are preferably located generally about the center line l of the mold . thus , the in pour of molten metal will initially flow by gravity feed into the mold cavity . as best seen in fig2 , the turntable 10 is attached via a clutch mechanism or coupling 40 and gearbox 42 to an electric motor 44 . the motor is controlled by a suitable electronic controller 46 that allows the ramp - up acceleration and / or speed of the motor to be adjusted as will be next described . the clutch mechanism or coupling 40 can be disengaged to allow the turntable to coast to a stop under its own inertia . if desired , a brake 48 may be included to assist in slowing or stopping rotation of the turntable at the appropriate point in the operating cycle . referring now to fig4 a - 4 e , a further explanation of the manner of filling the mold cavity under combined gravity feed and centrifugal force feed will now be provided . fig4 a - 4 e show successive stages of filling mold cavity 20 as the turntable progressively ramps up and then coasts down in angular speed . as illustrated at fig4 a , during the initial phase of the pour , the turntable may be stationary or it may be rotating slowly , such that gravity is the dominant force causing the poured metal to flow into the cavity as illustrated . fig4 b , 4 c and 4 d illustrate that the turntable is accelerated while additional molten metal is introduced into the cavity . note that the effects of centrifugal force are apparent at these stages of pour . this is evident because the surface of the molten metal “ s ” becomes increasingly tilted as the acceleration continues , until the surface lies in a substantially vertical plane , as illustrated in fig4 d . once the entire quantity of liquid metal has been introduced into the mold cavity , the driving force applied to the turntable is removed , allowing the turntable to gradually coast to a stop . during this coasting time , the metal will begin to solidify . once solidified , the turntable can be permitted to coast to a stop , or the mechanical brake may be used to assist in stopping rotation . with reference to fig4 b , note that the relative angle “ α ” between the surface “ s ” of the liquid metal and the vertical - most face of the interior cavity of the mold is greater than 0 degrees in fig4 b . thus , if the centrifugal force acting on the poured liquid metal were to remain constant throughout the pour , the incline of the surface “ s ” would remain the same and an air bubble might become trapped in the outer extremity of the part . the ingate filling technique overcomes this by further accelerated the turntable , as illustrated in fig4 c and 4 d , so that the centrifugal force causes the angle of the poured metal surface to equal or exceed the angle of the vertical - most interior surface encountered as the liquid level rises . thus , by the time the liquid metal pour has reached that shown in fig4 d , the angle “ α ” is essentially 0 , and any trapped gas will be purged . the amount of centrifugal force required to purge trapped gas will , of course , depend on the geometry of the part being manufactured , that is it will depend on the interior geometry and construction of the mold cavity . where the mold cavity is made of gas permeable material , trapped gas can be relieved through the permeable sidewalls of the cavity . in other embodiments where the mold cavity is impermeable , more care may need to be taken to ensure any trapped gas is purged . in the exemplary embodiment illustrated in fig4 a - 4 e , a centrifugal force on the order of 5 g ( 5 times the force of gravity ) achieves the desired result . a greater centrifugal force could be used , of course , but at some point degradation of the sand mold can occur . thus , the preferred technique is to maintain a substantially constant centrifugal force during all but the initial stages of the pour , where the constant centrifugal force is ( a ) sufficient to tilt the surface of the molten metal sufficiently to fill any voids in the cavity , and ( b ) safely below the point at which mold degradation may occur . fig5 is a graph depicting an exemplary ramp - up in the turntable speed during the pouring phase , followed by a coasting phase after the liquid metal has solidified . as illustrated in the graph and also as reflected in the equation below , the velocity of the turntable changes during the pour , in order to maintain a substantially constant centrifugal force ( g c ). the velocity varies with time based on several factors . as eq . 1 above illustrates , the rotational velocity of the turntable is proportional to the square root of the radius of rotation / metal mass ratio . in the equation , a constant centrifugal force g c is selected to lie within a range ( a ) sufficient to tilt the surface level of the molten metal so that air pockets are eliminated and ( b ) a high force that would damage or degrade the sand mold . although the rotational velocity v t is influenced by the centrifugal force g c , that velocity is not constant because both the radius of rotation r ( t ) and mass of the poured metal m ( t ) change as the pour progresses . to see this , refer to fig4 a - 4 e . it will be seen that the radius of rotation ( r ), measured from the axis of rotation of the turntable to the center of gravity of the liquid metal , changes as the level of molten metal rises . in general , the radius of rotation becomes shorter as the cavity becomes filled . similarly , the mass of the molten metal contained within the cavity increases as the cavity becomes filled . thus , the rotational radius / mass ratio is time - dependent . hence , the rotational velocity of the turntable must be controlled to reflect this time dependency . in one preferred embodiment , the controller 46 drives the motor 44 based on this relationship to achieve the desired ramp - up and coast behavior . the controlled velocity of the turntable is a function of time , and in this case time is a function of still further variables , namely the flow rate at which molten metal is introduced and the rate at which the molten metal solidifies . as illustrated in fig3 , molten metal is introduced through a sprue 32 with embedded filter 34 . this inlet structure acts as a restricted orifice that controls the rate at which liquid metal flows into the riser , and the riser also may include a restricted region through which metal flows into the cavity . depending on the geometries of the cavity being filled and upon the respective diameters of these restricted orifices , the liquid metal will flow into the cavity at a controlled rate . thus , given the final volume of the cavity , and this flow rate , the amount of time needed to fill the cavity and the requisite centrifugal force can be determined . as depicted in the graph in fig5 , the velocity of the turntable is ramped up over this filling interval where the acceleration or ramp - up rate is controlled to achieve a substantially constant centrifugal force in spite of the fact that the rotational radius and mass of the liquid metal are changing . after the cavity becomes filled , a centrifugal force greater than that of gravity is continued to be applied until the metal solidifies . this may be accomplished by maintaining the rotational rate of the turntable at the rate achieved when the cavity became completely filled . by maintaining the centrifugal force at this level , the liquid metal is forced to remain in the cavity until it cools . in this way , it is possible to precisely fill the cavity without relying on a large quantity of excess metal in the riser to present defects in the finished part . once the cavity has been entirely filled , and once the metal begins to solidify , it is possible to remove the driving force from the turntable , allowing it to coast to a stop on its own inertia . the driving force may be removed at a point where the liquid metal will have finally cooled before the turntable coasts to a speed below which molten metal could bleed out of the cavity . by judiciously choosing the point at which the driving force to the turntable is removed , the combined gravity and centrifugal force feed technique saves a significant amount of energy and maximizes the speed at which cast parts can be manufactured . the driving force shut - off point is largely controlled by the rate at which the liquid metal solidifies . as illustrated in fig6 , the first material received in the cavity ( at the end furthest from the sprue ) becomes to cool sooner and is thus at a cooler temperature than the last material received ( at the sprue end ). thus , at some point , material at the cooler end of the cavity will have solidified whereas material at the hotter end will still be in a molten state . thus , the mass of molten metal within the cavity is gradually reduced to 0 as the part solidifies further . because the centrifugal force is used to hold the molten metal in the cavity , the mass value in equation 1 gradually falls to 0 as the part solidifies . thus , the velocity requirements of the turntable may need to account for this effect to achieve ultimate control over the formation of the finished part with minimal waste . in this regard , while it is the goal to eliminate all waste material , in practice , there is usually a final small shrinkage defect at the point where the metal is last to cool . thus , it may be necessary to pour slightly more material than is required so that the final shrinkage defect occurs in the riser region which can be cut away and re - melted . because the size of the waste material is small , it is often possible to break away the waste portion by hand ( without the need to use grinding equipment and other energy - consuming power tools ). the gravity and speed - controlled centrifugal feed system can be implemented in a variety of different configurations . the turntable , for example could be replaced by a hub and spoke spider wheel in which the mold flasks are disposed on the spokes of the wheel . alternatively , the turntable might be replaced with a rotating drum , where the mold flasks are placed about the inner side wall of the drum . the feed system technique described herein lends itself well to economical , space - saving and energy - efficient plant floor layouts . exemplary of such is the layout shown in fig7 . as illustrated there , a conveyor system 50 delivers the mold flasks to various operating stations . thus at location { circumflex over ( 1 )}, a robot loader 52 lifts the flasks containing the sand mold assembly onto the conveyor where it is then transported at { circumflex over ( 2 )} to the metal pouring area 54 . the mold flasks are placed on turntable structures 53 that each has a drive coupling assembly on the underside . this coupling assembly mates with the electrically driven motor that applies the rotational velocity to that turntable when it is in the metal pouring area 54 . the ramp - up acceleration of the turntable is controlled as discussed above as metal is poured in a controlled amount into the in gate . once the cavities have been filled and the metal has sufficiently cooled , the conveyor transports the turntable to the inertia centrifugal area { circumflex over ( 3 )} where the turntable coasts under its own inertia to a final stop . the conveyor 50 is designed so that the final stop occurs near the mold dumping station { circumflex over ( 4 )}. at this station , the finished part is removed from the mold and treated conventionally to shot blast the surface and remove the riser . the flask then conveys onto the flask cleaning station { circumflex over ( 5 )} where it is ready for reuse at step { circumflex over ( 1 )}. the foregoing description of the embodiments has been provided for purposes of illustration and description . it is not intended to be exhaustive or to limit the invention . individual elements or features of a particular embodiment are generally not limited to that particular embodiment , but , where applicable , are interchangeable and can be used in a selected embodiment , even if not specifically shown or described . the same may also be varied in many ways . such variations are not to be regarded as a departure from the invention , and all such modifications are intended to be included within the scope of the invention . | 1 |
the invention will be described in greater detail hereinbelow by means of examples . unless indicated otherwise , the percentages given are to be understood as being by weight , based on the total composition . 42 . 82 g of polymethacrylic acid ( mw = 4000 ) are introduced into a suitable container equipped with a heating means and mechanical stirring , and the heating is set to 60 ° c . 0 . 40 g of sodium hydroxide ( 50 % naoh ) is then introduced , and it is ensured that the reaction mixture is homogeneous . 56 . 78 g of methoxypolyethylene glycol ( polyglycol m 2000 ) are then introduced , with continued stirring . a vacuum (− 0 . 8 bar ) is applied , and the heating is set to 100 ° c . when the water starts to distil , and as the temperature rises , the heating is gradually increased to 175 ° c . when the temperature has reached 175 ° c ., heating is continued for a further 4 hours . the reaction is stopped by removing the vacuum and stopping heating , when the methoxypolyethylene glycol content , measured by size exclusion chromatography , is less than 2 %. the polymer so obtained has an ester number of 20 . it is anhydrous and handleable at a temperature of 50 ° c . it is preferably used without further purification . table 1 below summarizes the proportions of raw materials employed in the preparation of product a . polymer a obtained as indicated above is formulated to 30 % dry extract and by incorporating 0 . 23 % of an antifoaming agent 1 and 0 . 02 % of an antifoaming agent 2 . the ph is adjusted to ph 7 by means of a neutralizing base ( sodium hydroxide ). in a rw 20 n rayneri mixer ( distributed by ika ) equipped with a deflocculating blade of the type having a diameter of 4 cm , 400 g of iron oxide suspension were prepared as follows . 195 . 2 g of water , 4 . 0 g of formulation b obtained as indicated above and 200 g of yellow pigment ( bayferrox 420 from lanxess ) were introduced in that order , and stirring is carried out for 10 minutes at a rate of 2000 rpm . 0 . 8 g of xanthan is then introduced as stabilizing agent , and stirring is continued for a further 5 minutes at a rate of 2000 rpm . example 1 is repeated , except that formulation b is replaced by 4 . 0 g of sokalan cp10 from basf ( polyacrylic acid solution ). in a rw 20 n rayneri mixer ( distributed by ika ) equipped with a deflocculating blade having a diameter of 4 cm , 400 g of iron oxide suspension were prepared as follows . 197 . 4 g of water , 2 . 0 g of formulation b obtained as indicated above and 200 g of black pigment ( bayferrox 330 from lanxess ) were introduced in that order , and stirring is carried out for 10 minutes at a rate of 2000 rpm . 0 . 6 g of xanthan is then introduced as stabilizing agent , and stirring is continued for a further 5 minutes at a rate of 2000 rpm . example 2 is repeated , except that formulation b is replaced by 2 . 0 g of sokalan cp10 from basf ( polyacrylic acid solution ). in a rw 20 n rayneri mixer ( distributed by ika ) equipped with a deflocculating blade having a diameter of 4 cm , 400 g of iron oxide suspension were prepared as follows . 157 . 8 g of water , 1 . 6 g of formulation b obtained as indicated above and 240 g of red pigment ( bayferrox 110 from lanxess ) were introduced in that order , and stirring is carried out for 10 minutes at a rate of 2000 rpm . 0 . 6 g of xanthan is then introduced as stabilizing agent , and stirring is continued for a further 5 minutes at a rate of 2000 rpm . example 3 is repeated , except that formulation b is replaced by 1 . 6 g of sokalan cp10 from basf ( polyacrylic acid solution ). the relative proportions of the components of the pigment suspensions prepared according to the above examples are summarized in the table below . in order to evaluate the color strength of the prepared pigment suspensions , mortars were prepared by incorporating the pigment suspensions at the step of producing the dry mortar which will be used to produce dry mortar blocks using a hydraulic press . a dry mortar according to the formula indicated in table 4 below was therefore first produced as follows . 1250 g of afnor sand and 350 g of cement ( hts superblanc du teil cp2 52 . 5 n ) are introduced into a 3 - litre stainless steel bowl of a mixer ( of the power mix type distributed by krups ) equipped with a whip - type stirrer blade , and stirring is carried out for 30 seconds at power 3 . an amount equivalent to 3 g of dry matter of the suspension of reference j , rj , n , rn , r or rr and 102 g of water are then introduced in a period of 30 seconds , and stirring is continued for a further 4 minutes . the mortar has a ratio e effective / l equivalent of 0 . 29 . a mortar block is then produced from that mortar , as follows . 500 g of colored mortar are introduced into a mould of dimensions 7 × 12 × 3 cm , and then pressing is carried out in a hydraulic press at 130 bar for 10 seconds . the block is removed from the mould and left under an ambient atmosphere for one week . the coloring of the mortar block so obtained is evaluated as follows . 7 days after production of the mortar , calorimetric measurements are carried out by means of a minolta cr 310 calorimeter at the surface of the mortar block in three different locations without efflorescence . the average of those three measurements is recorded in table 5 below . a comparison of the colorimetry values recorded for the blocks of the examples referenced n and rn shows that the coefficients a and b are almost identical , while the clarity ( parameter l ) is lower for the block colored with formula n as compared with that colored with formula rn . these results show that the nature of the dispersing agent used in the formulation of a pigment suspension is significant . more precisely , those results demonstrate the improvement in the color strength of a pigment suspension intended for coloring a dry mortar when the latter is formulated with an alkylene polyoxide polycarboxylate rather than with a polyacrylic acid . the gain in color strength is estimated at 4 . 0 % ( l rn − l n / l rn ). a comparison of the colorimetry values recorded for the blocks colored with suspension j and rj shows that the block colored with formula j has values for b and saturation which are higher than those of the block colored with formula rj . it is deduced that the color observed on the block colored with formula j is deeper than that observed on the block colored with formula rj . this result shows the value of formulating a pigment suspension with alkylene polyoxide polycarboxylate rather than with a polyacrylic acid , the estimated gain in color strength is accordingly 2 . 0 % ( s rj − s j / s rj ). a comparison of the colorimetry values recorded for the blocks colored with suspension r and rr shows a difference in the coefficient a and in the saturation value l . those values are accordingly higher for the mortar block colored with formula r than those of the block colored with formula rr characteristic of a deeper color . this result shows the gain in color strength effected by the use of alkylene polyoxide polycarboxylate rather than a polyacrylic acid . for this test , the gain in color strength was estimated at 4 . 81 % ( s rn − s r / s rn ). | 2 |
it is an aspect of the present invention that solder - reflow after flip - chip solder - bump bonding can be used to improve the alignment accuracy between two substrates . since most solders have a melting point that is higher than the thermal budget of a typical pfa , however , it is a further aspect of the present invention to use indium - based solder bumps ( including pure indium ), which have a low melting point . it is well known , however , that indium - base solders quickly develop a surface oxide that inhibits their use in bump bonding applications . it is a further aspect of the present invention , therefore , that reduction of the surface oxide on indium - based solder bumps is done while the solder bumps are contained within a chamber having a controllable environment . a pick - and - place tool having access into the chamber is then used to roughly align and bond the two substrates once the surface oxide is sufficiently reduced . after bonding , the two substrates are heated to melt the indium solder enabling them to reflow in a manner that reduces their surface energy by substantially minimizing their surface area . the solder bumps are provided in an arrangement that affords sufficient force during solder reflow that the solder bumps can induce relative motion between the two substrates , thus resulting in more precise alignment . fig1 depicts a schematic drawing of a cross - sectional view of an integrated focal plane array and read - integrated circuit in accordance with an illustrative embodiment of the present invention . device 100 comprises substrate 102 , substrate 104 , and solder joints 106 . substrate 102 is a portion of a read - out integrated circuit chip that includes a plurality of circuits 108 , interconnects 110 , and bond pads 112 . the plurality of circuits 108 collectively defines a read - out integrated circuit . circuit 108 is a conventional read - out circuit for interfacing to a photoreceptor element of a focal plane array . circuit 108 is one of a plurality of such circuits that collectively define a read - out integrated circuit . interconnects 110 are conventional electrically conductive traces that electrically couple circuit 108 with bond pads 112 . bond pads 112 are conventional bond pads suitable for enabling solder - bump bonding of the roic with a focal - plane array . substrate 104 is a portion of a focal - plane array chip that comprises a plurality of avalanche photodiodes 114 , each electrically coupled with a pair of bond pads 116 . the plurality of avalanche photodiodes 114 collectively defines a focal - plane array . bond pads 112 are arranged in a first arrangement on substrate 102 . in similar fashion , bond pads 116 are arranged in a second arrangement on substrate 104 . the first and second arrangements of bond pads are complimentary such that when substrates 102 and 104 are positioned face - to - face , the layouts of the two arrangements of bond pads substantially match . each of bond pads 112 and 116 includes a surface that wets the material of solder joints 106 . each of bond pads 112 and 116 has a center region having surface area , a 1 , that is exposed , while layer 118 covers the remaining area of the bond pad as well as regions of substrate 102 and 104 that surround these center regions . layer 118 comprises a material , such as silicon nitride , that does not wet the material of solder joints 106 . solder joints 106 are solder bumps of substantially pure indium . indium is preferably used for solder joints 106 due to its low melting point . in the prior art , however , indium is not typically used due to the fact that it readily forms a surface oxide that can impair its utility as a bonding material . this is particularly true in a production environment , where reliability and repeatability of solder joint characteristics are paramount . in some embodiments , solder joints 106 comprise a solder other than pure indium . fig2 depicts a schematic drawing of a cross - sectional view of a system for enabling hybrid integration of a focal - plane array and a read - out integrated circuit in accordance with the illustrative embodiment of the present invention . system 200 comprises chamber 202 , tool 204 , gas system 206 , and chuck 208 . chamber 202 is a substantially enclosed chamber suitable for controlling the environment that surrounds substrates 102 and 104 . substrate 102 comprises solder bumps 210 and substrate 104 comprises solder bumps 212 . solder bumps 210 are arranged in a first arrangement on the surface of substrate 102 . solder bumps 212 are arranged in a second arrangement on the surface of substrate 104 , wherein the first and second arrangements are complimentary such that they substantially match when the substrates are positioned in a face - to - face orientation . in some embodiments , only one of substrates 102 and 104 comprises solder bumps . by controlling the environment within chamber 202 , desorption of surface oxide on the solder bumps can be effected , as described below and with respect to fig4 and 4 a - d . in some embodiments , chamber 202 includes ports for enabling gas to escape the chamber , for example , during an oxygen purge when oxygen is displaced by hydrogen pumped into the chamber . tool 204 is a conventional pick - and - place tool suitable for controlling the relative position between substrates 102 and 104 . tool 204 controllable holds and releases substrate 104 and typically has up to six - axis control capability . gas system 206 is a system for controllably introducing one or more gasses into chamber 202 . in the illustrative embodiment , gas system 206 is configured to introduce argon and hydrogen into chamber 202 ; however , it will be clear to one skilled in the art , after reading this specification , how to specify , make , and use alternative embodiments of the present invention wherein gas system 206 introduces one or more suitable gasses other than argon and hydrogen into chamber 202 . gasses suitable for use in embodiments in accordance with the present invention include , without limitation , hydrogen , argon , nitrogen , forming gas , sulfur hexafluoride , chlorine - containing gasses , and the like . in some embodiments , gas system 206 includes gas - heating apparatus for controlling the temperature of a gas that is being introduced into chamber 202 . chuck 208 is a conventional vacuum chuck for securing a substrate . in some embodiments , chuck 208 can also control the temperature of a substrate mounted in the chuck and / or an electrical bias on the substrate . fig3 depicts operations of a method for integrating two substrates in accordance with the illustrative embodiment of the present invention . fig3 is described with continuing reference to fig1 and 2 and fig4 a - d . method 300 begins with operation 301 , wherein substrates 102 and 104 are put into rough alignment . fig4 a - d depict schematic drawings of cross - sectional views of substrates 102 and 104 at different points in a hybrid integration process in accordance with the illustrative embodiment of the present invention . fig4 a depicts substrates 102 and 104 while positioned in rough alignment with one another but while their respective solder bumps are not in contact . substrates 102 and 104 are depicted while enclosed by chamber 202 . rough alignment can be attained with conventional pick - and - place tools , such as tool 204 . examples of suitable pick - and - place tools include the palomar 3800 die bonder , etc . in the illustrative embodiment , each of solder bumps 210 and 212 is disposed on their respective bond pad such that its extent exceeds the perimeter of the bond pad . in other words , the cross - sectional area , a 2 , of each of solder bumps 210 and 212 where it meets its respective bond pad is greater than the surface area of the bond pad , a 1 . it should be noted that solder bumps 210 and 212 are depicted as hemispheres . in some embodiments , at least one of solder bumps 210 and 212 has a shape other than at operation 302 , surface oxide 402 is reduced on surface 404 of solder bumps 210 and 212 . surface oxide 402 is reduced by first purging chamber 202 of oxygen and filling chamber 202 with heated hydrogen gas . elevating the temperature of solder bumps 210 and 212 in the presence of hydrogen enables the reduction of surface oxide 402 . once surface 404 is substantially oxide - free , the temperature of the hydrogen environment is reduced but the environment in chamber 202 remains substantially oxygen - free . after reduction of surface oxide 402 , each of solder bumps 210 and 212 projects above the height of its respective bond pad by height h 1 . fig4 b depicts substrates 102 and 104 while positioned in rough alignment with one another and after the reduction of surface oxide 402 , but while solder bumps 210 and 212 are not in contact . at operation 303 , solder bumps 210 and 212 are brought into close proximity , but not into contact , by tool 204 . this results in a separation distance between bond pads 116 and 118 of distance d 1 . in some embodiments , alignment features are included on each of substrates 102 and 104 to facilitate the rough alignment of solder bumps 210 and 212 as well as establish a separation distance between substrates 102 and 104 after operation 303 . fig5 a and 5b depict alignment features for facilitating alignment of solder bumps in accordance with an alternative embodiment of the present invention . alignment feature 500 comprises probe 502 and receiver 504 . fig5 a depicts probe 502 and receiver 504 prior to engagement . fig5 b depicts probe 502 and receiver 504 after engagement . probe 502 is a substantially hemispherically shaped projection that is located on substrate 102 at a point outside the arrangement of solder bumps 210 . receiver 504 is a substantially circular annulus that is located outside the field of solder bumps 212 on substrate 104 . typically , at least three probes and matching receivers are included on substrates 102 and 104 to ensure good lateral and rotational alignment . in some embodiments , probes 502 are located on substrate 104 and receivers 504 are located on substrate 102 . in some embodiments , at least one of probe 502 and receiver 504 is located within the arrangement of solder bumps on its respective substrate . at least one of probe 502 and receiver 504 typically comprises a material that can be shaped in three - dimensions and does not exhibit excessive friction . suitable materials for use in probe 502 and receiver 504 include , without limitation : cyclotene advanced electronic resins , such as benzocyclobutene ( bcb ); su - 8 ; polyimides ; photoresists ; dielectrics , such as nitrides , oxide , oxynitrides , etc . ; ceramics ; metals , solders ; and the like . in some embodiments , at least one of probe 502 and receiver 504 is formed as a recess in the surface of its respective substrate via an etch process . in operation , the thicknesses , t 1 and t 2 , of probe 502 and receiver 504 , respectively , as well as the width , w , of opening 506 in receiver 504 , are selected to provide good lateral and rotational alignment and to establish a desired separation between substrates 102 and 104 at the end of operation 303 . returning now to fig3 and 4 a - d , during operation 303 , tool 204 roughly aligns substrate 104 to substrate 102 such that d 1 is greater than the combined height of solder bumps 210 and 212 ( i . e ., d1 & gt ; 2h1 ). currently available production - scale aligner - bonders can typically attain lateral alignment accuracy of approximately 10 microns . probe 502 and receiver 504 are sized such that this level of accuracy enables their engagement , which then improves the lateral precision of the alignment between the substrates to within a few microns . accurate alignment of solder bumps 210 and 212 within a few microns is sufficient to enable reflow of the solder bumps to bring bond pads 112 and 116 into fine alignment , as described below . at operation 304 , solder bumps 210 and 212 are heated above their melting point . because the material of solder bumps 210 and 212 does not wet to layer 118 , it exhibits a very high contact angle where the solder bump material meets their respective bond pads . in some cases , for example , the solder bumps form substantially spherical shapes that project outward from their respective bond pads . as a result , the projection of bond pads 210 and 212 above their respective bond pads increases to height h 2 , which is greater than half the distance d 1 . due to this increase in their height , each of solder bumps 210 comes into physical contact with its corresponding solder bump 212 . during operation 304 , heated hydrogen gas typically flows into chamber 202 . fig4 c depicts substrates 102 and 104 after solder bumps 210 and 212 are in physical contact within chamber 202 . at operation 305 , substrate 104 is released by tool 204 . this enables substantially unconstrained relative motion between substrates 102 and 104 . in some embodiments , in order to improve the oxygen purge from chamber 202 , a vented cover is installed to block the access port through which tool 204 had access to substrate 104 . during operation 305 , each contacting pair of solder bumps 210 and 212 is kept at an elevated temperature for a dwell time sufficient to enable them merge into a single liquid solder joint 406 . fig4 d depicts substrates 102 and 104 after the formation of solder joints 406 . the temperature of solder joints 406 is maintained at an elevated temperature to enable them reduce their surface energy by substantially minimizing their surface area . the reduction of surface energy of solder joints 406 generates enough force to move substrate 104 relative to substrate 102 thereby improving the alignment of bond pads 116 and 112 . at operation 306 , once bond pads 116 and 112 are suitably aligned , the temperature of chuck 208 is reduced , which reduces the temperature of solder joints 406 enabling them to solidify into solder joints 106 , as depicted in fig1 . it is to be understood that the disclosure teaches just one example of the illustrative embodiment and that many variations of the invention can easily be devised by those skilled in the art after reading this disclosure and that the scope of the present invention is to be determined by the following claims . | 7 |
referring now to the figures in detail illustrating a preferred embodiment of a laser object seeker system , and first referring to fig1 and 3 , there are shown schematic representations of a seeker head 2 , e . g ., a cylindrical , tapered or conical head , moving forward in direction 4 , also constituting the seeker &# 39 ; s head axis . on the seeker head 2 there are located a plurality of laser proximity sensors ( ps &# 39 ; s ) 6 to 6 ″″ and 8 to 8 ″″ ( see fig1 and 3 ) pointing sideways into the sea water 10 . one or more of the ps &# 39 ; s 6 to 6 ″ emit a laser beam 12 in the direction of the sea water 10 . the laser wavelength of the beams is selected so as not to penetrate the sea water 10 and to be reflected from the sea surface 14 , back in direction 16 into at least one of the dedicated detectors of the ps &# 39 ; s 6 to 6 ″. further seen are a plurality of laser ps &# 39 ; s 8 to 8 ″″ pointing sideways and emitting laser beams 18 in the direction of the sea water 10 . the laser wavelength of the beams of these ps &# 39 ; s is selected to penetrate the sea water 10 , to be partially reflected from the sea water surface 14 and partially reflected by the sea bed 20 , back in directions 22 and 24 respectively , into dedicated detectors of ps &# 39 ; s 8 to 8 ″″. as the reflected amplitude and time of the beams are known , they are used to determine the various reflection distances , as per - se known . in this embodiment , the ps 6 ′ serves as a reference measuring distance to the surface 14 and ps 8 ′ measures the depth of the sea bed 20 . while in the shown embodiment , the ps &# 39 ; s point sideways , in other embodiments the ps &# 39 ; s may be arranged on the seeker &# 39 ; s head 2 to point at a downwardly angle forwards in the direction of flight . also , the seeker &# 39 ; s head 2 may be rotatable about its axis . computing means for differentiating between the reflections received from the sea water surface , possibly from the sea bed and from a seaborne object may be included in the seeker &# 39 ; s head or in any other part of the airborne vehicle . fig2 illustrates a schematic representation of the seeker head 2 , moving forward in direction 4 and having a plurality of ps &# 39 ; s 6 to 6 ′ and 8 to 8 ″″ pointing sideways . at least one of the ps &# 39 ; s 6 to 6 ′ emits a laser beam 12 in the direction of the sea surface 14 where seaborne object 26 , e . g ., a boat is present . the laser wavelength is selected not to penetrate the seawater 10 and to be reflected in direction 16 from the sea water surface 14 or from the seaborne object 26 into the dedicated detectors of ps &# 39 ; s 6 to 6 ′. a plurality of laser ps &# 39 ; s 8 to 8 ″″ point sideways and emit laser beams 14 towards the sea water 10 . the laser wavelength of the beams is selected to penetrate the sea water 10 and to be partially reflected in direction 22 from sea water surface 14 , and sea bed 20 , into dedicated detectors of the ps &# 39 ; s 8 to 8 ″″. as can be seen , in this case , however , the reflection surface of the beam is the reflection from the seaborne object 26 in direction 22 . the reflected amplitude and time of the beam determine the various distances , as per - se known , with the ps 6 serving as a reference measuring distance to the water and the ps 8 measuring the sea depth . in fig4 a there is illustrated a signal produced by detectors of ps &# 39 ; s 6 to 6 ″″, while fig4 b shows the signals produced by the detectors of ps &# 39 ; s 8 to 8 ″ for sea water . in fig4 c there is illustrated signal produced by the detectors of ps &# 39 ; s 6 to 6 ″″ while fig4 d shows a signal produced by the detectors of ps &# 39 ; s 8 to 8 ′, which in this case , have equal timing and distance received from a seaborne object . the methods of operating the systems described with reference to fig1 to 4 will now be briefly described . according to an embodiment of a method of operation of the present invention , a single laser beam is used , where the laser beam is selected to enhance or reduce seaborne object laser reflection in comparison with the sea waves . according to a further embodiment of a method of operation of the present invention , there is provided a laser beam that penetrates the sea water , e . g ., green laser light , wherein the impingement on the seaborne object results in a single reflection as compared with a double reflection , one from the sea water surface and one from the sea bed , when the laser radiation impinges on the sea waves . a further method of operation of the present invention provides for two laser beams which are selected such that one penetrates the sea water , e . g ., green laser light , where the impingement of the laser radiation on the seaborne object forms a single reflection as compared with a double reflection , one from the sea surface and one from the sea bed , when laser radiation impinges on the sea waves , and a second beam of a non - penetrating wavelength , e . g ., a red laser , serving as a reference , where the impingement on the seaborne object or the sea waves results in a single reflection . according to still a further method of operation of the present invention , two laser beams are selected , one that penetrates the water , e . g ., green laser light , and a second , non - penetrating wavelength , e . g ., a red laser , where the two laser beams operate simultaneously and share an equivalent optical path using the same single detector , wherein each of the laser beams is modulated by a different rf carrier . the detector &# 39 ; s output rf signals are used to differentiate between the seaborne object and the sea , and the impingement on the object will result in a similar reflection pattern for both wavelengths ( displayed by similar , highly correlated temporal envelopes of received rf signals ), whereas the impingement from the sea will show variations in the reflection pattern between the two wavelengths , displayed by a lower correlation between the correspondingly received rf signals . a further method of operation of the present invention provides for multiple laser proximity detectors placed on the circumference of the seeker &# 39 ; s head , as shown in fig3 , enabling detection by a rotating seeker and either being redundant , or alternatively , enabling higher computation speed . according to a further method of operation of the present invention , laser proximity detectors based on time - of - flight are placed on the seeker , and are continuously utilized . similarly , laser proximity detectors based on phase detection may be placed on the seeker &# 39 ; s head , or laser proximity detectors based on triangulation computations , may be utilized . a further method of operation according to the present invention calls for laser proximity detectors data to be analyzed and processed by an on - board computing system and dedicated algorithms , and finally , according to yet a further method , multiple laser proximity detectors are oriented such as to impinge on the sea water surface at a distance higher than the target size , where the similarity or dissimilarity between the signals is used to distinguish between sea water and a target . it will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrated embodiments and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof . the present embodiments are therefore to be considered in all respects as illustrative and not restrictive , the scope of the invention being indicated by the appended claims rather than by the foregoing description , and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein . | 5 |
fig2 and 28 show the fourth and fifth lumbar vertebrae l4 and l5 , respectively , in a lateral view ( while in anatomic association ) and in a superior view ( separately ). the lumbar vertebrae ( of which there are a total of five ) are in the lower back , also called the “ small of the back .” as is typical with vertebrae , the vertebrae l4 and l5 are separated by an intervertebral disk 25 . the configuration of the vertebrae l4 and l5 differ somewhat , but each ( like vertebrae in general ) includes a vertebral body 10 , which is the anterior , massive part of bone that gives strength to the vertebral column and supports body weight . the vertebral arch 12 is posterior to the vertebral body 10 and is formed by the right and left pedicles 14 and lamina 16 . the pedicles 14 are short , stout processes that join the vertebral arch 12 to the vertebral body 10 . the pedicles 14 project posteriorly to meet two broad flat plates of bone , called the lamina 16 . seven other processes arise from the vertebral arch . three processes — the spinous process 18 and two transverse 20 processes — project from the vertebral arch 12 and afford attachments for back muscles , forming levers that help the muscles move the vertebrae . the remaining four processes , called articular processes , project superiorly from the vertebral arch ( and are thus called the superior articular processes 22 ) and inferiorly from the vertebral arch ( and are thus called the inferior articular processes 24 ). the superior and inferior articular processes 22 and 24 are in opposition with corresponding opposite processes of vertebrae superior and inferior adjacent to them , forming joints , called zygapophysial joints or , in short hand , the facet joints or facets . the facet joints permit gliding movement between the vertebrae l4 and l5 . facet joints are found between adjacent superior and inferior articular processes along the spinal column . the facet joints can deteriorate or otherwise become injured or diseased , causing lack of support for the spinal column , pain , and / or difficulty in movement . as described in this specification , a facet joint has a superior half and an inferior half . the superior half of the joint is formed by the vertebral level below the joint , and the inferior half of the joint is formed by the vertebral level above the joint . for example , in the l4 - l5 facet joint , the superior half of the joint is formed by structure on the l - 5 vertebra , and the inferior half of the joint is formed by structure on the l - 4 vertebra . a superior universal facet prosthesis 330 is shown in fig1 that embodies features of the invention . the prosthesis 330 is designated “ superior ” because it creates an artificial facet surface for the superior half of the facet joint . the artificial surface articulates with the inferior half of the facet joint . the prosthesis 330 allows for the replacement of injured , diseased and / or deteriorating components along the superior half of facet joints , to provide improved support for the spinal column . the universal facet prosthesis 330 may be constructed and configured in various ways . the universal facet prosthesis 330 may , e . g ., comprise a cup member 315 . the cup member 315 itself may be made of various materials commonly used in the prosthetic arts including , but not limited to , polyethylene , rubber , titanium , titanium alloys , chrome cobalt , surgical steel , or any other total joint replacement metal and / or ceramic , bony in - growth surface , sintered glass , artificial bone , any uncemented metal or ceramic surface , or a combination thereof . the cup member 315 may also be any appropriate shape including , but not limited to , rectangular , disc shaped , trough shaped , or cup shaped . the cup member may be fixed or anchored directly to a vertebra with poly ( methylmethacrylate ) bone cement , hydroxyapatite , screws , nails , bolts , anchors , break - away anchors and / or wires to facilitate any future removal of the prosthesis , or a combination thereof , or any other means known in the art . as shown in fig2 , the cup member 315 is made of any joint materials commonly used in the prosthetic arts , including , but not limited to , metals , ceramics , titanium , titanium alloys , tantalum , chrome cobalt , surgical steel , bony in - growth surfaces , artificial bone , uncemented surface metals or ceramics , or any combination thereof , preferably covered with a bony in - growth surface . in the illustrated embodiment , the cup member 315 is fixed to a stem 310 , e . g ., pre - welded , or glued with a biocompatible adhesive , or removably secured using a frictional morse taper . if desired , the stem 310 can incorporate one or more fins or ribs ( not shown ), extending outward from the stem 310 , which desirably reduce and / or eliminate rotation of the stem 310 once positioned within the targeted bone . in addition , the stern 310 can be cannulated , if desired , to allow the use of guide pins during insertion of the stem , as is well known in the art . the stem 310 may itself be made of any joint materials commonly used in the prosthetic arts , including , but not limited to , metals , ceramics , titanium , titanium alloys , tantalum , chrome cobalt , surgical steel , bony in - growth surfaces , artificial bone , uncemented surface metals or ceramics , or a combination thereof . in a preferred embodiment , the stein 310 is covered with a bony in - growth surface . in the illustrated embodiment , the cup member 315 carries a surface member , which is made of a material , e . g . polyethylene , ceramic , or metal , which provides glide and cushioning ability for any potential contacting components , such as the articular head members described below . in one embodiment ( see fig2 b ), the surface member 325 can be formed in a gently upwardly curving shape , similar in shape to a catcher &# 39 ; s mitt . in another embodiment ( see fig2 c ), the surface member 325 is rectangular in shape with rounded corners . the cup member 315 is sized to be larger than the articulating superior half of the facet joint , to allow for motion of the joint . the surface member 325 may be a separate component that is fixed to the cup member 315 , e . g ., with a biocompatible adhesive , screws , nails , or comprise a formed part of the cup member 315 . the surface member 325 may also be held into the cup member 315 with compressive forces or friction ( e . g ., using a morse taper ). as shown in fig2 a and 2 b , the stem 310 a could alternately comprise a threaded portion , such as in a pedicle screw , with the head or pedestal 315 a incorporating a depression 316 a sized to accommodate a hexagonal driver or other surgical driving tool well know in the art . in addition , the prosthesis 320 a could incorporate a lower insert 321 a sized to fit into the depression 316 a in the head 315 a . if desired , the insert 321 a could comprise a morse taper . in this embodiment , the stem 310 a can be screwed into the bone , with the insert 321 a positioned or otherwise secure within the depression 316 a . the stem 310 a could be placed by tapping without screwing . if revision surgery is required , or some other condition required removal of the prosthesis , the insert 321 a can be removed from the stein 310 a , and the stem 310 a can subsequently be removed from the bone . as fig2 a shows , the stem 310 a can also include an enlarged projection or collar 311 a abutting the cup member 315 a . the collar 311 a serves to prevent unintended ingress of the stem 310 a further into the pedicle , beyond a desired distance . fig1 depicts a spondylolisthetic spine with slippage at the l4 - l5 joint between the l4 and l5 vertebrae . fig3 and fig4 depict a universal facet prosthesis 330 which has been installed into an l5 vertebra 105 to replace the inferior half 305 of a facet joint . in one embodiment , the stem 310 of universal facet prosthesis 330 is fixed into the l5 vertebra 105 with poly ( methylmethacrylate ) bone cement , hydroxyapatite , a ground bone composition , or a combination thereof . in another embodiment , both the stem 310 and the cup member 315 are fixed to a vertebra with stainless steel wire to provide additional stability . the new support provided by a universal facet prosthesis 330 helps correct degenerative spine diseases such as spondylolisthesis , spinal stenosis , or any spine disease . as demonstrated by comparing fig1 showing a spondylolisthetic spine with slippage between the l4 vertebra 100 and the l5 vertebra 105 with fig3 where the diseased superior half 305 of the facet joint has been replaced with a superior universal facet prosthesis 330 of the present invention , correcting spondylolisthesis at the l4 - l5 joint and preventing further spondylolisthesis . similarly , where correction of scoliosis and / or kypho - scoliosis is desired , the size and / or shape of the prosthesis may be chosen to re - orient the affected level ( s ) of the spine . the superior universal facet prosthesis 330 described above may be used as a replacement for the superior half of one or more of facet joints at any facet joint at any level of the spine . in the preferred embodiment , the universal facet prosthesis 330 is used to replace the superior half of one or more facet joints in one or more facet joints . the superior facet prosthesis 330 is designed such that it has the appropriate cephalad and caudad directions as well as the appropriate medial / lateral angulation for the given level of the spine where the implant occurs . in further embodiments , one or more surfaces of a universal facet prosthesis 330 may be covered with various coatings such as antimicrobial , antithrombotic , and osteoinductive agents , or a combination thereof . see , e . g ., u . s . pat . no . 5 , 866 , 113 , which is incorporated herein by reference . these agents may further be carried in a biodegradable carrier material with which the pores of the stem and / or cup member of certain embodiments may be impregnated . see , e . g ., u . s . pat . no . 5 , 947 , 893 , which is also incorporated herein by reference . in still further embodiments of the present invention , a universal facet prosthesis may be attached to strengthened or fortified bone . vertebrae may be strengthened prior to or during fixation of the prostheses using the methods , e . g ., described in u . s . pat . no . 5 , 827 , 289 , which is incorporated herein by reference . this type of bone strengthening is particularly suggested for osteoporotic patients who wish to have facet replacement . b . surgical method for facet replacement using the superior universal facet prosthesis a surgical procedure that embodies features of the invention replaces the superior half of a facet joint with the superior universal facet prosthesis 330 described above . the surgical procedure comprises exposing the spinous process , lamina , and facet joints at a desired level of the spine using any method common to those of skill in the medical arts . the prominent bone 306 b ( see fig5 ) may then be rongeured using any means common in the field . the superior facet 305 may also be trimmed , as depicted in fig6 , to decompress the nerve root 203 . a reamer 400 , or any other instrument that is useful for grinding or scraping bone , may be used to ream the facet 305 b into the pedicle 304 b as depicted in fig7 and fig8 . in a preferred embodiment ( see fig9 ), an opening 407 is made into the vertebral body 107 with a broach 405 . the universal facet prosthesis 330 b is installed into the opening 407 made by the broach 405 , as shown in fig1 . the opening 407 may be partly filled with bone cement , hydroxyapatite , or any bone adhesive before installation of the universal facet prosthesis 330 b . in an alternative embodiment , the stem 310 of the superior universal facet prosthesis 330 may be constructed in such a way that the superior universal facet prosthesis 330 can be directly screwed or tapped into the vertebral body 107 . in another arrangement , the cup member 315 of the universal facet member 330 may additionally be fixed to the vertebral body 107 with bone cement , hydroxyapatite , or any other biocompatible adhesive . in yet another arrangement , a universal facet prosthesis without a stem 310 may be attached to the vertebral body with poly ( methylmethacrylate ) bone cement , hydroxyapatite , screws , nails , bolts , anchors , break - away anchors to facilitate later removal of the prosthesis , or a combination thereof , or any other means known in the art . in a further embodiment of the present invention , the universal facet prosthesis 330 may be fixed into strengthened or fortified bone . vertebrae may be strengthened prior to or during fixation of the prosthesis using the methods described in u . s . pat . no . 5 , 827 , 289 , which is incorporated herein by reference . this type of bone strengthening procedure is particularly suggested for osteoporotic patients who wish to have facet replacement surgery . an inferior lamina / facet prosthesis 500 that embodies features of the invention is shown in fig1 . the prosthesis 500 is designated “ inferior ” because it creates an artificial facet surface for the inferior half of a facet joint . the artificial surface articulates with the superior half of the facet joint . the prosthesis 330 allows for the replacement of injured , diseased and / or deteriorating components along the inferior halves of facet joints to provide improved support for the spinal column . the prosthesis 330 may span the distance from a region on one side of a vertebra to a region of the other side of the vertebra . it can thus replace both inferior halves of a facet joint . fig1 depicts a superior view of a vertebral body depicting sagitally oriented arthritic facets with lateral stenosis , showing how the spinal process 631 presses forward onto the nerve roots 205 and 200 . the prosthesis 500 allows for replacement of diseased and deteriorating inferior regions of the vertebra and partial replacement of lamina ( see fig1 ), which may be pressing on the spinal nerves , to relieve pain . the prosthesis 500 creates artificial facet surfaces for the inferior half of facet joints in the spine , which provide improved support for the spinal column . as fig1 shows , a superior universal facet prosthesis 330 , as described above , may also be installed to replace the superior halves of the facet joints and , with the inferior lamina / facet prosthesis 500 replacing the inferior halves of the facet joints , forming a total facet replacement system that can result in entire artificial facet joints along a length of the spinal column . alternatively , just the inferior half one or more facet joints , or just the superior half of one or more facet joints , may be replaced . the inferior and / or superior halves of facet joints may be replaced on one side of a given vertebra ( unilateral ), on the both sides of a given vertebra ( bilateral ), or a combination of each along a length of the spinal column . the inferior lamina / facet prosthesis 500 may be constructed in various ways . as shown in fig1 , the prosthesis 500 can comprise a base member 505 . the base member 505 may be made of any joint materials commonly used in the prosthetic arts , including , but not limited to , metals , ceramics , titanium , titanium alloys , tantalum , chrome cobalt , surgical steel , bony in - growth surfaces , artificial bone , uncemented surface metals or ceramics , or a combination thereof . the base member 505 may also be any appropriate shape to give appropriate support to the spine and to appropriately and sturdily attach to the inferior portions of a vertebral body . the base member 505 may be fixed or anchored directly to the inferior portion of a vertebral body with poly ( methylmethacrylate ) bone cement , hydroxyapatite , screws , nails , bolts , anchors , break - away screws to facilitate any future removal of the prosthesis , or a combination thereof , or any other means known in the art . in a preferred arrangement , as depicted in fig1 , fig1 , and fig1 , the base member 505 of the inferior lamina / facet prosthesis 500 is attached to each pedicle 102 a and 102 b with bilateral pedicle screws 520 a and 520 b . the base member 505 of the inferior lamina / facet prosthesis 500 may further be attached to the spinous process 630 with a trans - spinous - process screw 515 to provide additional stability . in another embodiment , the inferior lamina / facet prosthesis 500 may have a head member 510 for articulation with the cup member 315 of a superior universal facet prosthesis 330 or with a superior articular process of the adjoining vertebral body . the head member 510 may be made of various materials commonly used in the prosthetic arts including , but not limited to , polyethylene , rubber , tantalum , titanium , chrome cobalt , surgical steel , bony in - growth surfaces , ceramics , artificial bone , or a combination thereof . the head member 510 may further be any shape which facilitates attachment to the rest of the inferior lamina / facet prosthesis 500 and to smooth connection to , and movement in orientation to , a universal facet prosthesis 330 or a superior articular process of an adjoining vertebral body . in one embodiment , a head member 510 is attached to the base member 505 of the inferior facet / lamina prosthesis 500 with poly ( methylmethacrylate ) bone cement , hydroxyapatite , screws , nails , bolts , anchors , or any other means known in the art . the head member 510 may also be removably attached by frictional engagement ( e . g ., using a morse taper ). in a preferred embodiment ( see fig1 and 12 ), the inferior facet / lamina prosthesis 500 comprises two head members 510 a and 510 b formed in the shape of an articular head . the head members 510 a and 510 b preferably each have a morse taper 512 at their upper surface to allow them to lock into the base member 505 of the inferior facet / lamina prosthesis 500 . of course , either or both head members 510 a and 510 b could be formed integrally with the prosthesis 500 . in the preferred arrangement , a complete prosthetic facet joint 560 is provided ( see fig1 ), in which the head members 510 a and 510 b articulate with the cup member 315 of the superior universal facet prosthesis 330 . in further embodiments , one or more surfaces of the inferior lamina / facet prosthesis 500 may be covered with various coatings such as antimicrobial , antithrombotic , and osteoinductive agents , or a combination thereof . see , e . g ., u . s . pat . no . 5 , 866 , 113 , which is incorporated herein by reference . these agents may further be carried in a biodegradable carrier material with which the pores of the base member and / or any screws , bolts , or nails of certain embodiments may be impregnated . see , e . g ., u . s . pat . no . 5 , 947 , 893 , which is incorporated herein by reference . in other arrangements , an inferior lamina / facet prosthesis 500 may be attached to strengthened or fortified bone . vertebrae may be strengthened prior to or during fixation of the prosthesis using the methods described , e . g ., in u . s . pat . no . 5 , 827 , 289 , which is incorporated herein by reference . this type of bone strengthening is particularly suggested for osteoporotic patients who wish to have facet replacement . b . surgical method for partial inferior lamina / facet replacement using the inferior lamina / facet prosthesis a surgical procedure that embodies features of the invention replaces inferior lamina and articulated processes with the inferior lamina / facet prosthesis 500 as described above . the surgical procedure exposes the spinous process , lamina , and facet joints at a desired level of the spine using any method common to those of skill in the medical arts . as fig1 shows , an inferior one eighth to one half of the spinous process 302 may be cut along the spinous process resection line 610 and removed , if the spinous process appears diseased or damaged . the cutting and removal of the spinous process may be performed using any means common in the field . as shown in fig1 and 17 , the inferior half of the facet joint may also be cut at or near the inferior facet resection line 600 . in a preferred embodiment ( see fig1 and 17 ), most of the lamina 615 is preserved , as is the facet joint capsule 625 , which may be opened and folded back . in a preferred embodiment , the facet joint capsule 625 may be cut perpendicular to its direction . the inferior half 621 of the facet joint 620 may then be retracted from the superior half 622 . once the facet joint 620 is separated , the cut inferior bone 615 of the upper joint ( i . e . the cut inferior portion of the l4 vertebra in the l4 - l5 joint ) may be removed . alternatively , it may be possible to remove the cut inferior bone 615 while simultaneously separating the facet joint 620 . in a preferred embodiment ( see fig1 and 19 ), a superior universal facet prosthesis 330 is then installed as previously described . alternatively , the superior universal facet prosthesis 330 may be installed before the inferior bone is removed or even cut . an inferior lamina / facet prosthesis 500 as described above may be placed onto the facet joints and over the spinous process . the inferior lamina / facet prosthesis 500 may be fixed or anchored to the vertebral body with poly ( methylmethacrylate ) bone cement , hydroxyapatite , screws , nails , bolts , anchors , break - away screws , or a combination thereof to facilitate any future removal of the prosthesis , or any other means known in the art . in the preferred embodiment ( see fig1 , fig1 , and fig1 ), the inferior lamina / facet prosthesis 500 is attached to each pedicle 102 a and 102 b of the inferior facets with bilateral pedicle screws 520 a and 520 b and is further attached to the spinous process 630 with a trans - spinous - process screw 515 to provide additional stability . a head member 510 of an inferior lamina / facet prosthesis 500 may be articulated into the cup member 315 of the superior universal facet prosthesis 330 , or into an inferior half of a facet joint if the inferior half has not been replaced , to create a complete prosthetic facet joint . in an alternative embodiment , as depicted by fig1 , the inferior facet resection line 610 may be a v - type cut . if a v - type cut is used , an appropriately shaped inferior lamina / facet prosthesis 550 should be used , such as depicted in fig2 . the inferior facet resection line may alternatively be cut in other ways , which are apparent to one of skill in the art of orthopedic surgery and will require inferior lamina / facet prostheses of varying shapes to appropriately fit the cut vertebra . in a further embodiment of the present invention , a universal facet prosthesis and / or an inferior lamina / facet prosthesis may be fixed into strengthened or fortified bone . vertebrae may be strengthened prior to or during fixation of the prosthesis using the methods described , e . g ., in u . s . pat . no . 5 , 827 , 289 , which is incorporated herein by reference . this type of bone strengthening procedure is particularly suggested for osteoporotic patients who wish to have facet replacement surgery . a hemi - lamina / facet prosthesis 700 that embodies features of the invention ( see fig2 ) may be used to replace parts of a lamina and inferior processes , some or all which may have been removed in a primary procedural bone resection , ( i . e . with or without wide decompressive laminectomy ). the hemi - lamina / facet prosthesis 700 may be designed similarly , or even identically , to the inferior lamina / facet prosthesis 500 described above , depending on how much of the bone is removed . the hemi - lamina / facet prosthesis 700 may be constructed in various ways . in one embodiment , hemi - lamina / facet prosthesis 700 may , e . g ., comprise a base member 705 . the base member 705 may be made of any joint materials commonly used in the prosthetic arts , including , but not limited to , metals , ceramics , titanium , titanium alloys , tantalum , chrome cobalt , surgical steel , bony in - growth surfaces , artificial bone , uncemented surface metals or ceramics , or a combination thereof . the base member 705 may be any shape which gives appropriate support to the spine and can be appropriately attached to the bone of the remaining lamina . the base member 705 may be fixed or anchored directly to the inferior portion of a vertebral body with poly ( methylmethacrylate ) bone cement , hydroxyapatite , screws , nails , bolts , anchors , break - away screws to facilitate any future removal of the prosthesis , a combination thereof , or any other means known in the art . in a preferred embodiment ( see fig2 ) of a prosthesis for hemiarthroplasty ( depicted as cut line 800 and further described below ) without decompressive laminectomy , the base member 705 of the hemi - lamina / facet prosthesis 700 is attached to superior pedicle 102 b with a pedicle screw 720 . in another preferred embodiment , the base member 705 of the hemi - lamina / facet prosthesis 700 may further be attached to the spinous process 630 with a trans - spinous - process screw 715 to provide additional stability . in a preferred embodiment ( see fig2 and 25 ) of a prosthesis for hemiarthroplasty with wide decompressive laminectomy , the hemi - lamina / facet prosthesis 700 comprises at least one base member 705 . the base member 705 may further comprise a pedicle attachment hole 725 through which a pedicle screw 720 , or a nail , anchor , break - away anchor , bolt , or any other fastening means , may be installed to help secure the hemi - lamina / facet prosthesis 700 to the inferior pedicle . in the preferred embodiment , the base member 705 may also have at least one lamina attachment hole , with two lamina attachment holes 741 and 742 pictured in fig2 , to further secure the hemi - lamina / facet prosthesis 700 to the remaining laminal bone with screws , nails , anchors , break - away anchors , bolts , or any other fastening means . parts of the hemi - lamina / facet prosthesis 700 which overlap bone may be additionally fixed with bone cement , or any biocompatible adhesive . a hemi - lamina / facet prosthesis 700 may further comprise a connection plate , similar to the connection plate 750 depicted in fig2 , to connect two base members , i . e . 705 a and 705 b , together . the connection plate 750 may be fixed to each base member 705 a and 705 b with a biocompatible adhesive , screws , nails , bolts , compressive force , a combination thereof , or any other means common to those of skill in the art . alternatively , a hemi - lamina / facet prosthesis 700 may further comprise at least one stabilization bar , similar to the stabilization bars 761 and 762 depicted in fig2 . a stabilization bar or bars may be fixed to each base member 705 a and 705 b with a biocompatible adhesive , screws , nails , bolts , compressive force , a combination thereof , or any other means common to those of skill in the art . a hemi - lamina / facet prosthesis 700 may have any type of bridging or stabilizing members , or no bridging members at all , and may be comprised of any number of base members to provide appropriate stability to the spine . the bridging members may be made of any joint materials commonly used in the prosthetic arts , including , but not limited to , metals , ceramics , titanium , titanium alloys , tantalum , chrome cobalt , surgical steel , bony in - growth surfaces , artificial bone , uncemented surface metals or ceramics , or a combination thereof . in another embodiment , a hemi - lamina / facet prosthesis 700 may have a head member 710 for articulation with the cup member 315 of a superior universal facet prosthesis 330 or with the superior articular process of an adjoining superior pedicle . the head member 710 may be made of various materials commonly used in the prosthetic arts including , but not limited to , polyethylene , rubber , titanium , chrome cobalt , surgical steel , bony in - growth sintering , sintered glass , artificial bone , or a combination thereof . the head member 710 may further be any shape which allows it to attach to the rest of the hemi - lamina / facet prosthesis 700 and to smoothly connect to , and move in orientation to , the universal facet prosthesis 330 or superior articular facet of the adjoining superior pedicle . in one embodiment , the head member 710 is attached to the rest of the hemi - lamina / facet prosthesis with poly ( methylmethacrylate ) bone cement , hydroxyapatite , screws , nails , bolts , anchors , a combination thereof , or any other means known in the art . the head member 710 may be removably attached , using , e . g ., a morse taper . in a preferred embodiment , hemi - lamina / facet prosthesis 700 comprises a head member 710 made in the shape of an articular head . the head member 710 preferably has a morse taper at its upper surface to allow it to lock into hemi - lamina / facet prosthesis 700 . in further embodiments , one or more surfaces of a hemi - lamina / facet prosthesis 700 may be covered with various coatings such as antimicrobial , antithrombotic , and osteoinductive agents , or a combination thereof . see , e . g ., u . s . pat . no . 5 , 866 , 113 , which is incorporated herein by reference . these agents may further be carried in a biodegradable carrier material with which the pores of the base member and / or any screws , bolts , or nails of certain embodiments may be impregnated . see , e . g ., u . s . pat . no . 5 , 947 , 893 , which is incorporated herein by reference . in still further embodiments of the present invention , a hemi - lamina / facet prosthesis 700 may be attached to strengthened or fortified bone . vertebrae may be strengthened prior to or during fixation of the prosthesis using the methods described , e . g ., in u . s . pat . no . 5 , 827 , 289 , which is incorporated herein by reference . this type of bone strengthening is particularly suggested for osteoporotic patients who wish to have facet replacement . b . hemiarthroplasty with or without wide decompressive laminectomy using the hemi - lamina / facet prosthesis a surgical procedure that embodies features of the invention removes at least part of a lamina and at least one superior portion of a facet joint and replacing it with a hemi - lamina / facet prosthesis 700 as described above . the general surgical procedure is generally similar to the inferior lamina / facet replacement previously described , with the main difference being the types of cuts made into the laminal bone , and that two separate prostheses are used to replace the superior portions of two facet joints ( left and right ) of a given vertebra . one embodiment of the surgical procedure comprises exposing the spinous process , lamina , and facet joints at a desired level of the spine using any method common to those of skill in the medical arts . the inferior facet joint and part of the lamina may be cut with a hemiarthroplasty resection line 800 as depicted in fig2 for a hemiarthroplasty . the lamina may additionally be cut for a wide decompressive laminectomy along the decompression resection line 810 as depicted in fig2 . the inferior facet joint may be cut on one side or both sides of the lamina . likewise , the lamina may be cut along a decompression resection line on one side or both sides . in a preferred embodiment of a hemiarthroplasty without a wide decompressive laminectomy , leaving the cut inferior facet bone 300 in place , the facet joint capsule 625 may be opened and folded back . in the preferred embodiment , the facet joint capsule 625 may be cut perpendicular to its direction . the inferior half 621 of the facet joint 620 may then be retracted from the superior half 622 . once the facet joint 620 is separated , the cut inferior facet bone 825 may be removed . alternatively , it may be possible to remove the cut inferior facet bone 825 while simultaneously separating the facet joint 620 . in a preferred embodiment of a hemiarthroplasty with a wide decompressive laminectomy , a superior universal facet prosthesis 330 is then installed as previously described , and depicted in fig1 . a base member 705 of hemi - lamina / facet prosthesis 700 as described in any of the embodiments above may be placed onto at least one facet joint and at least one pedicle as depicted in fig2 , and over the spinous process if it has not been removed for hemiarthroplasty without decompressive laminectomy as depicted in fig2 . the hemi - lamina / facet prosthesis 700 may be fixed or anchored to the vertebral body with poly ( methylmethacrylate ) bone cement , hydroxyapatite , screws , nails , bolts , anchors , break - away screws to facilitate any possible future removal of the prosthesis , a combination thereof , or any other means known in the art . in the preferred embodiment , as depicted in fig2 , fig2 , and fig2 , the hemi - lamina / facet prosthesis 500 is attached to each pedicle with bilateral pedicle screws 720 . a hemi - lamina / facet prosthesis 700 that may be used in hemiathroplasty without wide decompressive laminectomy , depicted in fig2 , may further be attached to the spinous process 630 with a trans - spinous - process screw 715 to provide additional stability . a hemi - lamina prosthesis 700 that may be used in hemiathroplasty with wide decompressive laminectomy , as depicted in fig2 , 24 , and 25 , may further be attached to remaining laminal bone with screws , bolts , nails , anchors , or breakaway anchors through at least one lamina attachment hole 741 to provide additional stability . in embodiments where a hemi - lamina / facet prosthesis 700 with more than one base member 705 is installed , a connection plate , depicted as connection plate 750 in fig2 , at least one stabilization bar , depicted as stabilization bars 761 and 762 in fig2 , or any other connecting or stabilizing means known in the art , may be installed with the base members to provide additional stability to the spine . at least one head member , depicted as head member 710 in fig2 , 23 , 24 , and 25 , of a hemi - lamina / facet prosthesis 700 may be articulated into a cup member of a superior universal facet prosthesis 330 to create a prosthetic facet joint capsule . the embodiments may be used to replace one or more facet joints for the entire length of the spine from s1 to t11 , on one side of a given vertebra , or both sides of a given vertebra , or a combination thereof along a length of the spine . if only one facet joint at a given level is to be replaced , the unilateral arthroplasty prosthesis for the inferior half of the joint may be fixed to the superior ipso - lateral pedicle and include a box fitted over the spinous process , combined with screw fixation . the spinous process box is similar to the spinous process box in the bilateral total facet arthroplasty embodiment previously discussed . in a further embodiment of the present invention , a universal facet prosthesis 330 and / or a hemi - lamina / facet prosthesis 700 may be fixed into strengthened or fortified bone . the vertebrae may be strengthened prior to or during fixation of the prosthesis using the methods described , e . g ., in u . s . pat . no . 5 , 827 , 289 , which is incorporated herein by reference . this type of bone strengthening procedure is particularly suggested for osteoporotic patients who wish to have facet replacement surgery . fig2 and 30 show an inferior prosthesis 26 that embodies features of the invention . the prosthesis 26 is designated “ inferior ” because it creates an artificial facet surface in the inferior half of a facet joint . the artificial surface articulates with the superior half of the facet joint . the prosthesis 26 is particularly well suited to single - sided procedures and / or for procedures involving vertebral bodies which are not symmetrical . when the processes on one side of a vertebral body are differently spaced from those on the other side of the same body , the prostheses on each side would desirably be of differing sizes as well . moreover , it is often difficult and / or impossible for a surgeon to determine the precise size and / or shape necessary for a prosthesis until the surgical site has actually been prepared for receiving the prosthesis . in such a case , the surgeon typically needs a family of prostheses possessing differing sizes and / or shapes immediately available during the surgery . the surgeon cannot wait for a custom - fitted device to be created during the surgery , so a number of prostheses of varying sizes and / or shapes must be available for each procedure . the prosthesis 26 can be conveniently formed in different sizes and shapes , to offer an array of prostheses 26 from which the surgeon can pick and choose as surgery proceeds . this allows a surgeon to create a “ custom ” implant during the surgical procedure . in the illustrated embodiment ( see fig2 and 30 ), the prosthesis 26 comprises a body 28 sized and shaped to span the distance between a pedicle 14 and an inferior articular process 24 on the same side of a vertebral body ( see fig3 ). the body 28 may be formed of a material commonly used in the prosthetic arts including , but not limited to , polyethylene , rubber , titanium , chrome cobalt , surgical steel , bony in - growth sintering , sintered glass , artificial bone , or a combination thereof the upper section of the body 28 desirably includes an opening 32 . the opening 32 accommodates a pedicle screw 34 ( see fig4 ), which secures the upper end of the body 28 into the pedicle 14 of the vertebral body . the opening 32 could be elongated , to allow for varying orientations and / or sizes of the pedicle screw 34 . the remainder of the link body 28 can be secured to the exterior of the vertebra using , e . g ., biocompatible adhesive . the lower section of the body 28 is oriented to serve as the superior half of a facet joint . the lower section of the body 28 desirably incorporates a head 30 . the head 30 can be permanently affixed to the body 28 , using , e . g ., adhesive . alternatively , the head can be frictionally secured , e . g ., using a morse taper , for removal and replacement ( as fig4 shows ). like the body 28 , the head 30 can be formed of a material commonly used in the prosthetic arts including , but not limited to , polyethylene , rubber , titanium , chrome cobalt , surgical steel , bony in - growth sintering , sintered glass , artificial bone , or a combination thereof . the head 30 possesses a curvilinear shape that desirably curves along a gradual arc ( as fig4 shows ), or can present a “ button ” shape . if desired , the lower section of the joint link body 28 could be angled , to more naturally mimic the orientation of a non - diseased facet joint . in one alternative embodiment , the lower section of the joint link body 28 could rotate relative to the upper section , and could be rotationally secured in a desired position by a surgeon using a locking screw or other locking means known in the art . such an embodiment would allow the surgeon to alter the orientation of the lower section to fit the particular needs of a patient during the actual surgical procedure . in use ( see fig3 ), the head 30 articulates with the superior half of the facet joint . the superior facet 22 can comprise the natural superior articular process itself ( as fig3 shows ), or it can comprise a superior prosthetic facet created , e . g ., by the previously described universal facet prosthesis 330 ( as fig4 shows ). the surface member 320 of the universal facet prosthesis 330 can comprise a metal material made of , e . g ., titanium , cobalt , chrome , etc ., or a plastic material such as , e . g ., polyethylene , or a ceramic material . thus the surgeon can select the same or different materials to form the joint interface between the head 30 and facet prosthesis 330 . fig3 and 35 show another embodiment of an inferior universal prosthesis 36 that embodies features of the invention . the prosthesis 36 , like the prosthesis 26 , is designated “ inferior ” because it creates an artificial facet surface in the inferior half of the facet joint . the artificial surface articulates with the superior half of the facet joint . like the prosthesis 26 , the prosthesis 36 is particularly well suited to single - sided procedures and / or for procedures involving vertebral bodies which are not symmetrical . the prosthesis 36 comprises a body 38 sized and shaped to span the distance between a pedicle 14 and an inferior articular process 24 ( see fig3 ). the body 38 may be formed of the same types of material as the link body 28 . like the link body 28 , the upper section of the joint link body 38 desirably includes an opening 42 , to accommodate a pedicle screw 34 ( see fig3 ), which secures the upper end of the body 38 into the pedicle 14 of the vertebral body , in similar fashion as generally shown in fig4 . as before described with reference to the link 26 , the opening 42 in the link body 38 could be elongated , to allow for varying orientations and / or sizes of the pedicle screw 34 . the remainder of the link body 28 can be secured to the exterior of the vertebra using , e . g ., biocompatible adhesive . unlike the link body 28 , the link body 38 includes an intermediate opening 44 ′ in use ( see fig3 ), the spinous process 18 ( if present ) can extend through the opening 44 , to stabilize the link body 38 on the vertebral body . desirably , a trans - spinous - process screw 45 can be used to provide additional stability . the lower section of the joint link body 38 is oriented to serve as the inferior half of a facet joint . the lower section of the joint link body 38 desirably incorporates a head 40 which can be constructed in the same fashion as the head 30 of the link 26 . like the head 30 , the facet head 40 can be permanently affixed to the body 38 or can be secured in with a frictional fit ( e . g ., using a morse taper ) for removal and replacement . like the head 30 , the head 40 can be formed of a material commonly used in the prosthetic arts . in use ( see fig3 ), the head 40 articulates with the superior half of the facet joint with the next adjacent vertebra level . as before explained for the link 26 , the superior facet 22 can comprise the natural superior articular facet 22 itself , or it can comprise a prosthetic facet created , e . g ., by the previously described universal facet prosthesis 330 . fig3 shows a superior prosthetic link 26 ′ that also embodies features of the invention . the prosthetic link 26 ′ is designated “ superior ” because it creates an artificial facet surface in the superior half of a facet joint . the artificial surface articulates with the inferior half of the facet joint . the superior prosthesis link 26 ′, like the prosthesis 26 , is particularly well suited to single - sided procedures and / or for procedures involving vertebral bodies which are not symmetrical . a stem 37 extends out from the upper end of the link 26 ′. the stem 37 is inserted ( by screwing or tapping ) into the pedicle , to thereby secure the link 26 ′ to the vertebral body . as fig3 shows , the upper end of the link 26 ′ is shaped to form a cup 36 , which articulates with the inferior half of the facet joint . the inferior half of the facet joint can comprise the natural inferior articular process 24 itself ( as fig3 shows ), or it can comprise the head 30 of an inferior prosthesis 26 or link 26 ′ attached to the next adjacent upper vertebra level ( as fig3 shows ). the lower end of the link 26 ′ can also carry a head 30 for articulation with the superior half of a facet joint with the next adjacent lower vertebra . the superior half of the facet joint can comprise the natural superior articular process 22 itself , or it can comprise the cup of a link 26 ′ attached to the next adjacent lower vertebra level . it can thus be appreciated that the link 26 ′ is well suited for use in procedures requiring replacement of multiple levels of facet joints , and can be interlinked in superior and inferior pairs , like a structure formed out of interlinking tinker - toy pieces . the link 26 ′ also allow subsequent surgeries to build upon already replaced levels , rather than requiring the removal and replacement of an existing implant to accommodate replacement of failing facet joints in an adjacent level . it should be appreciated that the upper end of the prosthesis 36 can also be shaped to form a cup to articulate with the superior half of the facet joint with the next adjacent upper vertebra level . the prosthesis 26 , 36 , or link 26 ′ are well suited for use in a single side of the vertebral body , such as where the facet joints need only be replaced on a single side of the vertebral body . the prosthesis 26 , 36 , or link 26 ′ are also well suited for use in a dual - sided procedure where the vertebral body is either symmetrical or non - symmetrical . in this arrangement , other prostheses 26 , 36 , or links 26 ′ can be secured on the opposite side of the vertebral body , allowing both sides of the vertebral body to be treated . because the surgeon can pick prostheses 26 , 36 , and links 26 ′ of varying sizes , depending upon the size of the vertebral site , and can individually position each prosthesis 26 or link 26 relative to the vertebral body , the surgeon can tailor the linked implant system to the individual &# 39 ; s needs . fig3 shows a universal prosthetic joint link assembly 56 that embodies features of the invention . the joint link assembly 56 is particularly well suited to double - sided procedures and for sequential , multiple level procedures . in the illustrated embodiment ( see fig3 ), the joint link assembly 56 comprises two criss - crossing link bodies 58 and 60 . each body 58 and 60 ( shown mutually separated in fig3 and 38 , respectively ) may be formed of a material commonly used in the prosthetic arts including , but not limited to , polyethylene , rubber , titanium , chrome cobalt , surgical steel , bony in - growth sintering , sintered glass , artificial bone , or a combination thereof . as fig3 shows , the link bodies 58 and 60 are desirably locked together for use at an intermediate key - way 62 , to form the x - shaped , crisscrossing assembly 56 . the key - way 62 is formed by a shaped opening 68 in one body 60 ( see fig3 ) and a mating shaped key 70 in the other body 58 ( see fig3 ). the key 70 nests within the opening 60 ( as fig3 shows ), to frictionally hold the bodies 58 and 60 together and resist relative rotation between the bodies 58 and 60 . of course , the shape of the opening 68 and key 70 can vary . in fig3 , 37 , and 38 , the opening 68 and key 70 are generally square or rectilinear in shape . in fig3 , an alternative link body 58 is shown , which possesses a key 70 ′ that is generally octagonal in shape , sized to nest within a corresponding octagonal opening in the other link ( not shown ). in this arrangement , the two link bodies 58 and 60 can be mutually assembled in different arcuately spaced orientations , allowing for variations in facet joint size and positioning . if desired , the key - way 62 could alternately be formed in a tooth and gear arrangement , which would desirably allow a multiplicity of potential arcuately spaced orientations for the two link bodies 58 and 60 forming the assembly 56 . the key 70 desirable peripherally defines an opening 72 ( see fig3 ), through which the spinous process 18 can ( if present ) project during use . this is generally shown in phantom lines by fig4 . alternatively the link bodies 58 and 60 could be formed in a criss - crossing shape as a single , unitary body . the upper section of each link body 58 and 60 desirably includes a cup 64 . the cups 64 form the left and right superior halves of a facet joint and , in use , articulate with the left and right inferior halves of the facet joint . a stem 65 extends out from the upper end of each link body 58 and 60 . the stem 67 is inserted ( by screwing or tapping ) into the pedicle , to thereby secure the link bodies 58 and 60 to the vertebral body . in use , the sterns 67 secure the upper end of the bodies 58 and 60 into an opposite pedicle 14 of a vertebral body . as fig4 best shows , the bodies 58 and 60 are each sized , shaped and mutually oriented to span the distance between a pedicle 14 on one side of the vertebral body and the region of the inferior articular process on the opposite side of the vertebral body . the remainder of the link bodies 58 and 60 can be secured to the exterior of the vertebra using , e . g ., biocompatible adhesive . a trans - spinous - process screw 63 can also be used to provide additional stability . the lower section of each link body 58 and 60 is oriented to serve as the inferior half of a facet joint . as fig4 shows , the link body 58 , secured to the right pedicle , is positioned to serve as the inferior half of the facet joint on the left side of the vertebra . the link body 60 , secured to the left pedicle , is positioned to serve as the inferior half of the facet joint on the right side of the vertebra . for this purpose , the lower section of each link body 58 and 60 desirably incorporates a head 66 . as before explained , the head 66 can be permanently affixed to each body 58 and 60 or it can be secured in a frictional way using , e . g ., a morse taper for removal and replacement . like the bodies 58 and 60 , the head 66 can be formed of a material commonly used in the prosthetic arts including , but not limited to , polyethylene , rubber , titanium , chrome cobalt , surgical steel , bony in - growth sintering , sintered glass , artificial bone , or a combination thereof . in use , the heads 66 articulate with the superior halves of the left and right facet joints with the next adjacent vertebra level . as earlier described with reference to the single link structures , the superior halves of the facet joints can comprise the natural superior articular process 22 itself , or it can comprise a prosthetic facet created , e . g ., by the cups 64 of another link assembly 56 secured to the next adjacent lower vertebra . the interlocking of the criss - crossing link bodies 58 and 56 increases the strength of the overall link assembly 56 . the link assembly 56 distributes forces to both of the pedicles ( and the spinous process , if desired ), rather than relying upon fixation to a single pedicle . like the link 26 ′, the link assembly 56 is well suited for implantation in procedures requiring replacement of multiple levels of facet joints , and can be interlinked in superior and inferior pairs , like a structure formed out of interlinking tinker - toy pieces . like the link 26 ′, the link assembly 56 also allows subsequent surgeries to build upon already replaced levels , rather than requiring the removal and replacement of an existing implant to accommodate replacement of failing facet joints in an adjacent level . the size and shape of any prosthesis disclosed herein are desirably selected by the physician , taking into account the morphology and geometry of the site to be treated . the shape of the joint , the bones and soft tissues involved , and the local structures that could be harmed if moved inappropriately , are generally understood by medical professionals using textbooks of human anatomy along with their knowledge of the site and its disease and / or injury . the physician is also desirably able to select the desired shape and size of the prosthesis and its placement in and / or around the joint based upon prior analysis of the morphology of the targeted joint using , for example , plain film x - ray , fluoroscopic x - ray , or mri or ct scanning . the shape , size and placement are desirably selected to optimize the strength and ultimate bonding of the prosthesis to the surrounding bone and / or tissue of the joint . other embodiments and uses of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein . all documents referenced herein are specifically and entirely incorporated by reference . the specification and examples should be considered exemplary only with the true scope and spirit of the invention indicated by the following claims . as will be easily understood by those of ordinary skill in the art , variations and modifications of each of the disclosed embodiments can be easily made within the scope of this invention as defined by the following claims . | 0 |
referring to fig1 , a module isolation device in accordance with one embodiment of this invention is illustrated at 10 . the module isolation device is employed to receive oxygen permeate from an ion transmission membrane ( itm ) oxygen module 12 . exemplary itm oxygen modules are disclosed in u . s . pat . no . 5 , 681 , 373 , the subject matter of which is hereby fully incorporated by reference . also , as discussed earlier , itm oxygen modules are described in taylor et al . u . s . pat . no . 5 , 681 , 373 . this latter patent previously has been incorporated by reference herein . the oxygen permeate from the itm oxygen module 12 is the purified oxygen removed from an oxygen - containing gas ( e . g ., air ) that initially is directed into passageways 14 provided between the membrane units 16 of the module . the membrane units 16 include a dense , mixed conducting oxide layer through which oxygen permeates . the oxygen permeate , i . e ., the purified oxygen , is directed out of the module 12 through ceramic stack manifold 18 and a ceramic to metal seal 20 into inlet 22 of the module isolation device 10 . still referring to fig1 , the module isolation device 10 includes an outlet passage 26 downstream of the inlet passage 22 for receiving the flow of permeate oxygen . optionally , the outlet passage 26 can include a flow restricting orifice 28 through which the oxygen passes prior to entering an oxygen collecting header or plenum 30 . the flow restricting orifice 28 , if needed , is designed to provide sufficient back pressure in the event of increased flow from the module 12 , such as from a leak , to increase the pressure acting on a rupture disk ( described in detail hereinafter ) to a value higher than the pressure encountered during normal operation of the module 12 . the higher pressure resulting from a malfunction of the itm oxygen module 12 will rupture the rupture disk to isolate the module , as will be discussed in detail later in this application . it should be understood that the oxygen collecting plenum 30 generally is associated with one or more additional itm oxygen modules that are arranged in series or parallel , such that the oxygen permeate from all of the modules flow into and through the common oxygen collecting plenum 30 . a unique feature of this invention resides in the construction and operation of a module isolation valve 40 forming part of the module isolation device 10 . the valve 40 is designed to permit the flow of oxygen permeate from the inlet passage 22 through the outlet passage 26 when in an opened condition and to prevent the flow of the oxygen permeate to the outlet passage when in a closed condition . the module isolation valve 40 includes a valve seat 42 , a valve stem 44 including a valve member 46 at one end thereof , and a rupture disk 48 having a first face 50 engaging an opposed end 52 of the valve stem 44 . the rupture disk 48 includes a second face 54 in flow communication with a low - pressure header 56 through a conduit 58 . if desired , heat insulation material 60 optionally can be provided around the valve stem 44 adjacent the rupture disk 48 . it should be noted that when insulation material 60 is employed it is a porous material , e . g . alumina fiber , to permit flow communication of the oxygen permeate flowing into the module isolation device 10 through the inlet 22 with the first face 50 of the rupture disk 48 when the module isolation valve 40 is in an opened condition . the flow of oxygen permeate is schematically indicated by the arrows depicted in fig1 . it should be noted that the specific construction of the ceramic to metal seal 20 does not constitute a limitation on the broadest aspects of this invention . exemplary ceramic to metal seals usable in this invention are described in u . s . pat . no . 6 , 302 , 402 , the subject matter of which is hereby incorporated by reference . in the illustrated embodiment , the valve member 46 is in the form of a globe valve , however , other types of linear - action valves , e . g ., gate valves , angled valves , etc ., would work equally well in the invention . exemplary types of valves usable in this invention are disclosed in standard references , such as perry &# 39 ; s handbook of chemical engineering , chapter 10 . it should be understood that the materials employed to construct the module isolation valve 40 need to be chosen to be compatible for service in the hot oxygen product stream . an exemplary material is a nickel superalloy , such as haynes 214 or haynes 230 , sold by haynes international of kokomo , ind . alternatively , parts of the valve could be constructed of structural ceramics such as alumina , silicon carbide or silicon nitride . the rupture disk 48 needs to be designed for proper operation at the temperature of use in the system . this disk 48 either can be exposed to the operating temperature of the oxygen process stream , or it can be insulated from the process stream , such as by employing insulation material 60 , and thereby operate at a lower temperature . having described the structural arrangement of elements in the module isolation device 10 , the manner in which the device functions to isolate the module 12 from other modules joined to the module isolation device 10 through one or more common headers ( e . g ., oxygen collecting plenum 30 ) will now be described . during an upset condition , such as when a large leak develops in the itm module 12 , the flow exiting the module into the inlet passage 22 of the module isolation device 10 will increase . due to the flow resistance of the module isolation device 10 and the oxygen collecting plenum or manifold 30 , the pressure inside the module 12 also will increase . if a flow restrictor is employed between the module 12 and the oxygen collecting plenum or header 30 , ( e . g ., flow restricting orifice 28 ) the pressure inside the module 12 will increase even further . this increase in pressure is transmitted through the isolation device 10 against the first face 50 of the rupture disk 48 . this pressure increase resulting in an overpressure condition for the rupture disk 48 will cause the disk to rupture , or burst . when the rupture disk ruptures it no longer supports the lower end 52 of valve stem 44 , and the stem will drop under the force of gravity , the pressure drop across the valve member , and the viscous drag of the gas around the valve member 46 in the case of certain types of valves , such as globe valves . in this latter position the valve member 46 seats against valve seat 42 to close valve 40 and stop the flow of gas exiting from the itm oxygen module 12 to the oxygen collecting plenum 30 . this causes the pressure on the upstream side of the valve member 46 to further increase to the pressure of the high - pressure gas , which further assists in maintaining a good seal between the valve member 46 and the valve seat 42 . once the valve member 46 seats against the valve seat 42 , the oxygen collecting plenum or header 30 is isolated from the leak , thereby preventing contamination of the purified oxygen from the failed module 12 . in the illustrated embodiment , wherein the low pressure header 56 is a separate header from the oxygen collecting plenum or header 30 , a check valve in the conduit 58 , schematically indicated at 62 , is desired to prevent a backflow of gas from the low pressure header 56 into the permeate oxygen plenum 30 after the rupture disk 48 fails . that is , the check valve 62 precludes low pressure gas from the header 56 from passing through the opening in the ruptured disk 48 and into the oxygen collecting plenum 30 through outlet passage 26 of the isolation device 10 . referring to fig2 , a module isolation device 100 is depicted , which includes a number of elements that are the same as the elements employed in the module isolation device 10 . the elements in the module isolation device 100 that are the same as elements in the module isolation device 10 are identified by the same numerals , but with a suffix “ a .” suffice it to state that the module isolation device 100 disclosed is fig2 functions to receive permeate oxygen from ion transport membrane module 12 a in the same manner as described above in connection with the module isolation device 10 disclosed in fig1 . the only difference between the module isolation device 100 and the module isolation device 10 is in the manner in which the low pressure header 56 a of the module isolation device 100 is provided to communicate with the second face 54 a of the rupture disk 48 a . specifically , in the module isolation device 100 the oxygen collecting plenum or header 30 a is placed in direct communication with the second face 54 a of the ruptured disk 48 a through a conduit 102 of any desired configuration , whereby the low pressure flow of oxygen into the plenum 30 a through flow restricting orifice 28 a also constitutes the low pressure gas communicating with the second face 54 a of the ruptured disk 48 a . thus , the oxygen collecting plenum 30 a actually functions as the low pressure header in the module isolation device 100 . by employing this latter arrangement the purity of the oxygen in the oxygen collecting plenum 30 a is ensured , and there is no need to provide a check valve , similar to the check valve 62 employed in the module isolation device 10 , in order to prevent the backflow of low pressure gas through the ruptured disk 48 a into the oxygen collecting plenum 30 a . such a check valve is not required because the gas that is capable of flowing through the ruptured disk 48 a in a reverse direction actually is the same purified oxygen that is collected in the oxygen collecting plenum 30 a . referring now to fig3 , a pair of module isolation devices 200 and 300 are connected with an itm syngas module 12 b on the airfeed line into the module and the spent air effluent from the module , respectively . components of module isolation devices 200 , 300 that operate in the same manner as components in the module isolation device 10 will be referred to by the same numerals , but with the suffixes “ b ” and “ c ,” respectively . the operation of itm syngas modules are well known in the art and the specific construction thereof does not constitute a limitation on the broadest aspects of this invention . during operation of an itm syngas module 12 b a high - pressure synthetic gas , e . g ., methane or other light hydrocarbon gas , is directed through passageways 14 b of the module 12 and into engagement with permeate oxygen extracted from air fed into the module to thereby form the syngas . in the discussion that follows the module isolation device 200 will sometimes be referred to as the “ fresh gas isolation device ,” “ fresh air isolation device ” or by words of similar import , and the module isolation device 300 will sometimes be referred to as the “ spent gas isolation device ,” “ spent air isolation device ,” “ effluent isolation device ” or by words of similar import . although the description that follows describes a preferred embodiment in which the fresh oxygen - containing gas is air , in accordance with the broadest aspects of this invention other oxygen - containing gases can be employed . in the illustrated embodiment , a fresh air feed header 202 receives fresh air to be directed into the itm syngas module 12 b . this fresh air feed is directed into the fresh air isolation device 200 through an optional flow - restricting orifice 204 , and then through outlet conduit 206 of the device . the outlet conduit 206 communicates with air feed inlet 208 of the module 12 b . the air feed inlet 208 is provided by a ceramic conduit or tube that is concentric with an outer ceramic conduit or tube 210 that is connected to a ceramic to metal seal 212 . it is through this outer conduit 210 that the spent gas ( e . g ., the gas from which oxygen ions have been removed in the itm syngas module 12 b ) is directed into the spent air isolation device 300 . it should be understood that the construction and operation of the spent air module isolation device 300 is identical to the construction and operation of the oxygen permeate isolation device 10 illustrated in fig1 , with the exception that the gas being isolated by the isolation device 300 is the spent air that gave up its oxygen to the synthetic gas , as opposed to pure oxygen removed from the air by the itm oxygen module 12 . however , the structural features and operation of the module isolation device 300 is otherwise identical to that described above in connection with the module isolation device 10 . as noted above , the air feed into module 12 b and the spent air effluent from that module are connected to the module through the concentric ceramic tubes 208 , 210 , respectively . each of these tubes is connected to metal piping through a ceramic to metal seal 212 . still referring to fig3 , the module isolation device 200 employs a module isolation valve 40 b upstream of the ceramic to metal seal 212 for the air feed leg . the module isolation device 300 employs a module isolation valve 40 c for the spent air effluent from the module 12 b , downstream of the ceramic to metal seal 212 for the spent air effluent leg . the flow of the fresh airfeed into the inner concentric tube 208 of the module 12 b is illustrated by arrows 214 , and the flow of spent effluent from the module 12 b is illustrated by arrows 216 . during normal operation , both of the module isolation valves 40 b , 40 c are opened . air feed passes from the airfeed header 202 through optional flow restricting orifice 204 , through the airfeed module isolation valve 40 b and through outlet conduit 206 communicating with the air feed inlet 208 into the itm syngas module 12 b . spent air exiting the module 12 b ( as depicted by arrows 216 ) passes through the spent air module isolation valve 40 c of the spent air isolation device 300 , through an optional flow - restricting orifice 28 c and into spent air header or plenum 30 c . the flow - restricting orifices 28 c , 204 , if needed , are designed to provide sufficient back pressure in the respective isolation devices 300 , 200 in the event of an increased flow from the module 12 b , such as from a leak , to thereby increase the pressure acting on the rupture disks 48 b , 48 c in both module isolation devices 200 , 300 to values sufficiently above the pressures normally encountered under steady state operating conditions . as in the embodiments illustrated in fig1 and 2 , the valve stems 44 b , 44 c of the module isolation valves 40 b , 40 c in the module isolation devices 200 , 300 are mechanically linked to the first face 50 b , 50 c of the rupture disks 48 b , and 48 c , respectively . in the illustrated embodiment , the mechanical linkage is created by the first face 50 b , 50 c of the rupture disks 48 b , 48 c actually supporting ends 52 b , 52 c of the valve stems 44 b , and 44 c , respectively . in the event of a malfunction of the module 12 b , resulting in the backflow of syngas through both the inner and outer concentric tubes 208 , 210 , respectively , the high pressure backflow causes the rupture disks 48 b , 48 c to rupture , resulting in a closure of the respective module isolation valves 40 b , 40 c in the module isolation devices 200 , 300 . this will prevent contamination of the spent air effluent and the fresh air infeed by the syngas . as in the earlier described embodiments , the second face 54 b , 54 c of the rupture disks 48 b , 48 c in the fresh air isolation device 200 and in the spent air isolation device 300 , respectively , are in full communication with respective low pressure headers 56 b , 56 c . in the embodiment illustrated in fig3 , the low pressure headers 56 b , 56 c are separate from the fresh air feed header 202 into the module isolation device 200 and the spent air or effluent collection plenum 30 c of the module isolation device 300 . in this arrangement , it is desirable to employ check valves 62 b , 62 c in conduits 58 b , 58 c that communicate the low pressure headers 56 b , 56 c with the second faces 54 b , 54 c of the rupture disks 48 b , 48 c , in the same manner as described above in connection with the module isolation device 10 illustrated in fig1 . specifically , these check valves 62 b , 62 c will prevent the flow of gas from the low pressure headers 56 b , 56 c into the airfeed header 202 of the fresh air isolation device 200 and into the spent air header 30 c of the spent air isolation device 300 , respectively . still referring to fig3 , in an alternative , and more preferred arrangement , the air feed header 202 is employed as the low pressure header in communication with the second face 54 b of the rupture disk 48 b in the fresh air module isolation device 200 , and the effluent plenum or header 30 c is employed as the low pressure header in communication with the second face 54 c of the rupture disk 48 c in the spent air isolation device 300 . this is achieved by providing conduits communicating the respective airfeed header 202 and the effluent air header 30 c with the region underlying the second faces 54 b , 54 c of the respective ruptured disks 48 b , 48 c , in the same manner that conduit 102 is employed in the module isolation device 100 illustrated in fig2 . in this latter arrangement there is no need for any check valves to prevent the flow of gas from the low pressure region underlying the rupture disks 48 b , 48 c into the air feed header 202 and spent air header 30 c of the module isolation devices 200 and 300 , respectively , since the low pressure region 56 b in the module isolation device 200 would contain the same air supply as in the air feed header 202 , and the low pressure region 56 c in the module isolation device 300 would contain the same effluent as in the spent air header 30 c of that module isolation device . by way of brief description , and still referring to fig3 , the backflow of syngas resulting from a malfunction of the module 12 b will cause a significant pressure increase in the module isolation devices 200 and 300 , to thereby cause the rupture disks 48 b , 48 c therein to rupture and the corresponding module isolation valves 40 b , 40 c to close , in a manner similar to that described in connection with the module isolation device 10 depicted in fig1 and the module isolation device 100 depicted in fig2 . the closing of valves 40 b , 40 c isolates the undesirable backflow of syngas from a damaged module 12 b into either the fresh air feed into isolation device 200 or the effluent out of the isolation device 300 . referring to fig4 - 6 , module isolation devices similar to module isolation devices 10 , 100 , 200 and 300 , respectively , are depicted . the embodiments depicted in fig4 - 6 represent the most preferred embodiments and overcome a problem that potentially exists with the embodiments illustrated in fig1 - 3 . specifically , in the embodiments depicted in fig1 - 3 , the ruptured disks constitute part of the described module isolation valves 40 , 40 a , 40 b and 40 c , and in the disclosed embodiments , actually engage the lower ends of their respective valve stems 44 , 44 a , 44 b and 44 c to normally bias the isolation valves into their opened condition . it was determined that during operation of the module isolation devices 10 , 100 and 300 , the flow of gas against the valve members ; particularly valve members 46 , 46 a and 46 c , during normal operation of the modules 12 , 12 a or 12 c caused the valve stems 44 , 44 a and 44 c to vibrate against the rupture disks 48 , 48 a , 48 c thereby creating the possibility of premature failure of those rupture disks . in other words , the vibration of the valve stems 44 , 44 a and 44 c against the rupture disks 48 , 48 a and 46 c , respectively , can cause those rupture disks to fail , and thereby cause the valve members 46 , 46 a and 46 c to seat against their respective valve seats 42 , 42 a and 42 c , even if no malfunction of the module 12 , 12 a or 12 c occurs . this clearly is undesirable . fig4 - 6 disclose module isolation devices that are identical to the module isolation devices 10 , 100 , 200 and 300 , respectively , except for the construction of the module isolation valves . specifically , wherein the module isolation valves 40 , 40 a , 40 b and 40 c employed in the embodiments illustrated in fig1 - 3 include respective ruptured disks 48 , 48 a , 48 b and 48 c as a component thereof , the module isolation valves employed in the embodiments illustrated in fig4 - 6 do not include the rupture disk as a component thereof . in fact , as will be explained hereinafter , the valve stem of the valve assemblies illustrated in the embodiments of fig4 - 6 do not engage the respective rupture disks at all , and actually are spaced from the rupture disks during movement between opened and closed conditions of the valves . referring specifically to fig4 , a module isolation device 400 is depicted for use in connection with an ion transport membrane oxygen module 12 d , in the same manner as the module isolation device 10 . components of the embodiment illustrated in fig4 that are identical to components of the embodiment illustrated in fig1 are identified by the same numerals , but with the suffix “ d ” and in many cases will not be discussed in detail herein , for purposes of brevity . the sole difference between the module isolation device 10 illustrated in fig1 and the module isolation device 400 illustrated in fig4 is that the preferred embodiment of the module isolation device 400 includes three additional elements ; namely , a stationary , perforated plate 402 connected to the module isolation device for supporting a crushable member 404 thereon , the crushable member 404 , preferably being a spring supported on the perforated plate 402 , and a stopper , or actuating member 406 affixed to the valve stem 44 d and movable with said valve stem . optionally a porous insulation member 60 d can be provided to insulate a downstream region of the isolation device 400 , if desired . as noted above , most preferably the crushable member 404 is a spring , which will not need to be replaced when the module isolation device 400 is repaired with a new rupture disk 48 d , after a rupture disk has ruptured because of a malfunction of module 12 d . specifically , when the module isolation device 400 is shut down for repair , the compressed spring 404 will return to its normal , uncompressed state , and therefore does not need to be replaced . a preferred type of spring is a wave spring . it should be noted that in this embodiment the lower surface 52 d of the valve stem 44 d is maintained out of engagement with the upper face 50 d of the rupture disk 48 d while the crushable member 404 acts against the actuating member 406 that is attached to the valve stem to normally maintain module isolation valve 40 d in an opened condition . in the embodiment of the invention illustrated in fig4 , the module isolation valve 40 d includes valve seat 42 d , valve stem 44 d including a valve member 46 d at one thereof , and a crushable member 404 , e . g ., a spring , retained on the stationary , perforate plate 402 and being compressible by an actuating member 406 attached to the valve stem . still referring to fig4 , in the event of a malfunction of the module 12 d the pressure within the isolation device 400 will increase to an undesirable level , and the rupture disk 48 d is engineered to rupture at that level . subsequent to the rupturing of the disk 48 d the increased flow acting upon the valve member 46 d produces a pressure differential that forces the actuating member 406 against the spring 404 ( or other crushable member ), to thereby cause the valve member 46 d to seat against the valve seat 42 d while compressing the spring or other crushable member . in the preferred embodiment , the lower end 52 d of the valve stem 44 d is maintained in a position where it does not move through the plane occupied by the rupture disk 48 d . as should be apparent , in the module isolation device 400 illustrated in fig4 any vibration imposed upon the valve member 46 d by the flow of oxygen during normal operation of the itm oxygen module 12 d will not cause the valve stem 44 d to vibrate against the rupture disk 48 d to thereby possibly cause a premature failure , or rupture , of that disk . turning to fig5 , a module isolation device 500 substantially similar to the module isolation device 100 depicted in fig2 is shown . components of the module isolation device 500 depicted in fig5 that are identical to components of the module isolation device depicted in fig2 are identified by the same numerals , but with the suffix “ e .” these latter components will not be described in detail herein , for purposes of brevity . in fact , it should be apparent that the difference between the module isolation device 500 shown in fig5 and the module isolation device 100 shown in fig2 is that the module isolation valve assembly 40 e in the fig5 embodiment is modified to the preferred form 40 d employed in the module isolation device 400 shown in fig4 . accordingly , components of the module isolation valve 40 e in the module isolation device 500 depicted in fig5 that are identical to components of the module isolation valve , 40 d in the module isolation device 400 depicted in fig4 are identified by the same numerals , but with the suffix “ e .” by way of brief explanation , in the event of a malfunction of the ion transport membrane oxygen module 12 e , resulting in an increased pressure within the module isolation device 500 , the increased pressure acts directly on the first face 50 e of the rupture disk 48 e to cause the rupture disk to rupture . thereafter , the increased flow of gas will act upon the valve member 46 e to move said valve member in a downward direction to seat the valve member against valve seat 42 e while compressing wave spring 404 e . as is described in connection with the module isolation device 400 disclosed in fig4 , in accordance with the broadest aspect of this embodiment of the invention the wave spring 404 e can be replaced with other types of crushable members , but most preferably the crushable member is in the form of a spring so that it will not need to be replaced when a module is repaired with a new rupture disk , after the original rupture disk fails due to a malfunction of the ion transport membrane module 12 e . turning to fig6 , module isolation devices 600 and 700 are depicted , which are similar to the module isolation devices 200 and 300 illustrated in fig3 , and provide exactly the same functions as these latter module isolation devices . moreover , the only difference between the module isolation devices depicted in fig3 and 6 is in connection with the construction of the module isolation valves employed in the isolation devices . components of module isolation devices 600 and 700 that are identical to components of module isolation devices 200 and 300 are designated by the same numerals , with the suffixes “ f ” and “ g ” respectively . components of the module isolation valves in the module isolation devices 600 and 700 that are identical to the components of the module isolation valve in the module isolation device 400 illustrated in fig4 are designated by the same numerals , also with the suffixes “ f ” and “ g ” respectively . suffice it to state , that the module isolation devices 600 , 700 employed in connection with an itm syngas module , as shown in fig6 , functions in the same manner as the module isolation devices 200 and 300 employed in the fig3 embodiment , with the exception of the structure and operation of the isolation valves . in particular , in the module isolation devices 600 and 700 the module isolation valves 40 f and 40 g are each constructed in the same manner as the module isolation valve 40 d employed in the module isolation device 400 , and move between opened and closed positions in the same manner as in the module isolation device 400 . thus , the module isolation valves 40 f and 40 g actually prevent their respective valve stems 44 f , 44 g from engaging the rupture disks 48 f , 48 g in the respective module isolation devices 600 and 700 , to thereby prevent premature failure of those rupture disks resulting from vibration of the valve stems against the respective rupture disks caused by the normal flow of gas in the respective module isolation devices 600 and 700 . the potential problem of premature rupturing of rupture disks , which is solved by the structure of the module isolation valves 40 f , 40 g in the module isolation devices 600 , 700 , respectively , is prevalent in a module isolation device intended to function in the manner of module isolation device 700 , wherein the flow of gas during normal operation of the itm module is in a direction against the rupture disk 48 g , which also is the direction tending to force or vibrate the valve stem against the rupture disk . it should be understood that the flow of fresh air and spent air through module isolation devices 600 and 700 is the same as the flow of fresh air and spent air through the module isolation devices 300 and 400 in the fig3 embodiment , with the module isolation valves 40 g and 40 h moving to a closed position after rupturing of rupture disks 48 f and 48 g , by the same mechanism that module isolation valve 40 d is moved into a closed position in the module isolation device 400 disclosed in fig4 . moreover , the low pressure headers 56 f and 56 g can be of the same construction and employed in the same manner as low pressure headers 56 c and 56 d in the module isolation devices 300 and 400 , respectively . alternatively , the low pressure region communicating with the lower faces 54 f , 54 g of rupture disk 48 f and 48 g can be provided by communicating the fresh air feed plenum 202 f with the lower surface of rupture disk 48 f through a connecting conduit , and by communicating the spent air plenum 30 g with the lower surface of rupture disk 48 g through a connecting conduit , essentially in the same manner as described in connection with the module isolation device 100 illustrated in fig2 and the modulation device 500 depicted in fig5 . when the fresh air feed is employed to provide the low pressure area behind rupture disk 48 f , and the spent air is employed to provide the low pressure area behind rupture disk 48 g , there is no need to provide check valves in the low pressure sections to prevent contamination of the fresh air feed in the air feed header 202 or contamination of the spent gas in the spent gas collecting plenum 30 g when rupture disks 48 f and 48 g , respectively , are ruptured . the reason why such check valves are not be required was explained earlier in connection with the isolation devices 200 , 300 ; modified to provide air feed plenum 202 as the low pressure area behind rupture disk 48 b and spent gas plenum 30 c as the low pressure area behind rupture disk 48 c . that explanation will not be repeated herein for purposes of brevity . although illustrated and described herein with reference to certain specific embodiments , the present invention is nevertheless not intended to be limited to the details shown . rather , various modifications may be made in the details within the scope and range of equivalence of the claims and without departing from the spirit of the invention . | 5 |
the apparatus 10 shown in fig1 for in - situ microscopy of cells in a culture medium encompasses a sample volume 12 between two windows 14 , 16 that are aligned perpendicular to the optical axis of a microscope lens 18 used to image cells 20 in the sample volume 12 . in the most simple embodiment , the windows 14 , 16 are glass plates . the embodiment shown here serves primarily for examining organic cells 20 . but in principle the present invention is not limited to such cells but is also suited for examining non - organic particles suspended in a liquid medium . the sample volume 12 is illuminated by an illumination arrangement 22 having a light source 24 and a condenser 26 operating in a so - called transmitted - light mode . in the case shown here , a bright - field illumination is employed , but any other type of illumination arrangement is also possible . if the illumination source and the lens 18 are located on the same side of the object , as is the case in an incident - light arrangement , the opposite window does not necessarily have to be transparent but in principle can also be an opaque rear wall of the sample chamber . the microscope lens 18 images the cells 20 on an electronic image sensor 28 connected to the image processing system 30 used for the electronic recording and processing of the image . furthermore , the image processing system 30 is also connected to a control unit 32 for controlling an actuator 34 which effects a linear shift of the window 16 of the sample volume 12 facing away from the microscope lens 18 . the depth d of the sample volume 12 in the direction of the optical axis can thus be altered by the actuator 34 . in addition , an adjustable diaphragm 36 , which can also be addressed by the control unit 32 , is arranged between the microscope lens 18 and the image sensor 28 . the depth of field of the lens 18 is determined by its numeric aperture . a high numeric aperture value results in a low depth of field , i . e . only a narrow range of the sample volume 12 is imaged in focus . the numeric aperture can be changed by either opening or closing the diaphragm 36 . in order to image a large number of cells 20 in the sample volume in sharp focus , prior to analysis , the thickness d is gradually decreased until all cells 20 lie in a single layer between the windows 14 , 16 . this process is shown in fig2 to 4 . fig2 corresponds roughly to the situation in fig1 , in which the culture medium can freely circulate throughout the sample volume 12 and the cells 20 can also move about freely . the thickness d is decreased by means of the actuator 34 , shown in fig3 , until a situation shown in fig4 is reached , where the cells are markedly flattened by the pressure exerted by the windows 14 , 16 . since the imaging of the cells 20 is continually controlled by the image processing system 30 , the latter , upon detecting flattening , sends a signal to the control unit 32 , which drives the actuator 34 in the opposite direction in order to regain separation value d of fig3 , in which the windows 14 , 16 have just made contact with the cells 20 without flattening them . this separation d is an optimum value for analyzing the cells 20 and thus the image obtained in fig3 can be employed in the analysis of various cell parameters , such as concentration , size , morphology and vitality . fig5 illustrates by means of a diagram the process of successively decreasing the thickness d of the sample volume 12 . here the diameter g in the image of a single cell 20 is plotted according to the separation d of the windows 14 , 16 . if an initially large separation d is gradually decreased , the apparent cell diameter g remains constant at first until the cells 20 are finally clamped between the windows 14 , 16 as shown in fig3 . at this point , which corresponds to the separation value d , the diameter g starts to increase dramatically as the separation d decreases . since the parameter g is permanently monitored by the image processing system 30 as the window 16 is moved , this point can be exactly determined so that the thickness d can be precisely set to the separation value d where the flattening process just starts to commence . if this point is overshot , making flattening already measurable , and the separation value d is undershot , the control unit 32 can increase the distance variable d until a situation is reached where d = d . the point where flattening commences can be stored by the image processing system 30 and must therefore not be determined at the start of each new measuring cycle but can be retrieved from storage for the immediate setting of the separation value d , thus shortening the measuring cycle . fig6 to 8 show images of cells 20 recorded by the image sensor 28 and processed by the image processing system 30 in such a manner that the individual fig5 to 7 can be assigned to fig2 to 4 . fig5 shows merely an unfocussed image of the cells 20 , as they are located outside the level of sharp focus of the lens 18 . once the separation distance d is attained , at which point a layer of cells 20 lie exactly between the windows 14 , 16 , then all cells 20 are located in the level of sharp focus and are imaged clearly . in this situation an optimum analysis of individual cell parameters can be conducted . furthermore , if the windows 14 , 16 are brought closer together , the cells are flattened , as clearly shown in fig7 . the diameter g increases and this increase can be detected by a image processing system 30 that has been appropriately programmed , so that the depth d of the sample volume 12 can be set in the manner described above . fig9 to 11 correspond to fig2 to 4 except that now cells 20 , 38 of different sizes are present in the sample volume 12 . in this case , cells 38 of a predetermined size can be used to set the separation value d of the windows 14 , 16 such that the windows 14 , 16 are brought together until the separation distance d is reached where a flattening of the cells 38 of the selected size occurs . the remaining cells 20 are disregarded here . if smaller cells 38 are used in the above example for setting the distance d , the larger cells 20 are naturally flattened to a very significant degree until they reach a state shown in fig1 . a severe deformation or even destruction of the larger cells 20 can be accepted in this case , since the image processing system can easily distinguish these cells from the cells 38 to be analyzed . for example , the destroyed cells 20 are simply subtracted from the examined region of imaging . it is also possible to include the larger cells 20 when setting the distance so that the windows 14 , 16 are only brought together to the point where a flattening of the larger cells 20 commences . this is the approximate situation shown in fig1 . fig1 shows a sample volume 12 having a free - floating carrier 40 and a number of cells 38 adhering to it . the carrier 40 involves polystyrene platelets having a diameter of 0 . 1 to 0 . 2 mm and a thickness of 20 μm . thickness d is reduced in order to observe the adherent cells 38 so that the carrier 40 pursuant to fig1 is flat in its orientation between the windows 14 , 16 and the cells 38 on the opposing surface sides are flattened by the surface pressure . but in this case , due to the adhesion of cells 38 on both sides of the surface of the carrier 40 , two layers of cells 38 are located in the sample volume 12 . in order to examine the cells 38 it is therefore necessary to select a low focus depth of the lens and to displace the object level , i . e . the region of sharp focus by the lens 18 , to one of the cell layers . in this case , therefore , the cell layer facing the lens or the cell layer located at the back side of the carrier 40 is selected and imaged . this is achieved by a corresponding adjustment of the microscope lens 18 or of the image sensor 28 . proper depth of field can be achieved by enlarging the numeric aperture and opening the diaphragm 36 so that the cell layer lying in front of or behind the image cell layer does not interfere with imaging . the process of setting the thickness of the sample volume 12 essentially corresponds to the case described above , but differs in that the cells 38 do not lie directly between the windows 14 , 16 but rather between one of the windows 14 , 16 and the carrier 40 . at the point of initial flattening of the cells 38 the distance d of the windows 14 , 16 is approximately that of the thickness of the carrier 40 plus the double value of the cell diameter . by virtue of this procedure it is possible , for example to determine quite easily the fouling density and the degree of intergrowth of the cells 38 on the carriers . fig1 shows a sample volume 12 with a wiper 42 that removes cells clinging to the windows 14 , 16 after the measuring process . this is advantageous because the adherent cells 38 are recorded again in every new measuring cycle and thus distort the obtained results . the wiper 42 is essentially an arm 44 with two opposing rubber lips 46 , 48 , made of silicone rubber , that abut the windows 14 , 16 . as shown in fig1 , this arm 44 is attached at one end to a pivotal axis 50 which moves it back and forth between the windows 14 , 16 , thus drawing the rubber lips 46 , 48 across the surfaces to clean the windows 14 , 16 . the image processing system 30 can be programmed to check the efficiency of the wiping action and to repeat it if necessary . in case the culture medium contains free - floating cells as well as carriers 40 , the image processing system 30 can make an assessment based on the image as to whether a carrier 40 or merely free - floating cells are suspended in the sample volume and can then set the separation value d according to the pre - stored values for each of these two cases . | 2 |
as seen in fig1 , an apparatus for wrapping a stack 1 of objects with a film 2 has a film - feed head 3 for feeding the film 2 and a pull - down device 4 for subsequently covering the stack 1 with the film 2 , typically by pulling it down over the stack 1 . the device 4 can be moved up and down on vertical posts or columns 25 by an unillustrated actuator , and the head 3 is mounted at the tops of the posts 25 . the apparatus also has a film supply in the form of a film coil 5 from which the film 2 is fed to the film - feed head 3 . the stacks 1 are moved horizontally past a wrapping station 27 formed by the apparatus according to the invention in a transport direction d by a conveyor shown schematically at 26 . according to the invention as also shown in fig2 , the film - feed head 3 has a base 6 and a support 7 rotatable about a vertical axis relative to the base 6 . here the rotatable support 7 is underneath the base 6 . the base 6 includes a film feeder 8 for pulling the film 2 off the spool 5 and advancing it to the rotatable support 7 . the base 6 also has guide rollers or deflection rollers 9 for the film 2 . preferably the film 2 is a tube , in particular with side gussets . the rotatable support 7 has a guide ring 10 connected to the base 6 and a film storer 11 carried on the rotatable support 7 underneath the guide ring 10 and whose function according to the invention is described in more detail below . the rotatable support 7 is also equipped with a film cutter in the form of a blade 12 that can cut a section 13 that may be tubular from the film 2 . the rotatable support 7 also has a film welder in the form of two welding bars 14 . using this film welder or these welding bars 14 , an upper end of the film section 13 may be welded together , to form a hood - shaped film section 13 , or for a simple flat film 2 a simple sheet . this hood - shaped film section 13 or this film sheet is then pulled down over the stack 1 by the device 4 . to this end , the rotatable support 7 also has an opener 15 for spreading the film section 13 or the tubular film section . preferably and here the opener 15 includes suction side plates 16 known per se for opening the tubular film . the apparatus according to the invention is used for wrapping stacks of objects 1 that in cross section or top view are not square , that is that are of different horizontal width w and length l dimensions where w ≠ l , and that are usually carried on pallets 17 that likewise in cross section or top view are not square . the instant invention is particularly applicable to a situation where as illustrated a nonsquare stack 1 or a nonsquare pallet 17 having for instance its width dimension w extending parallel to the conveying direction 26 is followed by a stack 1 having its length direction l parallel to the transport direction 26 , that is they are rotated relative to one another about respective vertical axes by 90 °. in principle , the two consecutively supplied stacks 1 and the respective pallets 17 described above may thus have the same dimensions or sizes . here they are rotated with respect to one another only by 90 °. to allow the film 2 or the tubular film to then be fed without constraint , according to the invention the rotatable support 7 is rotatable relative to the base 6 of the film - feed head 3 , here by 90 ° so that it can align with the workpiece stack 1 . the film storer 11 has two endless belts 19 carried on respective horizontally confronting end walls 18 of the support 7 and supporting two looping rollers 20 for the film 2 that extend between the continuous belts 19 and between the end walls 18 of the rotatable support 7 . in addition , guide rollers 21 for the film 2 are fixed to the continuous belts 19 , and likewise extend parallel to the rollers 20 between the end walls 18 of the rotatable support 7 . the continuous belts 19 are themselves spanned over two deflection rollers 22 , at least one of which is is driven by an unillustrated motor carried on the support 7 , and both of which are journaled permanently in the two end walls 18 . here the continuous belts 19 are chains , and the drive deflection roller 22 carries sprockets that mesh with the chains . only one end wall 18 and only one continuous belt 19 are visible in fig3 through 6 . the film 2 here is of the side - gusset type comprising a tube with two folded - in side gussets so that the tube as shown in fig1 has a width equal to somewhat more than the long dimension or length l of the stacks or packages being wrapped , and the gussets , open up to a dimension equal to the short dimension or width l of the stacks or packages being wrapped . thus for wrapping a package 1 whose length l is parallel to the conveyor direction 2 , the film 2 is fed from the feeder 8 to the base 6 of the rotatable support 7 , and specifically , past the film blade 12 and the welding bars 14 , and through the film storer 11 until reaching the opener 15 . the end of the film 2 is advantageously conveyed to the lower edges of the suction side plates 16 . the suction side plates 16 , which in fig3 are separated , are then brought together so that the film 2 is gripped and cannot advance between them . then the device 4 , which has gripped the leading end of the cut - off film section 13 , is pulled down on the columns 25 so that the spread tube section 13 is fitted over the package 1 . when a section of the film tube 2 sufficient to cover the entire package 1 has passed through the cutter 12 , the bars 14 are closed and the cutter 12 is operated to weld closed the upper end of the section and cut the section off the tube 2 . typically after being pulled over the stack or package 1 , the tube section 2 is heat shrunk either in the wrapping station 27 or downstream , or the tube section may be elastically stretched as it is pulled down and released to engage tightly around the package 1 . this is all generally standard . when , however , a package arrives at the wrapping station 27 offset by 90 ° the film 2 is fed through the storer 11 to the suction side plates 16 that are then closed . the film storer 11 is then started by moving the belts 19 such the looping roller 20 on the upper stretches of the continuous belts 19 carries the film 2 along to the right , and the looping roller 20 on the lower stretches of the continuous belts 19 carries the film 2 along to the left ( fig4 ). in the lower region of the film storer 11 , the film 2 passes over a film - guide roller 23 movable transverse to a covering direction u of the film 2 . in the position of fig4 , two opposite film sections 24 are engaged around the looping rollers 20 and are stored in the film storer 11 . the looping rollers 20 continue to move around the deflection rollers 22 of the continuous belts 19 so that the looping roller 20 previously on the upper stretches moves to the lower stretches , and the looping roller 20 previously on the lower stretches moves to the upper stretches ( fig5 ). the looping rollers 20 are moved further along the upper stretches and the lower stretches toward the center of the film storer by corresponding movement of the continuous belts 19 , resulting in the position illustrated in fig6 . the partial film sections 24 situated or stored in this manner in the film storer 11 have a total length that is considerable , and easily enough to reach from the top to the bottom of a relatively tall object or stack 1 . after the desired length of film has been stored ( fig6 ), the film feeder 8 and the continuous belts 19 are stopped . the bars 14 for welding the film section 13 are then closed , and the film section 13 is separated from the remaining film 2 by the film blade 12 . this is followed by rotation of the rotatable support 7 or the rotation of the guide ring 10 of the rotatable support 7 . the rotatable support 7 is advantageously rotated by 90 ° during the welding process and during cooling of the produced weld seam . rotation of the support 7 with the storer 11 therefore aligns the stored tube 2 with the crosswise workpiece 1 as shown in fig1 and 2 . for the covering operation , the film section 13 is opened by the opener 15 or by the suction side plates 16 , and , as the result of reverse movement of the continuous belts 19 , the film storer 11 releases the film section 13 , and , the pull - down device 4 draws the film section 13 down over the stack 1 . this is not illustrated in greater detail in the figures . | 1 |
in order to achieve these aims , the invention more specifically relates to a process for the chemical transformation of at least one complex chemical structure into at least one end product , characterized in that the chemical transformation involves at least one reduction reaction in a solvent in the supercritical state . in other words , the object of the invention is to aid , through controlled chemical reactions , the decomposition of effluents , molecules or complex chemical structures , at least one of the chemical reaction stages being a reduction . the term chemical transformation is understood to mean both the decomposition of the molecular or atomic system of the complex chemical structure or structures into one or more chemical structures with a simpler molecular system , and the chemical interaction of the varyingly complex molecular systems with one another or with the solvent in the supercritical state . the chemical interaction of molecular systems involves various reactions or solubilizations , whereof one or more are reductions . the reduction phenomenon means any reaction leading for one of the elements of the chemical structure to be decomposed to an electron gain . a definition will firstly be given of the supercritical state in which the reduction or reductions take place with respect to the solvent . for example , the solvent can be water , an alcohol such as ethanol , a water - alcohol mixture , or any other appropriate solvent . its choice is essentially dependent on the chemical structures which it is wished to transform . moreover , on the basis of on the one hand the specific physicochemical properties of supercritical fluids and on the other the reducing conditions making it possible to preserve certain functions for the end products resulting from the transformation , as a function of the structures to be treated , it is possible to terminate with the decomposition , or the formation of valorizable compounds , as will be shown hereinafter . according to the invention and in general terms , supercritical media have been used in order to increase the in situ reactivity and according to a specific aspect of the present invention to better control the chemical reactions able to take place in the medium . according to the particular nature of the chemical structures which it is wished to transform , the performance of the process can be adapted . in a first variant of the process , the latter can involve the following stages : a ) formation of a reaction fluid incorporating the complex chemical structure or structures in solution or suspension in the solvent , and at least one additive having a reducing character , e . g . if the reaction mechanism provided do not lead to an adequate reducing character under the use conditions , b ) bringing into the supercritical condition to bring about the chemical transformation and in the case where either the solvent , or one of the complex chemical structures which it is wished to transform , have a reducing character under supercritical conditions , a specific reducing additive is not indispensable during the formation of the reaction fluid . stage a ) is then merely the formation of a reaction fluid incorporating at least the complex chemical structure or structures in solution or suspension in the solvent , the solvent and / or at least one of the chemical structures of the reaction fluid having a reducing character under the supercritical temperature and pressure conditions of the solvent . this is the case with an example referred to hereinafter , wherein treatment takes place of deinking sludge of newspapers containing inks having a reducing character under supercritical conditions . the addition of an additive ( e . g . sodium hydridoborate ) can aid the transformation , but is not indispensable . it is also possible that none of the chemical structures or the solvent initially present in the reaction medium have a reducing character , but that at least one of them decomposes into a new chemical structure , which is reducing under supercritical conditions . stage a ) of the process then involves the formation of a reaction fluid incorporating the complex chemical structure or structures to be treated in solution or suspension in the solvent , with at least one of the complex chemical structures or the solvent transforming under supercritical conditions into a compound having a reducing nature . this is e . g . the case for the treatment of casein , which is transformed into light hydrocarbons and carbon . the supercritical conditioning essentially consists of increasing the pressure and temperature of the reaction medium to values exceeding the critical pressure and critical temperature of the solvent . moreover , the reaction fluid generally has 1 to 20 wt . % of complex chemical structures to be transformed . according to a special aspect of the invention , the reducing transformation can be described in terms of hydrogen equivalents necessary for obtaining the targeted end products during the same . in this case , it is possible to determine as a function of the sought end products a hydrogen equivalent chemical supply ( h . e . c . s .) necessary for the transformation and the composition of the reaction medium is modified in order to have in said medium a hydrogen equivalent chemical supply equal to or greater than the h . e . c . s . resulting from the composition of the reagents ( complex chemical structures , solvent ), optionally by means of an additive . through adjusting the h . e . c . s . it is not possible to orient the transformation towards particular end products such as e . g . ch 4 or c 2 h 6 , but also inhibits the possible corrosion of treatment equipment and devices under supercritical conditions by adjusting the h . e . c . s . to a value just above the h . e . c . s . required for obtaining the sought products . on returning to ambient pressure and temperature conditions , the products obtained from the transformation are separated using known processes such as sedimentation , distillation or a membrane method . according to a preferred and particularly advantageous embodiment of the invention , the inventors have shown that the supercritical range of the reaction fluid or medium could be divided into at least three large ranges or zones , which will be subsequently called range a , range b and range c . in the supercritical range of the reaction fluid or medium , range a is a range in which there are low temperatures and high pressures , i . e . the pressure is in excess of the critical pressure of the reaction fluid or medium and is the most suitable for the solubilization of complex chemical structures and / or products in the system or complex mixture or reaction fluid or medium , whilst the temperature is the lowest possible temperature ensuring that one is in the supercritical range of the complex mixture or system or reaction fluid or medium . in this range , the fluid has a density close to that of the liquid phase . thus , the solubility of the complex chemical structures is greatly facilitated in this range . in the supercritical range of the reaction fluid or medium , range b is a high temperature range , i . e . the temperature exceeds the critical temperature of the reaction medium and is the most suitable for the decomposition of products and / or complex chemical structures in the reaction fluid or medium , whilst the pressure is the lowest pressure ensuring that one is in the supercritical range of the complex mixture or system or the reaction fluid or medium . in this range , the fluid has a much lower density . the solubility of the complex chemical structures is reduced , but conversely the decomposition and / or dilution reactions are much greater . in the supercritical range of the reaction fluid or medium , range c is an intermediate range , where the temperatures and pressures are intermediate or complimentary of those defined for ranges a and b . thus , in this range there is both a solubilization of complex structures and a decomposition of said structures and an optimization can take place there between thermal decomposition and solubility . according to the invention , in this preferred embodiment it is possible to control the complex chemical transformation through one or more of these different ranges in order to obtain perfectly targeted , sought end products . thus , it is possible to carry out the treatment of the reaction medium containing at least one complex chemical structure in a single range or successively in two , three or more of these ranges , the order in which each of the ranges a , b and c . is traversed possibly being different . however , according to the invention , it is essential that throughout the process one remains within the supercritical range of the complex mixture or system or reaction fluid or medium . in other words , according to the invention , one is constantly in a monophase range , which is exclusively a supercritical range , unlike in the prior art as is e . g . defined by u . s . pat . no . 5 , 118 , 447 , where one is certainly in a monophase range , but not excluding the liquid state . thus , unlike in the present invention , particularly in this preferred embodiment , ep - a - 157 339 involves a hydrogenation by molecular hydrogen and is specifically limited to purification plant sludge , which is restrictive with respect to the aforementioned aims . the use of molecular hydrogen and the absence of an appropriate choice of pressure and temperature conditions in the supercritical range for favouring the reaction necessitate in said document the use of catalysts for the hydrogenation stage . the uncontrolled introduction of molecular hydrogen can displace the monophase equilibrium of the supercritical medium into two phases , i . e . liquid and gas . however , the present process controls the pressure and temperature conditions in a range , or in accordance with a cycle , in the exclusively supercritical range of the reaction medium or fluid , which favours the targeted chemical reactions . everything takes place in order to use all the hydrogen in atomic form available in the reaction fluid . if necessary , a supply takes place by means of hydrogen additives for which the binding energy between the hydrogen and the atom to which it is bonded is lower than the binding energy between the hydrogen atoms in molecular hydrogen . this addition can be controlled by h . c . e . s . under these conditions , there is no need to use catalysts . in the same way , the aforementioned u . s . pat . no . 5 , 118 , 147 describes a process where the aim is to be in a very restricted pressure and temperature range close to the limits of the supercritical range and it is even possible to leave the effluent to be treated in the liquid state , i . e . in a subcritical range . however , the process according to the invention imposes remaining in the supercritical range of the reaction fluid and permits a wide movement within this range . the nature of the chemical reactions which can take place within the fluid , i . e . the complex mixture or system in the supercritical state will consequently depend : on the one hand on the parameters p and t , which condition the aptitude for the initial complex chemical structure or its components to solubilize and the energy necessary for inducing the reaction or reactions , on the other hand characteristic parameters of the chemical conditions of the medium , namely essentially the h . e . s . c . value able to control the reduction stage , the ph - value , etc . the control of these various parameters , on the one hand parameters p and t and on the other the chemical parameters , makes it possible to orient at random the chemical reactions occurring as a function of the valorizable products which it is wished to obtain . this flexibility and control of the process make it possible to master the formation of the products obtained is not disclosed or suggested by the prior art documents and constitutes one of the surprising advantages and effects obtained by the process of the invention in this preferred embodiment . for example , if the process takes place solely in the above - defined range a , provided that the starting effluent or medium and the chemical complex structures therein allow it , compounds such as longchain hydrocarbons are preferably obtained . when only placed in range b or a reaction cycle starting in range a takes place , then continuing in range b , products such as short - chain hydrocarbons will be obtained . it is also possible to perform a cycle of reactions starting by the maximum solubilizing of the reagents in range a ( thus creating long chains ), followed by a displacement towards range b in order to progressively favour , on passing through range c , chain breaks induced by the temperature . according to this preferred embodiment of the invention and through control via the various ranges , there is a residence time in the supercritical range of the reaction medium much shorter than in the prior art and generally equal to or below 10 minutes ( e . g . between 1 and 5 minutes ) and can even be one or a few seconds or less ( 1 / 10 or 1 / 100 second ). therefore , in the process according to the invention there are fewer or virtually no more or less uncontrollable intermediate reactions leading to end products which are not desired . according to the invention , the chemistry of the process is perfectly controlled by the parameters indicated hereinbefore and more particularly by the temperature and pressure making it possible to adjust and optimize the reaction rate . thus , according to the invention there is an increase in the kinetics of the reaction by acting solely on the temperature and pressure without it being necessary to add a catalyst , which is obligatory in the prior art . on also acting on the h . e . c . s ., e . g . by increasing it by adding a hydride such as nabh 4 , it is possible to effect a supplementary orientation of the chemical reactions and direct them towards the production of specific products . thus , in the cases referred to hereinbefore , it is possible to obtain saturated as opposed to unsaturated long or short - chain products . other features and advantages of the invention can be gathered from the following non - limitative embodiments . fig1 is a diagram illustrating in diagrammatic manner a performance of a chemical transformation process according to the invention . fig2 is a graph representing on the ordinate the gas quantity ( exprssed in arbitrary units ) produced during a chemical transformation according to the invention , as a function of the time starting from the placing under supercritical conditions of the reaction medium . fig1 shows both the main stages of the process and their chronological order . a double arrow 1 designates the constitution of a reaction medium appropriate for the optimization of the reduction or transformation of at least one complex chemical structure . as designated by 2 , this is followed by the mixing and conditioning of the reaction medium corresponding to the supercritical state of the solvent used . the double arrow 3 designates the chemical transformation in supercritical conditions with at least one reduction reaction and the double arrow 4 designates the recovery , analysis and separation of the products of the transformation . a reactor 10 is respectively supplied by lines 12 , 14 , 16 and 18 with one or more complex chemical structures 20 , a solvent 22 and optionally one or more additives 24 . the chemical structure or structures to be transformed can be dissolved or suspended in the solvent in reactor 10 , which corresponds to lines 12 and 14 . it is also possible for the chemical structures to already be suspended or dissolved in a liquid phase constituting the solvent , which corresponds to line 12 and optionally 16 when the term solvent is broadened to complex chemical structure . for example , when it is wished to treat deinking sludge , the latter incorporates cellulose and inks in suspension in water . thus , the cellulose and inks are the complex chemical structures to be transformed and water is the solvent , whose quantity can be controlled . the chemical structure - solvent mixture is in this case formed prior to its introduction into the reactor ( line 14 ). on leaving the reactor 10 , references 28 and 30 designate the recovery and analysis of the transformation products . the recovered products are then separated into valorizable products 32 ( solid , liquid or gaseous ), i . e . which can be recycled and stored , and also non - valorizable products 34 . finally , the double arrow 5 indicates the control range of the process . in order to orient the transformation towards the targeted end products and for optimizing the desired reactions , it is possible to adjust the composition of the initial mixture . the control of the composition 36 is performed as a function of the analysis 38 of the products from the transformation . arrows 40 , 42 , 43 designate an initial adjustment of the composition of the reaction fluid , i . e . the chemical structure - solvent - reducing additive ( optionally ) mixture . in the case of a hydrogenation , the adjustment of the reaction fluid composition takes place with a view to having an adequate h . e . c . s . a control consists of checking the ph and / or h . e . c . s . of the reaction fluid . this control carries the references 46 and 48 . it should be noted that the adjustment of the ph and / or the h . e . c . s . in 46 and 48 can essentially take place by acting on the additive supply of the reactor 10 , but can also relate to the supply of chemical structures or solvent . in particular , one or more additives respectively controlling the reducing character , ph or h . e . c . s . can be dosed or metered . for example , during the transformation of a complex structure of formula c x h y o z m i and if the sought main end product from the reduction is ch 4 the h . e . c . s . can be defined as the hydrogen equivalent chemical supply for transforming all the carbon into ch 4 under the conditions of the experiment and taking account of the hydrogen equivalents already present in the initial complex structure . this h . e . c . s . can e . g . be defined in milligrams of reducing additive per gram of starting material . if it is imagined that the complex structure c x h y o z m i of mass 12x + y + 16z + z i ( z = mass of element m ) is diluted in 10 liters of solvent ( dissolving or suspending ), the h . e . c . s . can also be defined relative to the volume , i . e . per liter of solvent . thus , in order to transform 12x grams of carbon , it is necessary to have 4x grams of hydrogen , but y hydrogen equivalents already exist within the complex structure , so that the necessary h . e . c . s . is ( 4x - y ) grams or ( 4x - y ). 10 3 mg , i . e . ( 4x - y ) 10 2 mg / liter . the reducing additive quantity to be supplied will depend on its aptitude , e . g . to release hydrogens ( or hydrogen equivalents ) per gram . it is then introduced through the control . in the case where the reducing agent contains no hydrogen , it is necessary to take into account its aptitutde to trap oxygen in such a way as to maintain the ratio . ## equ1 ## moreover , one of the complex structures , or one of the products resulting from the decomposition of one of them can serve as a catalyst for obtaining targeted end products . the influence of different parameters governing the transformation can be gathered from the following examples . the following table i refers to a first experimental performance example of the invention , in which approximately 30 to 125 ml of reaction fluid with a ph of 7 containing in suspension 3 to 5 wt . % of sludge obtained from a deinking cell used for treating magazines ( coloured inks ) are treated under various conditions of pressure ( 30 & lt ; p & lt ; 90 mpa ) and temperature ( 500 & lt ; t & lt ; 600 ° c .) within a tight 150 cm 3 reaction enclosure . the reaction fluid quantity introduced into the enclosure then makes it possible to control , for a given temperature , the final pressure in accordance with its thermal expansion value . table i gives the evolution of the solubilization conditions of sludge as a function of the treatment parameters ( pressure p and temperature t ). the duration of the treatment ( duration of the period where p and t have constant values ) is 5 minutes . it should be noted that the solubility increases when the pressure decreases . the gas quantity produced is too low to be collected and analyzed no matter what the ph value ( acid , neutral or basic ). in a second experimental example , use is made of 30 ml of a reaction fluid with a ph of 7 containing in suspension approximately 3 to 5 wt . % of deinking sludge identical to that treated in example 1 . addition takes place of 5 ml of ethanol which , in the supercritical range , can induce a reducing character . after treatment under the optimum conditions resulting from example 1 ( 600 ° c ., 40 mpa , ph 7 , 5 min ), no longer is any solid residue observed . however , a certain number of gases are revealed , which essentially comprise methane ( ch 4 ). in a third experimental example , 55 ml of a reaction fluid containing in suspension very black sludge obtained from deinking cells for old newspapers , i . e . with a traditional ink highly charged in carbon materials ) are placed in an approximately 150 ml reaction enclosure . the pressure and temperature parameters are adjusted as a function of the relationship between the liquid phase volume introduced and that of the reaction enclosure . more particularly when the temperature is close to 600 ° c ., the pressure is approximately 60 mpa . the duration of the treatment is modified from 3 to 30 and then 60 minutes . from the initial ph value of 7 , the ph of the solution passes to 8 after transformation . a largely similar gas volume is collected after reaction in the three cases ( 3 , 30 and 60 min , at 600 ° c ., 600 bar , i . e . 60 mpa ). gas chromatographic analysis shows that the gas formed in mainly methane ( ch 4 ). thus , as a function of the nature of the ink used for printing , without adding a reducing additive , it is possible to obtain a gas energy source . the treatment can be optimized by adjusting the pressure and temperature conditions , but the duration of the treatment does not have a determinative effect . in a very similar manner , a fourth experimental example shows the influence on the results of the ph of the reaction medium prior to treatment . in this connection , the following table iii summarizes the results of a test where , as in the third example , 55 ml of a reaction fluid containing in suspended form very black sludge obtained from deinking cells for old newspapers are placed in a reaction enclosure with a volume close to 150 ml . the corresponding dry matter quantity with respect to the liquid phase is approximately 3 to 5 %. the temperature is kept constant ( 600 ° c . ), as is the duration of the treatment , which is 3 minutes . several experiments are performed at variable pressure ( from 60 to 100 mpa ) and for various ph values ( 4 , 7 , 13 ) without adding a reducing additive . a study of the following tables iii and iv shows that low ph values do not facilitate the reduction of the effluent into ch 4 . however , a pressure increase for the same ph value increases ch 4 formation . consequently it can be advantageous to adjust the ph of the reaction medium to a substantially neutral value ( ph ≈ 7 ) prior to the treatment , e . g . by adding thereto either a basic additive such as soda , or an acid , such as e . g . hydrochloric acid . a fifth performance example for the invention relates to the treatment of an effluent such as a hydrocarbon . in this example , 30 to 125 ml of a liquid phase containing approximately 3 wt . % of drained car change oil suspended in water are introduced into an approximately 150 ml reaction enclosure . the temperature is maintained at approximately 600 ° c ., the pressure being modified as a function of the reaction fluid quantity introduced into the enclosure . table v defines the experimental conditions used , as well as the main results obtained . study of table v shows that the increase in the pressure tends to favour the decomposition of the oil , as well as gas formation . this is made particularly apparent by a comparison of experiments b 2 and b 6 . the addition of an additive ( lithium hydridoborate ) giving the reaction fluid a reducing character also makes it possible to reduce the pressure at which the treatment is performed , as shown by experiment b 7 . in experiment b 7 , a reducing additive such as libh 4 has been added in proportions of approximately 0 . 5 g for 50 ml of reaction fluid . the additive addition also leads to a virtually complete decomposition of the oil and to a greater gas production . fig2 is a graph obtained by chromatographic analysis and illustrates the influence of the reducing additive on the evolution of gas . curves b 6 and b 7 respectively correspond to the evolution of gases during experiments b 6 and b 7 . it would appear that the nature of the gases is substantially the same , mainly for the first peak due to ch 4 , but the quantity is greatly increased by adding a reducing agent . the optimization of the latter also makes it possible to control the nature and purity of the gas phase obtained as a function of the degree of reduction . it is thus possible to e . g . control the production of saturated or unsaturated hydrocarbons during the treatment . this example relates to metal hydroxide sludge and demonstrates that it is possible in this case to evaluate the function of various parameters ( pressure , temperature , duration ) on their transformation . the experimental results of this example appear in table vi , which shows that the range 600 ° c ., 600 bar ( 60 mpa ) lead to a significant sludge decomposition . the residual solid weight is low . the treatment time does not have a determinative function . it should also be noted that the aqueous phase resulting from the treatment is colourless . an analysis of the main constituents contained in this aqueous phase shows that it completely satisfies the standards controlling discharge into the environment . this example relates to grape pressing residues after fermentation and shows that it is possible to apply the process to such combined complex chemical structures . use is made of 19 g of this mixture in the presence of 50 cm 3 of water , followed by raising to a temperature of 600 ° c . and a pressure of 800 bar . after 5 minutes under these experimental conditions , the mixture is restored to normal conditions ( ambient pressure and temperature ). there is a formation of a gas phase containing various hydrocarbons , a liquid phase containing various chemical compounds , particularly terpene derivatives , and a solid phase constituted by pulverulent carbon and weighing approximately 1 g . to the mixture of complex chemical structures identical to that treated in example 7 is added 0 . 1 g of sodium hydridoborate for 19 g of starting matter and 50 cm 3 of water , which is treated for 5 minutes at 600 ° c . and 900 bar . after returning to normal conditions , there is an increase in the volume of the gas phase constituted by light hydrocarbons demonstrating the function of the hydrogen equivalent chemical supply . a liquid phase containing carbon in suspension is also extracted from the reactor . the carbon weight is approximately 1 g . 50 cm 3 of ethanol are introduced into a nickel - cobalt based alloy 150 cm 3 reactor . the reactor is raised to a temperature of 600 ° c ., with a pressure of approximately 800 bar . the duration of the treatment under these conditions is maintained at 1 minute , the reactor then being brought to normal conditions . after opening the reactor , the formation of light hydrocarbons resulting from the decomposition of the alcohol in part of the supercritical range is observed . 125 cm 3 of ethanol are introduced into the same reactor as in example 9 . the reactor is heated to 275 ° c ., the pressure being close to 550 bar . this treatment is maintained for approximately 2 minutes . after returning to normal conditions and opening the reactor , there is no gas phase and the liquid phase present is constituted by ethanol . this example relates to a combination of complex chemical structures of the casein type . use is made of 5 g of casein in the presence of 50 cm 3 of water . the mixture is then raised to 600 ° c . and the pressure reached is approximately 850 bar . after 10 minutes under these conditions , there is a return to normal conditions . on opening the reactor , there is a formation of a gas phase constituted by light hydrocarbons , a liquid phase containing various short - chain chemical compounds and very finely divided carbon in suspension . the final carbon weight is approximately 0 . 15 g . this example relates to a combination of complex chemical structures derived from milk and known as lactoserum . use is made of 50 cm 3 of lactoserum and 0 . 1 g of nahb 4 ( sodium hydridoborate ). it is raised to a temperature of 600 ° c ., the pressure reached being approximately 750 bar . after such a treatment lasting 15 minutes , there is a return to normal conditions . after opening the reactor , an inflammable gas phase constituted by light hydrocarbons is formed , as well as a liquid phase with a few carbon particles in suspension . the following examples 13 to 15 aim at testing with and without h . e . c . s ., the decomposition of starting products identical to those of ep - a - 157 339 in the aforementioned ranges a , b and c . in examples 13 to 15 , the reaction fluid is constituted by water at a ph of 7 with 1 wt . % biological sludge in suspension . this example is solely in range a . 13a -- one volume of 32 ml of reaction fluid is treated at a temperature of 400 ° c . and a pressure of 2000 bars ( 200 mpa ) for 10 minutes . after return to normal p and t conditions , it is found that the sludge has largely been decomposed , only leaving a few solid particles in suspension . no gas phase is produced . after separation and analysis , it is found that the liquid phase mainly contains hydrocarbons between c5 and c8 . 13b -- for a same volume of 32 ml , a treatment identical to that described in 13a is performed , but to the reaction fluid is added 0 . 6 g of sodium hydridoborate in order to increase the h . e . c . s . of the medium . for a temperature of 400 ° c . and a pressure of 1850 bars ( 185 mpa ), the treatment time is 10 min . on return to normal conditions , there is a better decomposition of the sludge than for example 13a . in particular , the quantity of solid particles has decreased compared with 13a . thus , the increase of h . e . c . s ., linked with the addition of nabh 4 , has made it possible to continue the chemical reactions in the supercritical phase . no gas phase was collected . after separation and analysis of the liquid phase , it is found to mainly contain hydrocarbons between c5 and c8 . 14a -- the treatment of 54 ml of the predetermined reaction fluid is performed under the following conditions : passage into range a ( p = 200 bars ( 200 mpa ) t = 400 ° c . for 10 min ), then the pressure is lowered and the temperature increased in order to obtain 500 bars ( 50 mpa ) and 600 ° c . ( range b ), the latter conditions being maintained for 10 min . on returning to normal conditions , there is a decomposition of the sludge , which is more complete than in examples 13a and 13b , which is particularly indicated by a clarification of the liquid phase and the presence of far fewer solid particles . a gas phase is also formed . the separation and analysis of these phases revealed the presence of hydrocarbons from c5 to c8 in solution and methane , ethylene , acetylene , ethane , propane and isobutane in the gas phase . the methane is in the majority ( approximately 56 %), the other constituents being ethane ( approximately 17 %), propane ( approximately 12 . 5 %) and unsaturated hydrocarbons of the ethylene or acetylene type in trace form ( approximately 0 . 8 %). 14b -- the addition of 0 . 6 g of nabh 4 to the reaction fluid leads , after treatment under the same conditions as in 14a to an even more complete decomposition of the sludge , which corresponds to a maximum decomposition obtained for the series of tests 13a , 13b , 14a , 14b ( clarification of the liquid phase and disappearance of the solid particles ). a larger gas volume is recovered than in example 14a . in example 14 , as in example 13 , the h . e . c . s . increase ( linked with the addition of nabh 4 ) made it possible to continue the chemical reactions . analyses of the various phases demonstrated the presence of c5 to c8 hydrocarbons in the liquid and methane , ethylene , acetylene , ethane , propane , butane and isobutane in the gas phase . methane is in the majority and its presence increases substantially ( 71 %) compared with 14a ( 56 %). there is also an increase in the ethane percentage ( approximately 20 %). it is pointed out that the larger gas quantity collected can be attributed to a desorption and a decomposition of hydrocarbons of the liquid phase ( c5 to c8 ) into lighter saturated molecules , said phenomenon being induced by the h . e . c . s . increase . after passing into range a , a volume of 32 ml of reaction medium with the addition of 0 . 6 g of nabh 4 is treated at a pressure of 1100 bars ( 110 mpa ) and a temperature of 600 ° c . for 10 minutes . after returning to normal conditions , there is a decomposition of the biological sludge relatively less complete than that observed in the preceding examples ( 13a , 13b , 14a , 14b ). no gas phase was collected . analysis of the liquid phase shows that it contains in solution c5 to c8 hydrocarbons . table i__________________________________________________________________________ treatment conditions residue time weight liquid ph afterref . ph t (° c .) p ( mpa ) ( min ) ( g / l ) colour treatment gas__________________________________________________________________________a control7 -- -- -- -- light grey -- -- a filtered7 -- -- -- 4 . 121 chestnut -- -- a1 7 500 95 5 1 . 752 light yellow 7 - 8 tracesa2 7 500 40 5 0 . 613 grey - chestnut 7 - 8 tracesa4 7 500 72 5 1 . 593 yellow - chestnut 7 - 8 tracesa5 7 500 30 5 0 . 281 yellow - chestnut 7 - 8 tracesa8 7 600 60 5 traces very light 7 - 8 tracesa9 7 600 40 5 traces very light 7 - 8 tracesa12 7 600 90 5 traces very light - 8 tracesa14 5 600 40 5 zero very light 9 - 10 tracesa15 10 600 35 5 traces yellow 9 - 10 traces__________________________________________________________________________ table ii__________________________________________________________________________treatmentconditions residue time weight liquidref . t (° c .) p ( mpa ) ( min ) ( g / l ) colour ph gas__________________________________________________________________________b -- -- -- 16 . 2 colourless 7 -- b - 4 - 3 - 3400 30 3 10 . 6 chestnut , 7 traces precipitationb - 4 - 3 - 30400 30 30 10 . 5 chestnut , 7 traces precipitationb - 6 - 6 - 3600 60 3 7 . 7 colourless 8 ch . sub . 4 pre - dominant and other alkanesb - 6 - 6 - 30600 60 30 7 . 4 colourless 8 ch . sub . 4 pre - dominant and other alkanesb - 6 - 6 - 60600 60 60 7 . 2 colourless 8 ch . sub . 4 pre - dominant and other alkanes__________________________________________________________________________ table iii__________________________________________________________________________experimentalconditions initial time final gas gasref . ph t (° c .) p ( mpa ) ( min ) liquid appearance ph quantity analysis__________________________________________________________________________br 7 600 60 3 light + grey deposit 7 - 8 ++ ch . sub . 4br . sub . 1 4 600 60 3 dark + black deposit 6 - 7 0 - br . sub . 2 4 600 100 3 dark + black deposit 6 - 7 + ch . sub . 4br . sub . 10 13 600 50 3 light grey + grey deposit 8 + ch . sub . 4__________________________________________________________________________ the symbols -, +, ++, +++ respectiveiy designate an inadequate presence for analysis of a given product , a limited presence , an average presence and a strong presence of the product . table iv______________________________________ph timeinitialt (° c .) p ( mpa ) ( min ) solution gas______________________________________3 - 4 600 60 3 everything solubilized none darker coloured solution3 - 4 600 100 3 than with 600 ° c ., 600 large bar , ph = 7 quantity ( ch . sub . 4 , . . . ) 47 600 100 3 dark solution with the very large presence of a whitish gas quantity deposit ( ch . sub . 4 , . . . ______________________________________ ) table v__________________________________________________________________________ treatment conditions pre - time sence ph afterref . ph t (° c .) p ( mpa ) ( min ) of oil treatment gas__________________________________________________________________________b1 7 600 60 5 - 7 - 8 little (+) b2 7 600 45 5 +++ 7 - 8 too little (-) b6 7 600 110 - 70 5 + 7 - 8 (++) b7 7 600 50 5 + 9 - 10 (+++)(+ libh . sub . 4 ) __________________________________________________________________________ the symbols -, +, ++, +++ respectively designate an inadequate presence for analysis of a given product , a limited presence , an average presence and a strong presence of the product . table vi__________________________________________________________________________treatmentconditions residue time weight liquidref . t (° c .) p ( mpa ) ( min ) ( g / l ) colour ph gas__________________________________________________________________________a untreated -- -- -- 2 . 27 pale yellow 8 -- a - 4 - 4 - 3 400 40 3 2 . 03 colourless 8 tracesa - 4 - 3 - 30 400 30 30 2 . 01 colourless + 8 tracesa - 6 - 6 - 3 600 60 3 1 . 66 colourless ++ 9 predominance of nitrogen and oxygena - 6 - 6 - 30 600 60 30 1 . 62 colourless +++ 9 predominance of nitrogen and oxygen__________________________________________________________________________ | 8 |
fig1 shows a bottom , plan view of an electrode according to the present invention . the electrode is provided with an insulative electrode pad 10 , corresponding to the electrode pad illustrated in the above - cited u . s . pat . no . 4 , 817 , 634 , issued to holleman et al . incorporated herein by reference in its entirety . the pad 10 is a generally planar structure fabricated of silicone rubber , polyurethane or other flexible insulative biocompatible plastic . it is provided with a plurality of concentric , oval shaped grooves into which the braided carbon fiber electrodes are mounted . the periphery of the electrode pad 10 is provided with a dacron reinforcement mesh 12 , to assist in suturing the pad to the myocardium or to subcutaneous tissue , and to assist in preventing tearing of the pad . the dacron mesh , as illustrated , is limited to the external periphery of the electrode pad and does not extend into the area between the carbon fiber electrodes . the lead of fig1 is provided with four separate carbon fiber electrodes 14 , 16 , 18 and 20 . each of these electrodes takes the form of tubular braid of metallized carbon fibers , each laid in one of the oval shaped , concentric grooves in electrode pad 10 . each of the carbon fiber electrodes 14 , 16 , 18 and 20 is provided with an inner tubular core of silicone rubber , around which the tubular braid of carbon fibers is mounted . the carbon fibers are retained within the grooves in base pad 10 by means of medical adhesive , which bonds the tubular core within the carbon fiber braids to the pad 10 . each of the carbon fiber electrodes 14 , 16 , 18 and 20 exits the upper surface of the electrode pad at which point they are provided with tubular , insulative sheaths 22 , 24 , 26 and 28 , which cover the carbon fiber braids until they reach the proximal end of the lead . in the embodiment illustrated in fig1 each of the electrodes 14 , 16 , 18 and 20 may be provided with its own electrical connector . alternatively , the carbon fiber electrodes may all be interconnected at the proximal end of the lead to a single connector or , may be interconnected by means of a manifold , weaving , conductive adhesive or other structure at the electrode pad . in particular , it is anticipated that by employing the weaving methods employed to fabricate bifurcated woven vascular grafts , a single large bore braid may be reduced to multiple , smaller bore carbon braids for producing a carbon fiber electrode . such an alternative structure is illustrated in fig5 below . fig2 is a diagram of an alternate embodiment of a lead employing the present invention . it too is provided with an electrode pad 110 which corresponds to pad 10 in fig1 . pad 110 is similarly provided with a dacron enforcement mesh 112 around its external periphery . in the electrode fig2 only one carbon fiber electrode 114 is provided , mounted to the grooves within pad 110 to provide a spiral shaped electrode . on exiting the electrode pad , electrode 114 is provided with a insulative sheath 112 which extends to the proximal end of the lead . fig3 illustrates yet another alternative embodiment of a lead employing the present invention . in this embodiment , the carbon fiber electrode 214 is mounted to an insulative core which has performed or molded to follow a sigmoidal path . the configuration illustrated corresponds to that illustrated in the allowed u . s . patent application ser . no . 07 / 604 , 686 , of smits et al ., filed oct . 26 , 1990 , and incorporated herein by reference in its entirety . it is believed that this embodiment of the invention retains all of the advantages discussed in the smits application , associated with the sigmoidal configuration . in this case , only a single braided carbon fiber electrode 214 is provided , and it extends proximally within insulative sheath 222 , until the proximal end of the lead . assembly of the lead is accomplished by sliding the tubular carbon braid over the previously molded sigmoidal silicone rubber core , and subsequently molding the bridging member number 224 , suture pad 226 and the transition member 228 over the carbon electrode . the suture pad 226 , the bridging member 224 and the transition member 228 are all preferably fabricated of silicone rubber or other biocompatible , flexible insulative plastic and bond to the sinusoidal core through the interstices in the carbon braid . fig4 shows the basic structure of the carbon fiber electrode . a tubular braid 314 of metallized carbon fibers is shown extending from the distal end of an insulative sheath 324 . that portion of the tubular carbon braid which extends within the insulative sheath 324 forms the lead conductor . also illustrated is core 326 , located within the carbon fiber 314 .. this core may be tubular or solid and , in the case of electrodes as in fig3 may be provided with an internal wire or other reinforcement . the core may simply follow the path of the carbon fibers , as mounted to a base pad , as illustrated in fig1 and 2 or may itself impart a curved configuration to the carbon fiber electrode as illustrated in fig3 . the core may extend the length of the braid 314 or may be limited to that portion of the braid exposed to the exterior of sheath 322 . fig5 is an illustration of yet another embodiment of an electrode according to the present invention , in which the weaving techniques employed to produce bifurcated tubular structures in the context vascular grafts have been applied to the context of implantable defibrillation leads . as illustrated , a single , large diameter tubular carbon fiber braid 430 is split into two smaller segments and then split again to form four parallel tubular segments 414 , 416 , 418 and 420 . mounted within segments 414 , 416 , 418 and 420 are silicone rubber or other plastic core members . the tubular carbon fiber braid may be backfilled with silicone rubber in other areas , in order to prevent tissue ingrowth into the braid in the areas of the bifurcations . the large diameter braid 430 is covered with an insulative sheath 422 , extending to the proximal end of the lead , at which point an electrical connector is mounted to braid 430 . as illustrated , the carbon fiber electrode structure is mounted to a flexible , insulative backing member 410 , which may be provided with grooves corresponding to the desired configuration of the carbon fiber electrode . as in the embodiments illustrated in fig1 and 2 , the carbon fiber electrode may be retained within the grooves by means of silicone rubber medical adhesive . alternatively , the backing member 410 may be dispensed with , and the electrode used without a backing member , either subcutaneously or epicardially in a manner analogous to the electrode illustrated in fig3 . the carbon fibers employed to make the tubular braided structures illustrated in the present application are carbon fibers provided with a nickel coating of approximately 0 . 05 - 1 . 5 microns in thickness . this material is commercially available from chemetronics research , located in white plains , n . y ., which can weave the fibers into various textile configurations on request . the individual fibers are aggregated into bundles and the bundles thereafter are woven into a hollow , tubular braid having a inner diameter of approximately 1 - 5 mm . preferably , the fibers are provided with a coating of platinum , iridium , gold or other biocompatible low resistivity metal . the coating may be applied to individual fibers or to the fiber braid using sputtering techniques . alternatively , the nickel plated fibers may be provided with a gold overcoating using standard electrodeless deposition processes . the above embodiments illustrate a variety of leads which may be fabricated in accordance with the present invention . however , they are intended to be exemplary , rather than limiting with regards to the claims which follow | 0 |
embodiments of the present invention relate generally to a system , method , and / or apparatus for managing battery charge cycles in order to maximize the useful life of one or more batteries . the useful life of many types of batteries may be extended by minimizing the total charge on the battery over the life of the battery . the total charge may be minimized by delaying the initiation of the charge cycle so that it is completed immediately before the battery is used . the total charge in the battery over its life may also be reduced by charging the battery to less than its maximum capacity during a charge cycle . embodiments of the present invention may use both of these mechanisms and others to minimize the charge on the battery over the battery &# 39 ; s life . in one embodiment , the battery &# 39 ; s charge cycles are managed by a smart battery charger . the smart battery charger identifies a particular battery and associates the particular battery with a usage history . the usage history may be stored on the battery charger or in memory that is part of the battery . in another embodiment , the charge cycles are managed by a device utilizing the battery , such as a laptop computer , a cell phone , a pda , a power tool , a hand - held scanner , or other device . embodiments of the present invention may utilize one or more computer - storage media with computer - executable instructions or computer - readable data embodied thereon . computer - storage media include both volatile and nonvolatile media , removable and nonremovable media , and contemplate media readable by a database , a switch , and various other network devices . the computer - storage media is nontransitory . by way of example , and not limitation , computer - storage media comprise media implemented in any method or technology for storing information . examples of stored information include computer - useable instructions , data structures , program modules , and other data presentations . media examples include , but are not limited to , information - delivery media , ram , rom , eeprom , flash memory or other memory technology , cd - rom , digital versatile discs (“ dvd ”), holographic media or other optical disc storage , magnetic cassettes , magnetic tape , magnetic disk storage , and other magnetic storage devices . these technologies can store data momentarily , temporarily , or permanently . turning now to fig1 , a smart battery charger 100 suitable for managing charge cycles on a plurality of batteries in order to prolong the operation life of the batteries is shown , in accordance with an embodiment of the present invention . the smart battery charger 100 includes a body 105 that houses the components of the battery charger 100 . the housing may be plastic , metal , aluminum , or other suitable material . the battery charger 100 includes charging port 110 and charging port 130 . the charging port 110 is shown with battery 112 , battery 114 , battery 116 , battery 118 , battery 120 , and battery 122 . the charging port 130 is shown with battery 132 , battery 134 , battery 136 , battery 138 , battery 140 , and battery 141 . as can be seen , each charging port holds six batteries . embodiments of the present invention are not limited to charging ports that hold six batteries . for example , an exemplary battery charger may include just a single charging port . the charging port 110 and the charging port 130 are sized and shaped to receive one or more batteries . though not shown in fig1 , each battery port includes a charging plug that couples with a charging port on the battery . the charging plug and the charging port couple to enable an electrical current to pass between the battery charger 100 and an individual battery placed in the charger . in one embodiment , charging port 110 and charging port 130 are sized to fit the battery plus the box in which a battery is packaged . each of the batteries in fig1 is shown outside of a box or casing in which a battery may typically be shipped . in the embodiment where the battery is charged while in a shipping package , the shipping package may have openings that allow access to the charging ports on the battery . the shipping package may also have an opening allowing a communications plug on the battery charger to couple with a communications port on the battery . the communications port allows a computer - storage media in the battery to be accessed by the battery charger when the battery and charger are coupled together . charging a battery in a packaging box may be useful to charge the battery immediately prior to shipment to a use point . thus , in this embodiment , the smart battery charger 100 would be used to charge batteries prior to their first use . the batteries could be left on a shelf within the shipping package uncharged until they are ready to be shipped , at which time they could be placed in the battery charger 100 and charged . the first charge cycle could then be recorded on memory within the battery and then the battery could be shipped to the customer . a battery charger at the point of use could utilize the initial usage and charging information to estimate the future life of the battery more accurately . the battery charger at the point of use may be a different battery charger than the one used prior to shipment . charging the battery for the first time as the battery is shipped and on an as - needed basis may benefit warranty programs offered to battery customers . for example , leaving a charged , or partially charged , battery on a shelf prior to shipment to a customer decreases the useful life of the battery . a vendor with inconsistent shelf time may be forced to offer a shorter warranty to avoid warranty claims . however , by starting the “ life ” of the battery at the time of shipment the predictability of the useful life the battery is increased and a longer warranty may be offered . a warranty could also be based on the total energy delivered by the battery , which is roughly the sum of the amount of energy put into the battery at each charge cycle . offering a warranty based on total energy delivery may not be possible unless the charge - cycle details are recorded . the total energy used may be recorded in the battery as each charge and use cycle is recorded . in addition to charging the battery while in a shipping box or outside of the device in which the battery is used , the battery charger may also couple with the device in which the battery is used . thus , the battery charger could include a cradle for receiving a device and coupling with the battery in the device for the purpose of charging the battery and exchanging information with the battery . in this case , the ports in the battery couple with plugs in the battery charger via the device in which the battery is located . thus , the plugs in the battery and the ports in the battery charger may not be in direct contact with each other . as used throughout the present application , communicatively coupling occurs when a communication is passed from the charger to the battery or from the battery to the charger . multiple conduits and devices may carry the communication between the battery and the charger . the charger and battery do not need to be in direct contact even when a plug on the battery is described as coupling with a port on the battery charger or vice versa . similarly , a conductive couple occurs when an electrical current is able to pass between the battery and the charger . multiple conduits and devices may carry the current . the charger and battery do not need to be in direct contact for a conductive coupling to occur even when a plug on the battery is described as coupling with a socket on the battery charger or vice versa . in another embodiment , the battery charger connects to the device and the battery in the device through one or more cables . continuing now with fig1 , the body 105 of the battery charger 100 defines an opening 190 into which battery packaging may be stored . as can be seen , battery packaging 194 may be collapsed and placed into the opening . a door 192 may cover the opening 190 and secure the battery packaging within the body 105 . storing a battery packaging 194 within the battery charger facilitates recycling the battery at the end of the battery &# 39 ; s useful life by making a return package readily accessible to the user of the battery . the battery charger 100 includes a display 180 . the display 180 may display information related to one or more batteries within the battery charger 100 . for example , the display 180 may display the percent charged 182 for a particular battery , an identifier 184 for the particular battery , the current charge cycle 186 for the particular battery , and the remaining estimated life 188 of the particular battery . the remaining life may be determined by calculating how long it will take for the remaining usage cycles to be used if the present usage pattern for the battery continues into the future . the remaining usage cycles may be calculated by subtracting the total cycles on the battery to date from the expected lifetime charge cycles . the information for an individual battery may be accessed by pushing a button adjacent to a battery . for example , the information related to battery 112 may be accessed by pushing the button 142 . similarly , buttons 144 , 146 , 148 , 150 , 152 , 162 , 164 , 166 , 168 , 170 , and 172 may be pushed to access information related to the batteries adjacent to the respective buttons . the display 180 may be an lcd display , touch - screen display , or other suitable display type . other buttons ( not shown ) may allow the user to navigate menu options presented on the display 180 . turning now to fig2 , a line graph illustrating a usage history for a battery over the course of a five - day workweek is shown according to an embodiment of the present invention . the y axis 210 shows the charge percent on the battery . the x axis 220 shows the time and day . the solid line indicates smart charging on an as - needed basis in accordance with an embodiment of the present invention . the dash line indicates traditional charging which begins soon after the battery is placed in the battery charger . under the smart charging regime , on friday , from approximately 2 : 00 a . m . to 5 : 00 am , the battery is charged 230 from 40 to 100 % of capacity . at approximately 6 : 00 am to about 2 : 00 pm on friday , the battery is discharged 232 during use . as can be seen , the discharge cycle will be similar for both the traditional and smart charge cycles . as the battery ages , the discharge cycle may differ significantly for batteries charged under the traditional and smart charge cycles . under the traditional regime , charging 234 begins immediately upon the battery being placed in the battery charger at roughly 2 : 00 pm on friday . in contrast , under the smart charging , the charging 238 does not begin until about 2 : 00 am on monday . this allows the battery to remain at about 40 % charge capacity for an additional two days . the initiation of charging 238 begins with enough time to complete the charge cycle prior to the anticipated next usage at about 6 : 00 am on monday . the anticipated next usage may be determined based on previous usage cycles recorded for the battery . viewing the entire line graph 200 , it can be seen , for example , that the usage cycle typically begins at about 6 : 00 am on weekdays and concludes at 2 : 00 pm after an eight hour shift . embodiments of the present invention are not limited for use with batteries having a particular use / charge cycle . thus , the initiation of charging under a smart regime may begin with enough time to be completed before 6 : 00 am . in fig2 , the smart charge cycles are completed at 5 : 00 am , which is one hour before the battery &# 39 ; s anticipated usage . continuing with fig2 , once again at about 6 : 00 am , the battery begins to discharge 240 until it reaches 40 % capacity around noon on monday . again , under the traditional regime , the battery would initially begin charging 242 to full capacity at about 2 : 00 pm on monday . in contrast , by waiting until just before the battery would actually be used , charging 246 may begin at about 2 : 00 am on tuesday . this cycle essentially repeats each day on the remaining graph . from roughly 6 : 00 am until 2 : 00 pm on tuesday , the battery discharges 248 as it is used . under the traditional regime , the battery is charged 250 at roughly 2 : 00 pm . in contrast , under the smart regime the battery is charged 254 at roughly 2 : 00 am on wednesday . on wednesday , the battery discharges 256 during use . under the traditional regime , the battery is charged 258 at 2 : 00 pm on wednesday . under the smart regime the battery is charged 262 at 2 : 00 am the following day on thursday . the final use cycle occurs on thursday when the battery is discharged 264 . one final charge 266 under the traditional regime is shown . for the one - week period of time shown in fig2 , the battery charged under the traditional regime averages 91 % charged . in contrast , the battery charged under the smart regime averages 53 % charged . this difference may significantly extend the useful life of the battery . turning now to fig3 , an exemplary battery 300 for use in embodiments of the present invention is shown . the battery 300 includes a first charging port 302 and a second charging port 304 . the first and second charging ports 302 and 304 are sized and shaped to receive a charging plug from a battery charger . in one embodiment , the first and second charging ports 302 and 304 are simply exposed conductive contacts for contacting charging plugs on the battery charger . the first charging port 302 and the second charging port 304 are coupled to a wire or conduit that carries an electrical charge from the battery charger to the portion of the battery that holds the charge . in one embodiment , the battery 300 is a lithium ion battery . however , embodiments of the present invention are not limited to use with a particular type of battery . the battery 300 includes an identification 306 . in one embodiment , the identification 306 is a bar code . the bar code may be read by a scanner on the battery charger or other device to identify an individual battery and distinguish batteries from each other . in another embodiment , the identification 306 is an rfid tag that could similarly communicate a unique identification number to an appropriately equipped device or battery charger . identifying a particular battery is important for embodiments of the present invention to associate the batteries with a specific usage history , especially if the usage history is not stored on the battery . in one embodiment , the usage history for the battery 300 is stored on a computer - readable media 310 within the battery . the media 310 may be accessed by communications port 308 . communications port 308 is conductively coupled to the media 310 by a conduit 312 . the communications port 308 may interface with a plug on a battery charger or other device . in one embodiment , the media 310 also includes a unique identifier that is used by a battery charger or other device to identify a specific battery . turning now to fig4 , a method 400 of charging a battery is shown , in accordance with an embodiment of the present invention . as described previously , the method may be used on any battery that benefits from having a lower charge on the battery over the life of the battery . the primary benefit is extending the useful life of the battery . extension of the useful life of the battery may be evidenced by enabling the battery to be charged for additional cycles . a charge cycle consists of discharging the charge on the battery and recharging the battery to either full or less than full capacity . extension of the useful life of the battery may also be evidenced by the battery holding a full charge for additional charge cycles or any other measure by which the battery remains valuable to the user for a longer period of time . at step 410 , a battery is received . in one embodiment , the battery is received by placing the battery into a charging port on a battery charger . in another embodiment , the battery may be received by a device that uses the battery . at step 420 , a usage history for the battery is retrieved . in one embodiment , the usage history is retrieved from computer - readable memory or storage located in the battery . in another embodiment , the usage history for the battery is stored on the battery charger or device utilizing the battery . when the usage history is stored in a location other than in the battery , the individual battery may be identified by a unique identifier , such as a bar code or rfid tag or other mechanism . the usage history includes the charge on the battery over time . thus , the characteristics of a discharge cycle or a charge cycle may be determined from the usage history on the battery . the characteristics of interest include the beginning and end time for the discharge cycle and the energy used during a charge cycle . in one embodiment , the usage history may indicate that the battery has never been charged before . at step 430 , an optimal time to initiate a charge cycle on the battery is determined from the usage history . the optimal time is a time when the battery is likely to be next used minus a period of time required to complete the charge cycle . as illustrated previously in fig2 , if the next use cycle is to begin at about 5 o &# 39 ; clock and the charge cycle takes an hour to complete , then the optimal time to initiate a charge cycle on the battery would be roughly 4 o &# 39 ; clock . in one embodiment , a time buffer may be used to ensure that the charge cycle is completed in time for the next use cycle to begin . the buffer is illustrated by about a two - hour time period in fig2 . embodiments of the present invention are not limited to including a buffer . in one embodiment , the usage history is evaluated by a machine - learning algorithm that determines the optimal time . at step 440 , the optimal charge on the battery is determined from the usage history for the battery . the optimal charge is a minimum charge plus an amount of energy historically used during a single use cycle . for example , if 50 % of the battery &# 39 ; s capacity is typically used during a single - use cycle and the minimum charge is 20 %, then the optimal charge on the battery would be 70 %. charging the battery to the optimal charge reduces the total charge on the battery over the life of the battery . in one embodiment , an additional buffer is added to the minimum charge and the amount of energy historically used during a single cycle to calculate the optimal charge . at step 450 , a charge cycle is initiated at the optimal time , and the battery is charged during the charge cycle to the optimal charge . at step 460 , an updated usage history is generated based on the recent charging of the battery . at step 470 , the updated usage history is uploaded to a computer - readable media on the battery . in this case , the previously retrieved usage history would have been retrieved from the same computer - readable media on the battery . as stated previously , embodiments of the present invention are not limited to storing the battery usage data on the battery . the updated usage history may be stored on the battery charger or use device with the other usage history . at step 480 , a request to display information related to the battery is received . in one embodiment , the request is received by pushing a button adjacent to the battery in a battery charger . in another embodiment , the request is received when a user makes the request through a user interface on the device in which the battery is used . at step 490 , the information associated with the battery is displayed . the information includes the usage history , charge cycles on the battery to date , anticipated charge cycles left over the life of the battery , and anticipated energy delivery remaining in the battery . the anticipated energy delivery remaining in the battery is the rated - energy - delivery capacity of the battery minus the total energy delivered by the battery . the total energy delivered by the battery may be calculated by totaling the energy delivered in each charge cycle . the energy delivered during each charge cycle may be recorded on the battery memory or in memory in the battery charger . the rated - energy - delivery capacity may also be stored on the battery memory by a manufacture , vendor , or the battery charger . in one embodiment , if the usage history indicates that the battery has never been charged , a first charge amount is retrieved from memory in the device using the battery or a battery charger charging a battery for the first time . a usage history is then created and stored where appropriate based on the setup . turning now to fig5 , a method 500 of scheduling charge cycles for a battery in order to minimize an average charge on the battery over the life of the battery is shown , in accordance with an embodiment of the present invention . method 500 may be used to manage one or a plurality of batteries . at step 510 , an indication that a battery is coupled to the battery charger is received . this indication may be generated when a sensor in the battery charger detects the insertion of a battery . in one embodiment , the coupling of a charging port or a communications port in the battery with a charging plug or communications plug in the battery charger may serve as the indication that a battery has been coupled to the battery charger . though described as a plug in a port , the plugs and ports may simply be contacts suitable for communicating a current between the battery and the battery charger . the port does not need to have a socket into which the plug fits . in another embodiment , a plug is on the battery and a port is in the battery charger . further , the communications between the battery memory and the battery charger may be wireless . in addition , the charge to the battery could be delivered inductively without use of either a plug or socket in either the battery or the battery charger . at step 520 , a usage history for the battery is retrieved . as described previously , the usage history may be retrieved from memory in the battery charger or from memory located in the battery . at step 530 , the usage history is used to determine an optimal time to initiate a charge cycle in the battery . the optimal time is a time when the battery is likely to be next used minus a period of time required to complete the charge cycle for the battery . at step 540 , the charge cycle for the battery is initiated at the optimal time . as described previously , the charge cycle may include charging the battery to an optimal charge , which is determined based on the typical battery discharge during a use cycle . in one embodiment , the battery is just one of a plurality of batteries managed by the battery charger . the plurality of batteries managed by the battery charger may be interchangeable batteries . interchangeable batteries may be used interchangeably between similar devices compatible with the batteries . in one embodiment , when multiple batteries are managed by the battery charger , one of the plurality of interchangeable batteries is kept as a hot battery . the hot battery is fully charged and available for use outside of the typical or expected usage . in other words the hot battery is not charged based on an optimal time or charge but is fully charged as soon as it is placed in the battery charger . in another embodiment , at least one battery is kept fully charged , but an individual battery is not designated as a hot battery . in one embodiment , when a plurality of batteries are managed , the charge cycles between the batteries are managed to equalize the life of each battery within the plurality of batteries . the service life of a population of batteries is maximized by equalizing the wear on each battery over time . this may be done by indicating to users of the batteries which batteries should be used first or next . batteries with less overall usage should be recommended for next use . many different arrangements of the various components depicted , as well as components not shown , are possible without departing from the spirit and scope of embodiments of the present invention . embodiments of the present invention have been described with the intent to be illustrative rather than restrictive . certain features and subcombinations are of utility and may be employed without reference to other features and subcombinations and are contemplated to be within the scope of the claims . | 7 |
the invention will now be described with reference to the drawings . as shown in fig2 the continuous positive airway pressure ( cpap ) device 10 is connected to the proximal end of one lumen 2 of a double - lumen endotracheal tube 1 . normally , there is inserted in the end of the lumen a 15 millimeter connector over which a 22 millimeter connector fits . thus , a 22 millimeter diameter opening in the end of the cpap device to be connected to the single lumen of the double - lumen endotracheal tube would be appropriate . however , it is noted that the cpap device need not fit specifically over the 15 millimeter connector and could fit into a suction port of a double - lumen tube or into the bronchial port of the tube ( neither of which is shown ). a tapered cylindrical fitting 14 extends from the side of the cpap device and is attached to an oxygen tube 21 which , in turn , is connected to a source of oxygen 23 for delivering oxygen under pressure to the cpap device at a constant flow rate . a flow meter 22 for indicating the rate of oxygen flow is included in the oxygen tube 21 . as described with respect to fig1 one leg of the y - connector 6 is clamped by a clamp 7 for disconnecting the anesthesia circuit 4 from the lumen 2 which communicates with the non - ventilated upper lung 9 . the cpap device of my invention also includes a ventilating means v for continuously venting at least a portion of the oxygen supplied by the source 23 to the device 10 . according to the invention , the ventilating means can take different forms , as will be discussed in more detail below . an important feature of all the venting means of my invention is that there always exists an opening through which oxygen can escape , thereby avoiding a dangerous buildup of oxygen to a pressure which could cause overdistention of the non - ventilated lung 9 . in the preferred embodiment of the invention , as shown in fig3 the cpap device includes a long hollow inner cylinder 11 which may be formed of a clear plastic , such as polyvinylchloride . further , a shorter outer cylinder 12 is rotatably disposed snugly over the proximate end 13 of the long inner cylinder 11 . likewise , the shorter outer cylinder 12 may also be formed of a clear plastic . the end 13 of the cpap device 10 is designed to fit onto the proximal end of one lumen of a double - lumen endotracheal tube as discussed above . the distal end of the long inner cylinder 11 is closed by a removable cap 15 . normally , the cap 15 seals the distal end of the cpap device 10 . the cap 15 may be removed in order to slide the end of an anesthesia bag 24 ( fig2 ) over the end of the device . the bag would then fill with oxygen under pressure and , if squeezed , would be used to inflate the lung to which the cpap device is attached . as noted above , the cpap device includes a tapered cylindrical fitting 14 which extends from the side of the long inner cylinder 11 . the oxygen tube 21 is then attached to the fitting 14 to couple the device to the source 23 of oxygen . both the inner and outer cylinders of the cpap device have elongated slots 16 and 17 , respectively , which are aligned longitudinally such that , when the inner and outer cylinders are rotated with respect to one another , the slots line up to allow the venting of varying degrees of oxygen under pressure . hence , by rotating the inner and outer cylinders with respect to each other , the vent opening becomes larger or smaller , depending upon the overlap of the slots 16 and 17 . with the vent opening v maximally closed off , the greatest amount of pressure is generated within the system . on the other hand , with the slots 16 and 17 lined up so as to form the largest opening , the least amount of pressure is generated within the system . as shown in fig4 a , the shorter outer cylinder 12 is rotatably disposed on the long inner cylinder 11 so as to be retained by friction in a position to which it is manually rotated . however , as shown in fig4 b and 4c , the long inner cylinder may be formed with a projection 19 formed on its outer circumference . the projection 19 is engageable with one of a plurality of corresponding notches 20 formed on the inner circumference of the short outer cylinder . in this manner , as the shorter outer cylinder 12 is rotated with respect to the long inner cylinder , and the vent opening becomes larger , one of the notches 20 will catch on the projection 19 at a predetermined cpap level ( e . g ., 5 , 7 . 5 , 10 cm h 2 o cpap ) as denoted by the element numeral 18 . the projection is not required since the short outer cylinder is rotatably disposed in a snug manner on the long inner cylinder . also , an annular rib 25 may be included to engage with a corresponding groove 26 to aid in retaining the short outer cylinder in place . fig5 - 7 illustrate additional embodiments in which alternative forms of the venting means v are employed . in a second embodiment , as shown in fig5 the cpap device 110 comprises a single hollow cylindrical member 111 . again , the cylinder is preferably formed of a plastic , such as polyvinylchloride . as with the previous embodiment , the proximal end 113 of the cylindrical member 111 is connected to a single lumen of a double - lumen endotracheal tube . a tapered cylindrical fitting 114 , for connection with an oxygen tube , and a removable cap 115 are likewise included . in this embodiment , the venting means v takes the form of an elongated slot 116 passing through the wall of the cylindrical member 111 and extending in the longitudinal direction thereof . a slidable plastic tab 112 is disposed in the slot 116 . the tab 112 has a gripping means 117 which may be grasped by the user of the device and pushed or pulled in the longitudinal direction so as to form a smaller or larger vent opening 116 . thus , oxygen under constant , non - varying low levels of positive airway pressure may be transmitted to the non - ventilated lung of a patient during thoracic surgery . predetermined cpap levels are indicated by index marks 118 formed on the outer surface of the cylindrical member 111 adjacent to the slot 116 . fig6 illustrates another embodiment of the cpap device . structural elements similar to those illustrated for the previous embodiments are designated by the same reference numerals but preceded by the numeral 2 . the cpap device 210 is identical to the embodiment shown in fig5 with the exception of the venting means v . in this instance , the venting means takes the form of a plurality of holes 216 of specific calibers ( e . g ., 5 , 7 . 5 , 10 cm h 2 o cpap ) and passing through a hollow cylindrical member 211 . the holes 216 are spaced apart and arranged in a straight line so as to extend longitudinally of the hollow cylindrical member 211 . further , a tab or strip of plastic 212 has a plurality of plastic buttons or pins 217 formed thereon to serve as closure means for the corresponding holes 216 . again , there is always at least one hole open to allow continuous venting of oxygen . in operation , as the tab 212 is pulled and additional holes 216 are opened up , less cpap is produced . in a still further embodiment , as shown in fig7 again the cpap device is identical to the embodiments of fig5 and 6 with the exception of the venting means v . again , identical structural elements as described in previous embodiments are designated with the same reference numerals but preceded by the numeral 3 . in this embodiment , the hollow cylindrical member 311 is again formed with a series of holes 316 of specific calibers . the holes 316 are spaced apart and extend in a straight line longitudinally of the hollow cylindrical member 311 . further , several pins or buttons 312 serve as closure members to individually close the holes 316 . again , there is always at least one hole 316 open to provide venting of oxygen . therefore , with the closing of each additional hole 316 with an individual button 312 , the cpap level in turn increases and vice versa . from the above , it is clear that the embodiments disclosed in fig3 and 5 produce infinitely varying levels of cpap , going from the highest to the lowest level , while the embodiments of fig6 and 7 produce a limited number of discrete levels of cpap . the cpap device according to my invention includes the following advantages : ( 1 ) it is a self - contained device which consists of a single piece of equipment . ( 2 ) it is small , lightweight , and easier to use than alternative , bulky , cumbersome systems . ( 4 ) it eliminates the need for a pressure gauge which is common in the previous &# 34 ; homemade &# 34 ; systems . ( 5 ) it will be easily available to practitioners since it will come packaged with each double - lumen endotracheal tube . ( 7 ) it is safer to use than the &# 34 ; homemade &# 34 ; systems . the alternative prior art systems employ a &# 34 ; pop - off &# 34 ; valve which can be fully closed , allowing a dangerous buildup of pressure within the cpap system and the lung to which it is attached . in my invention , there is always some degree of venting present and thus dangerous pressure levels cannot occur . ( 8 ) it is easier to use than the previously described systems since it has graduated settings to give a precise amount of cpap without the need to precisely adjust a pop - off valve knob while inspecting a pressure gauge . ( 9 ) an attachment for an anesethesia bag allows the option of transiently delivering a higher pressure than the system would ordinarily deliver . this results in opening up previously collapsed alveoli . the cpap then keeps the alveoli from collapsing . ( 11 ) its size and shape make it uniquely compatible for attachment to a single lumen of a double - lumen endotracheal tube . it is contemplated that numerous modifications may be made to the cpap device of my invention without departing from the spirit and scope of the invention as defined in the following claims . | 0 |
fig1 depicts a heterostructure laser 100 . the active region 102 has blocking regions 104 adjacent thereto and extending laterally from opposite sides of active region 102 . blocking regions 104 may consist of a plurality of layers . the refractive index of the active region material differs from that of the blocking region material providing lateral optical confinement . the difference in refractive indices also provides the current blocking capability useful in limiting the laser drive current from leaking through the non - active region . in conventional heterostructure lasers the effective refractive index difference between the blocking region and the fundamental transverse mode of the active region is about 0 . 03 . this provides a single transverse mode for a 1480 nm pump laser with an active region stripe width of 2 . 4 μm . when the stripe width is increased an unwanted second transverse mode may arise . for example , when the stripe width is increased to 10 μm , the transverse electrical ( te ) mode with lowest loss is the te 06 . it is desirable to provide a laser structure having the fundamental mode , te 00 , with lowest loss for a stripe width of approximatelyl 10 μm . a 10 μm stripe width may be easily coupled to optical fibers having that width which are readily available . to achieve a single transverse mode with a stripe width of 10 μm , the blocking regions and active region may be comprised of like - materials . for example , ingaasp may be used both as blocking and active region materials . as used herein “ like - materials ” means materials comprised of the same elements but differing in the ratio of elements . reference to a particular material includes that material in a pure form or having impurities or dopants . the use of like - materials reduces the refractive index difference between the active and blocking regions such that the te 00 mode may spread over a larger width as compared , for example , to a heterojunction comprising conventional inp blocking regions and an ingaasp active region . advantageously , use of like - materials for the blocking regions also avoids significant lattice mismatch at the heterojunction of the active and blocking regions . lattice mismatch between materials making up the heterojunction may result in lattice defects . these defects may reduce radiative recombination efficiency thereby reducing the device life expectancy . thus , use of like - materials for the active and blocking regions may improve device quality and performance . to confirm the ability of the te 00 mode to spread over the larger width when the refractive index difference is decreased , simulations were performed for different block region compositions . fig2 a - c provide te modes with lowest loss for different blocking material refractive indices . the te modes depicted in fig2 a - 2c are produced by blocking materials having refractive indices of 3 . 160 , 3 . 180 , and 3 . 190 , respectively . as shown in fig2 b , the blocking material having a refractive index of 3 . 180 provides a fundamental transverse mode . this represents a refractive index difference between the active and blocking regions of 0 . 023 . in 0 . 95 ga 0 . 05 as 0 . 12 p 0 . 88 is an example of a material having this refractive index . the bandgap energy for the material is 1 . 267 ev with a corresponding wavelength of 0 . 979 μm . the bandgap energy is only 0 . 083 ev smaller than that of inp , and thus , should not degrade the blocking characteristics of the p - n junctions . single - mode rate equations were used to simulate light - current ( li ) characteristics of the larger stripe width obtained with the ingaasp material having a 3 . 180 refractive index . the li curve of a conventional high performance 1480 nm pump laser was modeled . for a waveguide width of 2 . 4 μm the simulated internal power loss is 12 . 5 cm − 1 and the confinement factor is 5 . 87 %. for a series resistance of 2 ohms , a spreading thermal impedance of 20 ° c ./ w , and a temperature dependent loss of 0 . 5 cm − 1 /° c ., the threshold current is 26 ma , the front facet power at 600 ma is 241 mw , and the roll - over current is 1200 ma , for a chip length of 1 mm . for a laser with the larger , 10 μm waveguide width a simulation was performed using an internal loss of 11 . 7 cm − 1 and a confinement factor of 6 . 18 %. because the series resistance and the spreading thermal impedance are inversely proportional to the waveguide width , it was determined that the larger waveguide series resistance was 0 . 48 ohms and the larger waveguide width spreading thermal impedance was 4 . 8 ° c ./ w . the calculated threshold current was 103 ma and the front facet power at 600 ma was 266 mw , and at 1600 ma the front facet power was 729 mw . fig3 shows the li curves 302 and 304 for the 2 . 4 μm waveguide width and the 10 μm waveguide width , respectively . a simulation was also produced for both horizontal ( x ) and vertical ( y ) far - field patterns of the 10 μm width waveguide laser . these patterns are depicted in fig4 a - b , respectively . the horizontal full - width - half - maximum ( fwhm ) far - field angle was 7 . 6 degrees and the vertical angle was 31 . 5 degrees . advantageously , this beam pattern is ideal for coupling to a cylindrical fiber lens and may provide a coupling efficiency of greater than 80 %. accordingly , a fiber coupled power of greater than 500 mw may be realized at 1500 ma . furthermore , the thermal power dissipation may be 1 . 74w at a laser driving current of 1500 ma , making it possible to package the device with a standard 14 pin butterfly enclosure . the simulations provided a basis for a design of the semiconductor pump laser having an active region material and a blocking region material wherein the refractive index difference between the two materials at the fundamental frequency is less than about 0 . 029 and wherein the laser has a single transverse mode . an exemplary refractive index difference range for the semiconductor laser is about 0 . 020 to 0 . 025 . it is desirable that the index of refraction of the active region material is greater than the refractive index of the blocking region material . in one embodiment of the invention the blocking region material is in 0 . 95 ga 0 . 05 as 0 . 12 p 0 . 88 . more generally the blocking material may , for example , comprise in 1 − x ga x as y p 1 − y wherein x is less than about 0 . 96 and y is less than about 0 . 90 . in another embodiment of the invention the active region material is gaas and the blocking region material is ingaasp . the composition of ingaasp may be chosen to obtain the desired refractive index difference between the active and blocking regions . the active region width of the laser may be greater than about 2 . 4 μm with exemplary ranges of about 3 . 0 μm to 15 μm , and about 8 . 5 μm to 10 . 5 μm . in a particular embodiment the laser has a refractive index difference between the active and blocking regions of about 0 . 020 to 0 . 025 and an active region width in the range of about 8 . 5 μm to 10 . 5 μm . embodiments of the invention provide a front facet power greater than or equal to about 500 mw with an illustrative range of 500 mw to 900 mw . a particular embodiment of the invention provides a laser with an active region having a width in the range of about 8 μm to 11 μm and having a front facet power in the fange of about 700 mw to 800 mw . the single mode transmission power of the laser is greater than about 300 mw , with an exemplary range of about 300 mw to about 550 mw . in one embodiment of the laser , blocking regions comprise a stack of at least one n - ingaasp , p - ingaasp pair , wherein an n - ingaasp layer is adjacent to a p - electrode and a p - ingaasp layer is adjacent to an n - electrode . the blocking regions may also be constructed with a semi - insulating layer . an illustrative example includes a semi - insulating layer between a p - inp layer and an n - inp layer . the refractive index differences described above may achieve confinement factors of greater than about 6 . 0 %, with an illustrative range of about 6 % to 7 %. embodiments of the invention may be applied to lasers of any wavelength but present technology will likely encourage use with lasers having wavelengths of 1480 nm and 980 nm for example . blocking capability generally increases as the blocking material bandgap energy increases . according to embodiments of the invention the blocking material may have , for example , a bandgap energy greater than 1 . 20 ev , with an illustrative range of about 1 . 20 ev to 1 . 40 ev . semiconductor laser 100 is fabricated by first providing substrate 106 which has an illustrative thickness in the range of about 50 μm to 150 μm with an exemplary thickness of 100 μm . active region 102 and blocking regions 104 are disposed on substrate 106 and have a refractive index difference of less than about 0 . 029 . in one embodiment of the invention the desired refractive index difference is achieved by forming the active and blocking regions of like - materials . active region 102 may have , for example , a thickness in the range of about 0 . 04 μm to 0 . 06 μm , and is disposed between blocking regions 104 . top layer 108 is disposed on blocking regions 104 and active region 102 , and may have , for example , a thickness in the range of about 2 μm to 4 μm with an illustrative thickness of about 3 μm . blocking regions 104 comprise a plurality of layers which may have thicknesses in a range of about 0 . 5 μm to 1 . 5 μm , with a demonstrative thickness of 1 . 0 μm . electrodes ( not shown ) are provided above top layer 108 and below substrate 106 and may have thicknesses in the range of about 3 . 5 μm to 4 . 5 μm . embodiments of the invention provide an active area having a high coupling efficiency to an optical fiber as compared to conventional lasers . for example , the coupling efficiency to a single mode fiber may be greater than about 75 %. embodiments of the invention are particularly applicable to fiber amplifiers , for example , erbium doped fiber amplifiers and raman fiber amplifiers . the laser of the present invention may be fabricated by any conventional method by which active and blocking regions may be formed wherein their refractive index difference at the fundamental frequency is less than about 0 . 029 . provided below as an example is a fabrication method for a mesa buried heterostructure distributed feedback laser which may be used to construct a laser according to embodiments of the present invention . a double heterostructure is grown over conventional first - order distributed feedback gratings that are etched into a substrate . the substrate may be , for example , inp . the double heterostructure may be grown by a variety of epitaxial techniques such as for example , liquid phase epitaxy , hybrid vapor phase epitaxy , and metalorganic vapor phase epitaxy . the double heterostructure may consist of a plurality of layers . an oxide layer , such as silicon dioxide for example , is deposited over the surface of the double heterostructure . stripes are photolithographically patterned in a direction perpendicular to the gratings . the silicon dioxide , or analogous layer , serves as both an etch mask during mesa etching and a growth mask during blocking layer growth which is performed using metalorganic vapor phase epitaxy . mesas are chemically etched to the desired width , for example , 1 . 0 - 3 . 0 μm . the mesas that are formed are vertical walled for several microns below the surface , thus providing good correspondence between the mesa width and the active width . after etching , semi - insulating blocking layers are regrown around the mesas by selective metalorganic vapor phase epitaxy . after metalorganic vapor phase epitaxy blocking layer regrowth , the sio 2 is etched away in hf , and hybrid vapor phase epitaxy is used to provide additional thickness to the double heterostructure . the wafers are processed using conventional n - and p - contacts . the wafers are thinned and the laser chips cleaved and bonded to copper or ceramic sinks . asymmetric high reflectivity anti - reflection mirror coatings are applied to the facets by electron beam evaporation to stabilize the single - longitudinal mode . the anti - reflection coating consists of amorphous zirconia with 10 % yttria and the asymmetric high reflectivity coating is yttria which is overcoated with silicon . the exemplary embodiments having been described in detail , many variations and modifications will become apparent to those skilled in the art . for example , structural variations or material modifications that provide or allow for refractive index differences of less than about 0 . 029 , and a single transverse mode with a power of greater than about 300 mw are within the spirit and scope of the invention . accordingly , it is intended that the invention not be limited to the specific illustrative embodiments but be interpreted within the full spirit and scope of the appended claims . | 7 |
the inventive plastic closure device is denoted in its entirety by 1 and comprises a bottom part 2 onto which a screw cap 3 can be releasably fastened to form a seal . optionally , the screw cap 3 can be fastened to the bottom part 2 by a guarantee band 4 as protection against prior opening , so that an intact guarantee band 4 is a sign of a plastic closure device 1 which has never previously been opened . the bottom part 2 comprises a normally cylindrically shaped discharge outlet 22 , on the outer face of which is arranged an external thread 21 and which is delimited by a flange 20 . the screw cap 3 has an internal thread ( not represented ), which can be brought into operative connection with the external thread 21 , whereby the plastic closure device 1 can be closed in a liquid - tight manner . the bottom part 2 can also be provided with a hinged cap , or a piercing element disposed in the bottom part 2 . it is only important that the plastic closure device 1 should have a bottom part 2 with discharge outlet 22 and a peripheral flange 20 . with the flange 20 , the bottom part 2 can be fastened directly or indirectly to a plastic film 5 , as shown in detailed representation in fig3 , wherein the plastic film 5 constitutes a part of a tubular bag ( not represented ). depending on use , the tubular bag can be filled with different liquids , wherein the liquid can be extracted from the discharge outlet 22 from the tubular bag following the removal of the cap . the opening in the tubular bag which is necessary beneath the discharge outlet 22 can be produced either by a corresponding device to the abovementioned piercing element , for instance , or can be made directly in the plastic film 5 of the tubular bag . the bottom side 200 of the flange 20 , which is facing away from the cap 3 , for instance a screw cap 3 , has an energy - introducing arrangement in the form of a plurality of energy - introducing ribs 23 , which skirt the round flange 20 and project away from the bottom side 200 of the flange 20 . the energy - introducing ribs 23 are here preferably at least approximately parallel to one another and are arranged at such a distance from the inner diameter of the flange 20 or of the discharge outlet 22 that they lie outside the region of the cap 3 . a non - releasable connection of the bottom part 2 to the plastic film 5 of the tubular bag is effected by means of ultrasonic welding . after the bottom part 2 has been placed with the bottom side 200 of the flange 20 on the plastic film 5 , a sonotrode 6 , which is usually of rotationally symmetric configuration , is positioned on the flange top side 201 , which is facing away from the energy - introducing ribs 23 . the sonotrode 6 is advantageously configured as a rotary sonotrode 6 , which has a receiving space 60 into which the bottom part 2 , where necessary with mounted cap 3 , can be received , while the bearing edge 61 of the sonotrode 6 has direct contact with the flange top side 201 . the ultrasonic energy is introduced into the region of the joining zone z at least approximately perpendicularly to the flange top side 201 , wherein the vibrational direction s of the sonotrode 6 is realized , say , longitudinally roughly parallel to the longitudinal axis of the bottom part 2 of the plastic closure device 1 . with an amplitude a , high - frequency mechanical vibrations , generated by a connected generator , are realized , which vibrations correspond to the working frequency of the sonotrode 6 . during the introduction of the mechanical ultrasonic vibrations , a static joining force f is applied at least approximately perpendicularly to the flange top side 201 during a welding time . the static joining force f points roughly in the vibrational direction s . the sonotrode 6 presses the bottom part 2 under the static joining force f against an anvil ( not represented ). as a result of the high - frequency ultrasonic vibration , the contact points between the plastic film 5 and the flange 20 is or are heated , whereby the integral connection between the bottom part 2 and the tubular bag or plastic film 5 ensues . the welded joint can be realized either directly between the flange bottom side 200 and the plastic film 5 of the tubular bag , or between the flange bottom side 200 and a plastic patch inside the tubular bag beneath the plastic film 5 of the tubular bag , wherein the ultrasonic vibration correspondingly introduces energy into the energy - introducing ribs 23 . after the actual welding operation also , the joining force f persists for a dwell time , wherein the flange 20 and the plastic film 5 cools under pressure . tests have shown that the plurality of energy - introducing ribs 23 should be arranged over a width b on the bottom side 200 , wherein the flange top side 201 , spanning the width b , should be fully covered during the welding operation by the bearing surface , here the edge 61 of the sonotrode 6 , in order to ensure an optimal energy input . the energy - introducing ribs 23 should be arranged approximately parallel at a distance apart b ′, wherein the energy - introducing ribs 23 and the flange bottom side 200 are distanced by a height h from the plastic film 5 . tests have shown that two or more , preferably three , energy - introducing ribs 23 over the width b lead to optimal liquid - tight welded joints . in comparison to methods according to the prior art , the static joining force f which is to be expended , and the overall expended power , was able to be reduced , wherein welded joints of equivalent quality are achievable . the height h is determined by the distance between the flange bottom side 200 and the elevation maximum of the energy - introducing ribs 23 , and thus by the plastic film 5 which is to be welded on . heights h of 0 . 2 to 0 . 4 mm were chosen . the energy - introducing ribs 23 , which in cross section are configured rounded into their end , have a radius r of 0 . 1 to 0 . 3 mm . the elevation maxima of the energy - introducing ribs 23 in the form of domes give rise , viewed in cross section , to roughly punctiform bearing surfaces against the plastic film 5 . the flanks of the energy - introducing ribs 23 enclose an angle α between 50 ° and 70 °, preferably of 60 °. the domes of the energy - introducing ribs 23 lie beneath the flange bottom side 200 on circular bearing lines or narrow bearing surfaces . the distance apart b ′ of adjacent energy - introducing ribs 23 of the energy - introducing arrangement is chosen between 1 mm and 1 . 5 mm , depending on the flange width b and width of the bearing edge 61 of the sonotrode 6 , so that , in the case of three parallel , and thus non - intersecting energy - introducing ribs 23 , the width b of the energy - introducing arrangement is about 2 . 5 to 2 . 7 mm . since thread flanks of the external thread 21 project partially over the flange top side 201 , the bearing edge 61 of the sonotrode 6 can usually be mounted onto the flange top side 201 such that it does not bear against the discharge outlet . it is important , however , that the edge 61 rests as flatly as possible on the flange top side 201 , lying opposite the energy - introducing arrangement on the flange bottom side 200 , wherein the ultrasonic energy can be optimally introduced by the sonotrode 6 into the flange 20 and the energy - introducing ribs 23 . in order to achieve a largest possible region of energy transfer to the flange 20 , the sonotrode 6 must be led as closely as possible past the thread flanks of the external thread 21 , so that a maximal contact surface on the flange top side 201 is covered . in series of tests which have compared the welding method according to the prior art , where only one energy - introducing rib is used , with the use of a plastic closure device 1 having a plurality of energy - introducing ribs , a significant reduction in the necessary static joining force f , and , above all , in the maximally necessary power , was able to be measured . here good results were manifested with the use of energy - introducing arrangements comprising two and three energy - introducing ribs 23 , wherein the best results were able to be achieved with three energy - introducing ribs 23 . the weld fastening of a bottom part of a plastic closure device according to the prior art is compared with a bottom part 2 with special energy - introducing arrangement comprising three energy - introducing ribs 23 on identical plastic films 5 each having a thickness of 5 mil , which corresponds to a thickness of ( 1 mil = 25 . 4 μm ) about 125 μm . the surface areas of the flange bottom sides 200 and flange top sides 201 of the known bottom part , as well as of the novel bottom part 2 , were identical , so that the results are comparable . in the case of more than three energy - introducing ribs , these must be reduced in thickness so as not to add further to the energy and power requirement . as a consequence , the volume of the material necessary for the welding would be too low , however , and the strength of the welded joint would be reduced . table 1 shows the direct comparison of the method parameters for fastening the known bottom part and the novel bottom part 2 respectively . in addition to a near halving of the necessary static joining force f and a reduction in the necessary inputted ultrasonic energy in combination with approximately equal amplitude a , the power to be expended for the entire ultrasonic welding operation was able to be significantly reduced . table 2 shows a comparison of the tensile force for the removal of a welded - on plastic closure devices according to the prior art and an inventive plastic closure device 1 or the bottom part 2 , with the use of three energy - introducing ribs 23 . the above - described bottom parts with identical surface areas of the flange bottom sides , after having been fastened on an identical plastic film 5 , were loaded after a while with the below - specified tensile forces under identical conditions . it can clearly be seen that the necessary tensile force or tensile force per unit of area for the detachment of the bottom parts , in the case of the bottom part 2 provided with the new energy - introducing arrangement , lies significantly above the comparison value of the traditional bottom part . as has been explained above , the present configuration of the bottom part 2 was able to bring about an improvement in the previously known welding methods , so that an energy - efficient , integral connection of bottom parts 2 of plastic closure devices 1 with plastic films 5 of tubular bags can be achieved , which connection additionally ensures a still stronger and more resistant connection between the bottom part 2 and the tubular bag . in order to enhance the welded joint , a situation in which the bottom side 200 , in the outer marginal region y of the flange 20 , comes into contact with the plastic film 5 during welding should be avoided . in order to prevent a part of the energy from being introduced into the plastic film 5 outside the desired joining zone z during the welding operation , the bearing of the bottom side in the marginal region y of the flange 20 is avoided by virtue of the fact that bottom side 200 is guided after the outer energy - introducing rib 23 in the direction of the flange top side 201 . this is illustrated in fig5 a . the strongly rounded marginal region y of the flange 20 is distinguished by the fact that the bottom side 200 merges into the flange top side 201 , wherein the distance of the bottom side 200 to the plastic film 5 corresponds to the height h of the energy - introducing rib 23 only directly at the outer energy - introducing rib 23 . as a result of the bottom side 200 in the marginal region y , said bottom side being curved away from the plastic film 5 , the welding energy remains limited to the joining zone z and thus no adhesion of the plastic film 5 occurs beneath the marginal region y of the flange 20 . as a result of this concentration of welding energy , the necessary energy can be additionally reduced . in fig5 b , a section through the flange 20 along the sectional line w - w according to fig2 is represented . here too , the bottom side 200 is curved after the outer , in this case second energy - introducing rib 23 strongly away from the plastic film 5 in the direction of the flange top side 201 , whereby the resulting marginal region y after the outer energy - introducing rib 23 is strongly curved and is distanced from the plastic film 5 . that surface area of the flange bottom side 200 which lies opposite the plastic film 5 is thus minimized , whereby almost no welding is performed in this marginal region y . the introduced energy is thus concentrated on the energy - introducing ribs 23 . | 1 |
fig1 is a schematic diagram of a lithium battery . the lithium battery has an anode 103 and a cathode 101 , and contains a stock of electrolyte . the anode material is made of a tin - based porous material of a general composition of sn — p — o having tiny pores , the inner surfaces or walls of the pores are laid with carbon or a carbonaceous material capable of electro - conductivity . for facilitating description herein , the tin - based porous material without the layer of carbon is termed tin based material , while the same material having a layer of carbon or carbonaceous material on the pore walls is termed an electrode composite material . the cathode is generally a material comprising lithium , such as lithuim cobalt oxide , lithium iron phosphate or some other electrochemically reversible lithium salts . the electrolyte is typically a mixture of organic carbonates such as ethylene carbonate as solvent and lithium hexfluorophosphate as solute . during battery discharge , positive lithium ion is extracted from the anode 103 and inserted into the cathode 101 with the simultaneous release of electron . if the cathode 101 is lithium cobalt oxide , the cathode 101 releases electrons as shown in the half - reaction : licoo 2 ⇄ li 1 - n coo 2 + n li + + ne − ( 1 ) therefore , cobalt ( co ) is oxidised from co 3 + to co 4 + during charging . the reverse occurs during discharging to reduce co 4 + to co 3 + . during battery charging , supply of electric current to the anode 103 converts lithium ion into lithium , which then ‘ alloys ’ into the tin - based anode 103 . conversely , the lithium ‘ dealloys ’ from the tin - based anode 103 during the discharging process . fig2 is an electron microscope picture of the tin - based material having a porous structure comprising tiny pores of different sizes . the tin in the tin - based material provides the electroactive element for attracting lithium insertion into the porous material , while phosphorus and oxygen forming part of the tin - based material has a function of spacing out and dispersing the tin . this also spaces out the attracted lithium ions . the dispersed tin provides spatial allowance for accommodating volume expansion of the anode during battery charging . therefore , the tiny pores provide a large surface area in the tin - based material for interacting with lithium ions . fig3 shows the surfaces or walls inside the pores 303 in the tin - based material 301 deposited with or coated with a carbonaceous material 305 such as a carbon layer to form an electrode composite material useable as battery anode . the carbonaceous layer 305 has better conductivity than tin - based material 301 and is able to attract lithium ions into the pore more strongly . treating the walls inside the pores 303 in this way provides the anode with both the structural benefits of tin - based material 301 for storing lithium and the electro - conductivity of the carbonaceous material 305 for attracting lithium ions . therefore , during lithium ion battery charging , lithium ions are attracted to migrate into the pores , and diffused through the layer of carbonaceous material 305 to contact the tin - based material , where the lithium ions are reduced and alloyed with tin in the tin - based material as a form of reversible lithium - tin alloy . accordingly , the anode is made of a porous material providing structural support for a more electro - conductive material laid on the surfaces or walls of the pores 303 . fig4 illustrates steps in a process to produce the anode material . accompanying fig5 a to 9 each illustrate a specific step in the process of fig4 . a solution of tin precursor 401 such as tin sulphate and a solution of phosphorous precursor 403 such as phosphorus acid are mixed to produce an intermediate tin - based material 301 a by precipitation . the reaction is generally not stoichiometric , as the intermediate tin - based material 301 a produced is not crystalline but has varying combinations of tin and phosphorous , oxide , hydroxide in an amorphous compound or mixture . various forms of tin may also form part of the intermediate tin - based material 301 a , including tin ( ii ) and tin ( iv ). fig5 a to 5 c show that the precipitation takes place in the presence of a surfactant 405 , the molecules of which immediately surrounding fine particles of the intermediate tin - based material 301 a as soon as the particles precipitate to form micelles 409 . in this way , the surfactant 405 provides a suspension of fine particles ; the micelles prevent particles of the tin - based material 301 from agglomerating into large , coarse particle clusters . a coagulant 410 is then introduced into the suspension with stirring . typically , the coagulant 410 is a long chain molecule having a relatively high molecular weight and which is attracted to the surfactant 405 . fig6 a and 6 b show how the coagulant 410 molecule wraps around the micelles 409 . fig4 and fig7 show how the high molecular weight of coagulant causes the mixture of coagulant , surfactant and particles of tin - based material to settle together in a mixture , as a solid deposit 413 . the solid deposit 413 is then recovered by filtration , washed with distilled water , and dried . washing remove unreacted phosphorous acid and any soluble salts . the dried solid deposit 413 is then subjected to heat treatment . the surfactant 405 is sufficiently volatile such that , when heated in a first heating stage , the surfactant 405 migrates through the dried solid deposit 413 , from within the solid deposit 413 towards the surface of the solid deposit 413 . the surfactant either has sufficient volatility inherently or the surfactant 405 comes attached with a methanal group such as formaldehyde which imparts volatility to the surfactant 405 . in this first heating stage , the temperature is typically & gt ;= 300 ° c . applied for & gt ;= 30 minutes in an atmosphere of air . in large scale production , time required for the surfactant 405 to be completely removed depends on specific conditions as the skilled man will know . during the heating , carbon substance on surface may be removed by oxidised as gases when exposed to oxygen in the air atmosphere . fig1 illustrates how the surfactant leaves 1101 the solid deposit 413 . as the surfactant 405 moves to the surface of the solid deposit 413 , the attraction between the anionic surfactant 405 and the cationic coagulant 410 moves the coagulant 410 along , towards the surface of the solid deposit 413 . fine particles of tin - based material 301 in the solid deposit 413 now left behind by the surfactant 405 are no longer enclosed in a micelle structure , and are then able to contact mutually and agglomerate into a somewhat unitary mass . nearer the surface of the solid deposit 413 , some of the fissures meet and merge to form larger fissures . eventually , the agglomerated solid deposit 413 has fissures resulting from the migration paths of the surfactant 405 and the coagulant 410 , which provide the pores in the tin - based material 801 . fig8 illustrates the so - produced porous tin - based material 801 . on reaching the surface of the solid deposit 413 , the surfactant 405 is either capable of evaporating into the surrounding atmosphere directly or is capable of breaking down into more volatile compounds or form gases in order to escape . if surfactant 405 should be oxidised into gases in order to be released , the atmosphere would be typically air . the coagulant 410 which moved together with the surfactant 405 towards the surface of the solid deposit 413 is not released into the atmosphere along with the relatively volatile surfactant 405 . this is due to the stronger binding force within the coagulant 410 . the pores 303 formed by the release of the surfactant 405 are therefore filled with the coagulant 410 . the porous tin - based material 801 is then placed in an atmosphere of inert gas , such as argon or nitrogen , and subjected to a second heating stage 1009 at a higher temperature . in practice , the heat may cause the coagulant 410 to move a little and be physically redistributed somewhat near the surface inside pores 303 without being vapourised away . the heat decomposes or carbonizes the coagulant 410 in situ to form a carbonaceous material 305 on the walls of the pores 303 , as illustrated in fig9 which corresponds to fig3 . carbonising the coagulant in situ , i . e . within the pores , allows for the walls of even tiny pores , fissure or cavities to be laid with a carbonaceous material 305 . the coagulant 410 can be any long chain molecule which is able to bind to the surfactant 405 surrounding the tin - based material 301 , and can decompose to form an electro - conductive layer on the walls of the pores . in this embodiment , the long chain molecule is preferably a carbon based molecule , such as a hydrocarbon polymer . the temperature for carbonization of the coagulant 410 is not a specific or constant temperature because the coagulant 410 comprises molecules of varying chain lengths , leading to a range of temperatures over which heating , melting and carbonation may occur . generally , the average temperature and duration , however , is preferably ≧ 500 ° c . for ≧ 2 hours . depending on the choice of surfactant 405 and coagulant 410 , the temperature causing the surfactant 405 to migrate and vaporise away in the first heating stage should preferably be insufficient to carbonise or decompose the coagulant 410 , in order for the different processes to be capable of being controlled separately . fig1 illustrates what happens to the mass of the dried solid deposit 413 in the two heating stages . the left - most bar 1003 shows the mass of the dried solid deposit 413 as 100 % before heat treatment . in the first heating stage 1005 shows thermal reaction 1005 resulting in a loss of mass 1005 , as show in the middle bar . the loss of mass implies that the surfactant 405 escapes from the solid deposit 801 . furthermore thermal reaction 1009 is observed at the subsequent treatment at a higher temperature of & gt ; 500 ° c . in an inert atmosphere . there is less loss of mass , as shown in the right - most bar 1011 , which implies that a large part of the mass of the coagulant 410 remains inside the porous tin - based material as a carbonaceous material on the pores 303 . fig2 shows the pores 303 in tin - based material 301 produced using the process may even achieve a desirable minimum pore size of & lt ; 1 μm . the coagulant is preferably cationic and the surfactant anionic in order to ensure sufficient attraction between the coagulant and surfactant , although it is possible that the surfactant may be cationic while the coagulant is anionic in reverse . the preferred surfactant 405 in this embodiment is an anion surfactant such as polymeric sulfonates with methanal group or polycarboxylare . an example of a corresponding coagulant is a cationic polymer such as polyamine , polyamide , polyether , polyethylamide , polyethylenimine or polyaziridine or any hydrocarbon or polymer which contains a group such as ethylene . the amount of coagulant 410 added to the mixture should , after carbonization , provide carbon content in the pores of the electrode composite material to between 5 to 20 wt % of the whole composite material . preferably , a thicker or denser layer of carbonaceous material 305 is formed in the deep end 307 of the pores 303 than at or about the mouths 308 of the pores 303 . more preferably , the amount or the thickness of the carbonaceous material 305 on the walls of the pores 303 gradually decreases from inside the pores 303 towards the mouth of the pores 303 . this is achieved by allowing a trace presence of oxygen in the generally inert atmosphere when carbonizing the coagulant 410 , which provides opportunistic oxidation of carbon only at the mouth of the pores 303 . the oxygen should be in trace but sufficient amount only to oxidise the easily - reached carbonaceous material 305 at , around or about the mouth of the pores 303 , but not carbonaceous material 305 inside the pores 303 . this localised oxidation of carbonaceous material generates a larger mouth at the carbon laid pores and may also generate more pores on the composite material by unclogging any pore mouth which are clogged with the carbonaceous material . having less carbonaceous material 305 at the mouth of the pore and more carbonaceous material 305 deep inside the pores creates a greater affinity for lithium inside the pores 303 . this provides and a sort of electrical gradient attracting lithium to move into and pack the deep end of the pores 303 , maximizing use of the porosity of the tin - based material 301 to interact with lithium ions . more preferably , only after it is deemed that the coagulant has completely carbonised in a completely inert atmosphere is the trace amount of oxygen introduced into the inert atmosphere . this prevents oxidation of the carbonaceous material 305 at the same time as the carbonaceous material 305 is forming in the pores 303 , and allows better control of the amount of oxidation of the carbon at the mouth of the pores 303 . fig1 illustrates a possible variation of the embodiment to that of fig3 , wherein a higher amount of surfactant used causes formation of a pulverised , or a more fractured or fragmented tin - based matrix . furthermore , a longer heating duration , higher trace oxygen content , and higher temperature range promote a pulverised form . fig1 illustrates a further possible variation of the embodiment of fig3 , wherein a prolonged second heating stage causes the atoms in tin - based matrix to realign and close up to contain smaller , narrower or fewer pores . as the skilled man would know , the product of the described embodiment is typically fine powder or granules , each particle being a tin - based material having pores laid with carbonaceous layer as described , which may be used for manufacture of electrodes in batteries . it should be noted that too much phosphorus in tin - based material 301 may present opportunity for lithium to bind to the phosphorus permanently , which reduces available electrolyte . preferably , the optimum range of phosphorus is & lt ; 30 wt %, and may be as low as 5 wt % in some embodiments , and the percentage of tin & gt ; 20 wt %, and is about 20 - 75 wt % in some embodiments . therefore , in a variation of the embodiment , it is possible to include a step in the process to reduce the tin in the tin - based material 301 so that any tin ( iv ) to tin ( ii ) or tin ( 0 ), such as , snp 2 o 7 to sn 2 p 2 o 7 or snp ; and or sno to sn2o to sn . for example , the carbonization of the coagulant 410 takes place in an atmosphere of reducing gas such as hydrogen or a hydrogen containing gas . having less oxide in the tin - based material 301 reduces the chance of lithium attaching to oxide permanently . care should be taken in this case to avoid introducing oxygen into a hydrogen atmosphere . thus , if a hydrogen atmosphere is used to reduce tin , the step of oxidation of the carbonaceous material around the mouth of the pores should be conducted as a separate step , either before or after . optionally , the tin based material is precipitated in a reducing medium to encourage formation of tin ( ii ) for higher tin to phosphorous ratio . exemplary embodiments of the present invention are described . although the description referred to particular embodiments , it will be clear to one skilled in the art that the present invention may be practiced with variation of these specific details . hence this invention should not be construed as limited to the embodiments set forth herein . for example , the skilled man knows that the term ‘ pores ’ refers to any fissure , fault line or cavity formed deep in the body or at the surface of the electrode composite material suitable for the purpose of providing a structure for the alloying of lithium to the tin - based material in a lithium battery charging process , and for the formation of any amount and form of carbonaceous material 305 on the walls inside the pores . in some practices , the pores are be termed ‘ mesopores ’ and the composite structure is a meso - porous structure . furthermore , the skilled man understands that ‘ removing ’ the surfactant from the coagulated precipitate to form pores in the tin - based material may include vaporising the surfactant away , or any other method . although it is mentioned that the tin - based material comprises a generally sn — p — o matrix , the skilled man understands that various other elements may be part of the matrix in practice , such as an amount of carbon inside the matrix leading to a general formula of sn — p — o — c . furthermore , although the phosphorus precursor 403 is described as phosphorous acid , other forms of phosphorus may be used , such as soluble potassium phosphate salts and sodium phosphate salts , capable of ion exchange reaction with the selected tin salt . furthermore , the types of tin precursors 401 may include any solution of tin salts that has an anion replaceable with a phosphorus based ion or the phosphate in phosphorus acid , such as tin fluoride , tin chloride , tin sulphate , tin fluoride or tin nitrate . some tin salts have limited solubility under specific conditions and it is within the knowledge of the skilled man to attend to these in practice . the surfactant 405 may be any molecule that can form micelles with the tin - based material 301 to prevent agglomeration of the tin - based material 301 , has the ability to bind to the coagulant 410 , and to disperse the formation of pores 303 inside the tin - based material 301 as evenly and as isotropically as possible , and may be referred to in other embodiments as plasticizers , superplasticiziers , surfactants , poloxamers and so on . although it is mentioned that carbonaceous material 305 is formed on the wall inside the pores , the carbonaceous material 305 may be simply carbon or any short chain carbon material , as long as the material may be laid well on the pore wall and has better conductivity than the surface of the pore wall . in a variation of the embodiment , the first and second heating stages 1005 , 1009 may be combined as one heating stage to eliminate the surfactant 405 to form pores 303 and carbonised the coagulant 410 to form the carbonaceous later on the wall of the pore 305 at the same time . this will depend on the choice of the surfactant 405 and coagulant 410 . although it has been described that the surfactant 405 is removed by heating in an atmosphere of air , it is possible that some choices of the surfactant 405 may allow the surfactant 405 to be vapourised by heating in an atmosphere of nitrogen , such as by evaporation or breaking of the surfactant without need of any oxidation in air . although the surfactant and coagulant in the coagulated precipitate have been described as preferably decomposable over a different temperature ranges , there could be overlapping temperature regions in practice . therefore , some decomposition of coagulant may take place in the first heating stage and oxidised as gases when exposed to oxygen in air , thus released together with the evaporating surfactant , creating larger pores . | 8 |
the embodiment ( s ) described , and references in the specification to “ one embodiment ”, “ an embodiment ”, “ an example embodiment ”, etc ., indicate that the embodiment ( s ) described may include a particular feature , structure , or characteristic , but every embodiment may not necessarily include the particular feature , structure , or characteristic . moreover , such phrases are not necessarily referring to the same embodiment . further , when a particular feature , structure , or characteristic is described in connection with an embodiment , it is understood that it is within the knowledge of one skilled in the art to effect such feature , structure , or characteristic in connection with other embodiments whether or not explicitly described . fig1 depicts a lithographic apparatus according to one embodiment of the invention . the apparatus includes an illumination system ( illuminator ) il configured to condition a radiation beam b ( e . g . uv radiation or euv radiation ), a support structure ( e . g . a mask table ) mt constructed to support a patterning device ( e . g . a mask ) ma and connected to a first positioner pm configured to accurately position the patterning device in accordance with certain parameters , a substrate table ( e . g . a wafer table ) wt constructed to hold a substrate ( e . g . a resist coated wafer ) w and connected to a second positioner pw configured to accurately position the substrate in accordance with certain parameters , and a projection system ( e . g . a refractive projection lens system ) ps configured to project a pattern imparted to the radiation beam b by patterning device ma onto a target portion c ( e . g . including one or more dies ) of the substrate w . the illumination system may include various types of optical components , such as refractive , reflective , magnetic , electromagnetic , electrostatic , or other types of optical components , or any combination thereof , for directing , shaping , or controlling radiation . the support structure supports , i . e ., bears the weight of , the patterning device . it holds the patterning device in a manner that depends on the orientation of the patterning device , the design of the lithographic apparatus , and other conditions , such as for example whether or not the patterning device is held in a vacuum environment . the support structure can use mechanical , vacuum , electrostatic , or other clamping techniques to hold the patterning device . the support structure may be a frame or a table , for example , which may be fixed or movable as required . the support structure may ensure that the patterning device is at a desired position , for example with respect to the projection system . any use of the terms “ reticle ” or “ mask ” herein may be considered synonymous with the more general term “ patterning device .” the term “ patterning device ” used herein should be broadly interpreted as referring to any device that can be used to impart a radiation beam with a pattern in its cross - section such as to create a pattern in a target portion of the substrate . it should be noted that the pattern imparted to the radiation beam may not exactly correspond to the desired pattern in the target portion of the substrate , for example if the pattern includes phase - shifting features or so called assist features . generally , the pattern imparted to the radiation beam will correspond to a particular functional layer in a device being created in the target portion , such as an integrated circuit . the patterning device may be transmissive or reflective . examples of patterning devices include masks , programmable mirror arrays , and programmable lcd panels . masks are well known in lithography , and include mask types such as binary , alternating phase - shift , and attenuated phase - shift , as well as various hybrid mask types . an example of a programmable mirror array employs a matrix arrangement of small mirrors , each of which can be individually tilted so as to reflect an incoming radiation beam in different directions . the tilted mirrors impart a pattern in a radiation beam which is reflected by the mirror matrix . the term “ projection system ” used herein should be broadly interpreted as encompassing any type of projection system , including refractive , reflective , catadioptric , magnetic , electromagnetic , and electrostatic optical systems , or any combination thereof , as appropriate for the exposure radiation being used , or for other factors such as the use of an immersion liquid or the use of a vacuum . any use of the term “ projection lens ” herein may be considered as synonymous with the more general term “ projection system .” as here depicted , the apparatus is of a transmissive type ( e . g . employing a transmissive mask ). alternatively , the apparatus may be of a reflective type ( e . g . employing a programmable mirror array of a type as referred to above , or employing a reflective mask ). the lithographic apparatus may be of a type having two ( dual stage ) or more substrate tables ( and / or two or more mask tables ). in such “ multiple stage ” machines the additional tables may be used in parallel , or preparatory steps may be carried out on one or more tables while one or more other tables are being used for exposure . the lithographic apparatus may also be of a type wherein at least a portion of the substrate may be covered by a liquid having a relatively high refractive index , e . g ., water , so as to fill a space between the projection system and the substrate . an immersion liquid may also be applied to other spaces in the lithographic apparatus , for example , between the mask and the projection system . immersion techniques are well known in the art for increasing the numerical aperture of projection systems . the term “ immersion ” as used herein does not mean that a structure , such as a substrate , must be submerged in liquid , but rather only means that liquid is located between the projection system and the substrate during exposure . referring to fig1 , the illuminator il receives a radiation beam from a radiation source so . the source and the lithographic apparatus may be separate entities , for example when the source is an excimer laser . in such cases , the source is not considered to form part of the lithographic apparatus and the radiation beam is passed from the source so to the illuminator il with the aid of a beam delivery system bd including , for example , suitable directing mirrors and / or a beam expander . in other cases the source may be an integral part of the lithographic apparatus , for example when the source is a mercury lamp . the source so and the illuminator il , together with the beam delivery system bd if required , may be referred to as a radiation system . the illuminator il may include an adjuster ad for adjusting the angular intensity distribution of the radiation beam . generally , at least the outer and / or inner radial extent ( commonly referred to as σ - outer and σ - inner , respectively ) of the intensity distribution in a pupil plane of the illuminator can be adjusted . in addition , the illuminator il may include various other components , such as an integrator in and a condenser co . the illuminator may be used to condition the radiation beam , to have a desired uniformity and intensity distribution in its cross section . the radiation beam b is incident on the patterning device ( e . g ., mask ma ), which is held on the support structure ( e . g ., mask table mt ), and is patterned by the patterning device . having traversed the mask ma , the radiation beam b passes through the projection system ps , which focuses the beam onto a target portion c of the substrate w . with the aid of the second positioner pw and position sensor if ( e . g . an interferometric device , linear encoder , or capacitive sensor ), the substrate table wt can be moved accurately , e . g ., so as to position different target portions c in the path of the radiation beam b . similarly , the first positioner pm and another position sensor ( which is not explicitly depicted in fig1 ) can be used to accurately position the mask ma with respect to the path of the radiation beam b , e . g ., after mechanical retrieval from a mask library , or during a scan . in general , movement of the mask table mt may be realized with the aid of a long - stroke module ( coarse positioning ) and a short - stroke module ( fine positioning ), which form part of the first positioner pm . similarly , movement of the substrate table wt may be realized using a long - stroke module and a short - stroke module , which form part of the second positioner pw . in the case of a stepper ( as opposed to a scanner ) the mask table mt may be connected to a short - stroke actuator only , or may be fixed . mask ma and substrate w may be aligned using mask alignment marks rm 1 and rm 2 and substrate alignment marks p 1 and p 2 . although the substrate alignment marks as illustrated occupy dedicated target portions , they may be located in spaces between target portions ( these are known as scribe - lane alignment marks ). similarly , in situations in which more than one die is provided on the mask ma , the mask alignment marks may be located between the dies . the depicted apparatus could be used in at least one of the following modes : 1 . in step mode , the mask table mt and the substrate table wt are kept essentially stationary , while an entire pattern imparted to the radiation beam is projected onto a target portion c at one time ( i . e ., a single static exposure ). the substrate table wt is then shifted in the x and / or y direction so that a different target portion c can be exposed . in step mode , the maximum size of the exposure field limits the size of the target portion c imaged in a single static exposure . 2 . in scan mode , the mask table mt and the substrate table wt are scanned synchronously while a pattern imparted to the radiation beam is projected onto a target portion c ( i . e . a single dynamic exposure ). the velocity and direction of the substrate table wt relative to the mask table mt may be determined by the ( de -) magnification and image reversal characteristics of the projection system ps . in scan mode , the maximum size of the exposure field limits the width ( in the non - scanning direction ) of the target portion in a single dynamic exposure , whereas the length of the scanning motion determines the height ( in the scanning direction ) of the target portion . 3 . in another mode , the mask table mt is kept essentially stationary holding a programmable patterning device , and the substrate table wt is moved or scanned while a pattern imparted to the radiation beam is projected onto a target portion c . in this mode , generally a pulsed radiation source is employed and the programmable patterning device is updated as required after each movement of the substrate table wt or in between successive radiation pulses during a scan . this mode of operation can be readily applied to maskless lithography that utilizes programmable patterning device , such as a programmable mirror array of a type as referred to above . combinations and / or variations on the above described modes of use or entirely different modes of use may also be employed . to control reticle alignment , the lithographic apparatus according to an embodiment of the invention includes a control system that is capable of controlling adjustments for each reticle alignment process . further , the lithographic apparatus includes an alignment sensor system which is arranged to measure information on the alignment of the reticle ( s ) as will be explained in more detail below . typically , the control system relates to a computer system ca including a processor pr for performing arithmetical operations , and a memory me . the processor pr is arranged to communicate with memory me . memory me may be any type of memory arranged to store instructions and data , such as a tape unit , a hard disk , read only memory ( rom ), non volatile random access memory ( nvram ), and random access memory ( ram ). the processor pr may be arranged to read and execute programming lines stored in memory me providing the processor pr with the functionality to perform reticle alignment and reticle alignment adjustments as will be described in more detail below . the processor pr may be specially provided to perform the described embodiment of the method , but may also be a central processor arranged to control the lithographic apparatus as a whole and now is provided with additional functionality to perform the described embodiment of the method . it should be understood that there may be provided additional computer system units , such as memory units , input devices , and read devices known to persons skilled in the art . moreover , one or more of them may be physically located remote from the processor pr , if required . the processor pr is shown as one box , however , it may include several processing units functioning in parallel or controlled by one main processor pr that may be located remote from one another , as is known to persons skilled in the art . although all connections in fig1 are shown as physical connections , one or more of these connections can be wireless . they are only intended to show that “ connected ” units are arranged to communicate with one another in some way . the computer system can be any signal processing system with any combination of analog , digital , or software technology arranged to perform the functions discussed here . before an exposure is done by the lithographic apparatus , several alignment procedures must be carried out , including a reticle alignment which has the purpose of aligning the reticle ma with the wafer stage wt . the basic reticle alignment procedure is described below . the reticle includes an image area im wherein the pattern that is to be transferred to the photoresist layer on the substrate would be projected . next to this image area , reticle marks ( or mask alignment marks ) rm 1 , rm 2 , rm 3 , and rm 4 are located . in this exemplary reticle layout the reticle marks are located adjacent to the corner regions of the image area , at a projected distance dy along the direction y from the center of the image area im . the image area im has a size ly along the direction y and a second size lx along the direction x . by means of an illumination beam , an aerial image of one or more of the reticle marks rm 1 , rm 2 , rm 3 , and rm 4 is projected on a respective image sensor arranged on the wafer stage wt as an alignment sensor . based on the image data collected from the one or more aerial images by the image sensor ( s ), positional parameters , i . e ., information on at least one of the position , rotation , and magnification of the reticle , are obtained . next , the information on magnification is used to adjust the projection system ps and the distance between the mask table mt that holds the reticle and the wafer stage wt to correct any deviation from the required position of the aerial image . it will be appreciated that the reticle alignment procedure may include more complex scenarios , but a detailed discussion of these scenarios is not relevant in view of the invention and is therefore omitted here . fig3 a - 3 e illustrate the effect of non - uniform reticle heating on overlay performance . fig3 a depicts an example of a measured field fingerprint at wafer level . the overlay accuracy is depicted by a grid of measurement points . an overlay error in each measurement point is indicated by an arrow . the size and direction of each arrow is a guide of the size and direction of the overlay error at the corresponding measurement point . fig3 b - 3 e depict examples of the overlay error distribution for various image size fields . for each image field the overlay error distribution oe is determined by plotting for each measurement point the overlay error as function of the radial distance . the radial distance is determined in relation to a center position of the respective image field . fig3 b depicts the overlay error distribution for an image field of 3 × 3 mm 2 for an exposure with dose of 204 mw / cm 2 and an exposure time of 313 s . fig3 c depicts the overlay error distribution for an image field of 5 × 5 mm 2 for an exposure with dose of 174 mw / cm 2 and an exposure time of 368 s . fig3 d depicts the overlay error distribution for an image field of 10 × 10 mm 2 for an exposure with dose of 126 mw / cm 2 and an exposure time of 506 s . fig3 e depicts the overlay error distribution for an image field of 20 × 20 mm 2 for an exposure with dose of 77 mw / cm 2 and an exposure time of 836 s . the dose of exposure as described here relates to a time averaged intensity at the reticle level . the exposure time as described here relates to the total time required for completion of the exposure of the image field . it is noted that in the above measurements the exposure time was taken longer than a heating time constant of the reticle to avoid non - saturation effects in the temperature distribution of the reticle . from fig3 b - 3 e , under the circumstances as given above , a non - linear relation between overlay error and radial distance exists indicative of a non - uniform heating of the reticle during exposure . the overlay error due to non - uniform heating of the reticle can be reduced by a correction method during reticle alignment which is explained here in more detail . first , in case of uniform reticle heating , the reticle has expanded in a substantially uniform manner . the expansion is , to a large extent , proportional to the temperature of the reticle . as a result , for a uniform expansion of the reticle , the correction method compensates the expansion by a change of the magnification settings of the projection system ps . since the expansion is uniform , the relative increase in the distance between the reticle marks rm 1 , rm 2 , rm 3 , and rm 4 ( say , xr ) will be proportional to the expansion of the image area of the reticle . a correction of the magnification cm , at a given time t , will thus be proportional to a measured expansion in xr . the expansion of the reticle can be derived from the reticle mark aerial image positions as measured by the image sensor ( s ) of the wafer stage wt . in case of non - uniform heating , the above mentioned correction by means of the measured expansion of the reticle mark ( s ) according to equation 1 , will typically underestimate the actual expansion of the reticle , since the region of the reticle where the reticle marks are located may have a lower temperature than the region of the image area , which is heated by the illumination beam during exposure . also , non - uniform heating is a dynamic effect , due to the fact that a stationary state ( or a saturation ) of the temperature distribution will be reached only after a finite time . in the correction method , the measured reticle expansion xr will be compensated for the predicted effect of heating induced expansion et ( t ) of the reticle as a function of time t , and applying the result as an estimated magnification correction cm ′ as a function of time t , i . e . as a function of exposure time t . this method is illustrated by equation 2 . the value of the weighting factor k may depend on the position of the reticle marks and the size of the illuminated image area ( which will be explained in more detail with reference to equation 6 ). cm ′( t )= k · xr ( t )+( 1 − k )· et ( t ) [ eq . 2 ] elaborating the above , the model predicted expansion in saturation of illuminated reticle regions es is directly related to the time averaged intensity at reticle level ir by a fixed proportionality constant c : where the time averaged intensity at reticle level ir , is given by : where n is a number of exposed fields per wafer , d is an exposure dose , m is a demagnification factor of the projection system , lt is a transmission of the projection system for the illumination beam , and te is the total time used to expose n fields . now , the predicted reticle expansion et of the illuminated reticle regions , at any given time t , can be calculated from equation 3 , by including the temporal effect of saturation by a time correction factor : finally , the estimated magnification correction cm ′( t ) follows from an optimal combination of the measured reticle expansion xr ( t ) and the model predicted value et ( t ), as illustrated by equation 2 . a suitable choice for the value of the weighting factor k therein , is affected by the position of the reticle marks and the size of the illuminated image area ( with reference to fig2 ): where ly is the length of the reticle in direction y and dy is the projected distance in direction y between the center of the reticle and the position of each respective reticle mark rm 1 , rm 2 , rm 3 , and rm 4 . thus , the weighting factor k is a factor determined by the layout of the reticle , i . e ., the size of the reticle and the location of the reticle mark with respect to the location of illuminated image area . based on equation 5 , an estimate for the reticle expansion e ( t ) at a given time t during exposure can be calculated for each of the measurements as shown in fig3 b - 3 e . the results are shown in table 1 . also , in table 1 , the results of the reticle expansion e0 as measured substantially at the center of the image area and the expansion xr of the reticle mark are included . the expansion xr measured at the reticle mark is smaller than the measured expansion e0 at the center of the reticle . at the same time , the calculated estimate e ( t ) for uniform heating is clearly much larger than the measured expansion e0 at the center of the reticle . both observations indicate that the expansion of the reticle is non - uniform and localized substantially in the ( exposed ) image area of the reticle . it is recognized that the measured expansion e0 at the center of the reticle can be estimated by the estimated magnification correction cm ′ as defined by equation 2 . from table 1 , it can be observed that cm ′ provides a better approximation ( with relatively smaller error ) than either xr or e ( t ). thus , during a sequence of exposures , an estimate for the actual expansion of the image area of the reticle can be obtained by measuring the expansion of the reticle mark in between exposures using the relation between cm ′ and xr according to equation 2 . it is noted that correction of the reticle expansion by a correction estimate cm ′ is not limited to a linear relation between expansion xr measured at the reticle mark and predicted reticle expansion et as defined by equation 2 . it will be appreciated that alternatively cm ′ may be determined from either a weighted non - linear relation or a weighted polynomial relation with xr and et . fig4 depicts a correction method 400 in accordance with an embodiment of the present invention . the correction method 400 seeks to compensate the effect of non - uniform reticle heating by means of a software feed - forward model . the model output is the temporal and spatial displacement of the reticle marks , which are computed using a temporal and spatial correction by a weighted average of the expansion xr measured at the reticle mark and a predicted temporal reticle expansion et . the input parameters which may be readily available from the control software of the lithographic apparatus , are the exposure energy ir , reticle transmission lt , exposure field size lx in direction x and ly in direction y , and the time constant for heating τ . further input to the model is the actual time that exposure is taking place . the interaction of the model output of the temporal and spatial displacement of the reticle marks with the reticle alignment measurement is illustrated in fig4 . in block 402 , the reticle alignment is measured in a manner known in the art . the processor pr determines information on positional parameters of one or more of the alignment marks rm 1 , rm 2 , rm 3 , and rm 4 by means of the image sensor as illustrated in fig2 . the positional parameters relate to at least one of position , orientation , and magnification of the aerial image of the measured reticle mark . in block 404 , the processor pr determines information on temporal and spatial displacement of the reticle marks according to the model described above using input parameters as described above . next , in block 406 the processor pr uses the information on temporal and spatial displacement of the reticle marks from block 404 , for correcting the measured reticle information from block 402 . the corrected reticle information is then used for determining an alignment of the reticle with the substrate table . as an output 408 the processor provides corrected reticle alignment data based on the estimated magnification correction cm ′ for use in an alignment procedure of the substrate and the reticle . such alignment procedure is carried out by the processor pr in a manner known in the art by controlling a position of the mask table mt and / or a position of the substrate table wt relative to each other . it is noted that the correction model 400 may operate in conjunction with a lens ( projection system ) heating model which provides a correction for a thermally induced lens magnification effect . during exposure the projection system is heated , in which the heating of the lens results in a change of the lens magnification ( relative to a magnification value at a reference temperature ). in case lens heating is corrected , the correction model includes a block 405 , in which the processor derives information on the change of magnification due to heating of the lens . the temperature - and / or time - based change of magnification is entered into block 406 , in which the processor applies the information on the lens magnification as a further parameter for correcting the obtained information on the positional parameters of the projected aerial image . although specific reference may be made in this text to the use of lithographic apparatus in the manufacture of ics , it should be understood that the lithographic apparatus described herein may have other applications , such as the manufacture of integrated optical systems , guidance and detection patterns for magnetic domain memories , flat - panel displays , liquid - crystal displays ( lcds ), thin film magnetic heads , etc . the skilled artisan will appreciate that , in the context of such alternative applications , any use of the terms “ wafer ” or “ die ” herein may be considered as synonymous with the more general terms “ substrate ” or “ target portion ”, respectively . the substrate referred to herein may be processed , before or after exposure , in for example a track ( a tool that typically applies a layer of resist to a substrate and develops the exposed resist ), a metrology tool and / or an inspection tool . where applicable , the disclosure herein may be applied to such and other substrate processing tools . further , the substrate may be processed more than once , for example in order to create a multi - layer ic , so that the term substrate used herein may also refer to a substrate that already contains multiple processed layers . although specific reference may have been made above to the use of embodiments of the invention in the context of optical lithography , it will be appreciated that the invention may be used in other applications , for example imprint lithography , and where the context allows , is not limited to optical lithography . in imprint lithography , a topography in a patterning device defines the pattern created on a substrate . the topography of the patterning device may be pressed into a layer of resist supplied to the substrate whereupon the resist is cured by applying electromagnetic radiation , heat , pressure , or a combination thereof . the patterning device is moved out of the resist leaving a pattern in it after the resist is cured . the terms “ radiation ” and “ beam ” used herein encompass all types of electromagnetic radiation , including ultraviolet ( uv ) radiation ( e . g . having a wavelength of or about 365 , 355 , 248 , 193 , 157 , or 126 nm ) and extreme ultra - violet ( euv ) radiation ( e . g . having a wavelength in the range of 5 - 20 nm ), as well as particle beams , such as ion beams or electron beams . the term “ lens ”, where the context allows , may refer to any one or combination of various types of optical components , including refractive , reflective , magnetic , electromagnetic , and electrostatic optical components . while specific embodiments of the invention have been described above , it will be appreciated that the invention may be practiced otherwise than as described . for example , the invention may take the form of a computer program containing one or more sequences of machine - readable instructions describing a method as disclosed above , or a data storage medium ( e . g . semiconductor memory , magnetic or optical disk ) having such a computer program stored therein . the descriptions above are intended to be illustrative , not limiting . thus , it will be apparent to one skilled in the art that modifications may be made to the invention as described without departing from the scope of the claims set out below . it is to be appreciated that the detailed description section , and not the summary and abstract sections , is intended to be used to interpret the claims . the summary and abstract sections may set forth one or more but not all exemplary embodiments of the present invention as contemplated by the inventor ( s ), and thus , are not intended to limit the present invention and the appended claims in any way . embodiments of the present invention have been described above with the aid of functional building blocks illustrating the implementation of specified functions and relationships thereof . the boundaries of these functional building blocks have been arbitrarily defined herein for the convenience of the description . alternate boundaries can be defined so long as the specified functions and relationships thereof are appropriately performed . the foregoing description of the specific embodiments will so fully reveal the general nature of the invention that others can , by applying knowledge within the skill of the art , readily modify and / or adapt for various applications such specific embodiments , without undue experimentation , without departing from the general concept of the present invention . therefore , such adaptations and modifications are intended to be within the meaning and range of equivalents of the disclosed embodiments , based on the teaching and guidance presented herein . it is to be understood that the phraseology or terminology herein is for the purpose of description and not of limitation , such that the terminology or phraseology of the present specification is to be interpreted by the skilled artisan in light of the teachings and guidance . the breadth and scope of the present invention should not be limited by any of the above - described exemplary embodiments , but should be defined only in accordance with the following claims and their equivalents . | 6 |
the concept is based on use of a regular 2 - 4 ″ pipe in carbon steel as carrier pipe and conduit for hydrate inhibitor 31 . this pipe also provides mechanical protection , stress relief and corrosion protection for all the internal components . all small bore tubing such as conduits for supply of chemicals 32 , conduits for hydraulic power fluid ( control system ) and electrical conductors 33 are accommodated inside the outer carrier 31 . the concept is illustrated in fig3 where the carrier pipe 31 ( hydrate inhibitor conduit ) contains a conduit for low capacity supply of chemicals , e . g . scale inhibitor or wax inhibitor , and an electrical cable 33 , e . g . a quad , metal clad . additionally there is provided a wire or a fibre rope 34 as well as a clamp / strap or other form of bundling mechanism 35 . the reason for this design is that the carrier pipe may be constructed from low cost carbon steel and protected against sea water based corrosion by means of coating and anodes , typically from zinc or aluminium as per standard sub sea design . the carrier and small bore tubes require no protection against common hydrate preventing chemicals , which are typically methanol or glycol . neither of the chemicals are good electrical insulators nor function as electrolytes thus facilitating corrosion . in such a medium a mixture of different metals may be pursued without risk of corrosion thus facilitating selection of material for each small bore tube according to service condition . control lines , for instance , are subject to extreme cleanliness requirements , this has often resulted in selection of 22 % cr or 25 % cr alloys for such service . it may happen occasionally that there is a requirement for bleeding back live hydrocarbons from the flow line through the hydrate inhibitor line , such that the inner surface of the carrier 31 is exposed to corrosive well fluids . such occurrences are rare and mostly of short duration and does not involve corrosion of any significance . many operators do not include this facility at all . a key feature in this methodology is the choice of electric conductors 33 and shielding against hydrate inhibitors , especially methanol . it is known that methanol acts aggressively on some isolators . it is therefore a requirement on control cables that all materials are compatible with methanol . the production of electric cable terminator penetrations in order to keep methanol away from other electrical parts is also problematic . according to the present invention , the electric conductors 33 , preferably arranged as quads , are laid down in welded diffusion resistant pipes with welded connections at both ends . this entails that the methanol only encounters extruded , rolled or welded metal surfaces along the entire length of the service pipeline , including the termination . such metal clad cables 33 are common in oil wells . they are in particular used for down - hole instrumentation and are designed for durable use in wells encountering high temperatures up to 150 ° c ., and are commonly available . typical voltages are 2 - 3 kv , i . e . voltages above the normal choice for control systems in sub - sea wells . in the design practice followed in the north sea , where the multiphase transport usually is protected against hydrates in the steady state by means of isolation and the maintenance of high temperatures through the entire transport distance , the diameter of the service pipeline only varies marginally for large or small fields , since only one well is injected with hydrate inhibitors at the time ( other oil fields may have may have other requirements and needs for methanol ). however , the dimensions of all the other pipes and electric conductors are dependent of the number of wells , e . g . the flow capacity requirement for a small number of wells is smaller than for a field with many wells being served by the same control cable . small fields only require pipes with small cross - sections as compared to the length of the control cable . since these pipes and electric conductors occupy space in the external pipeline for hydrate inhibitors and contribute to the reduction of the flow capacity , the arrangement according to the present invention will be especially suited for smaller fields . a larger number of larger pipes placed in the external pipeline will lead to a disproportionately large diameter of the external pipeline , driving up the price of this pipe even if the applied material is comparatively cheap . a pipe - based design with the same pipe specifications as for all other small pipes is usually applied for a control cable , in order to maintain symmetry in design and of mechanic forces . this often results in the guiding of low - dose chemicals , such as deposit and wax inhibitors , through over - sized and thereby unnecessarily expensive pipes ( the dimension usually is decided by the largest user , most often the low pressure supply to the control system ). for high - pressure fields , the requirements for a relatively large wall thickness of the external pipe increases , in addition to the increased requirements for the small , internal pipes for withstanding larger collapsing pressures . however , the requirement for the internal pressure capacity will increase correspondingly for all internal pipes ( this also applies for the control system described in this specification . note that for a traditional supply system with a separate pipes for control of the xmt - actuators , also known as the 207 bar system , the requirements for internal pressure will not increase . the system described here does not utilize a separate 207 bar pipe ). therefore , it may be concluded , as also may be shown by simple calculations , that the positioning of small pipes in the hydrate inhibitor does not increase the requirements for their wall thickness . the internal pressure is the deciding factor . small pipes usually have a higher capacity for external pressures than for internal pressures . it is only the number and the cross - sections of the internal pipelines that drive up the dimension of the external pipeline in regard to a conventional concept as shown in fig1 and 2 . the most important consideration in regard to a practical implementation of a control cable of this kind is the fabrication of the pipeline . two methods may be used : 1 . pulling the center element trough an already welded external pipeline , or 1 . pulling the center element trough an already welded external pipeline several kinds of pipes suited as an external pipeline according to the present invention are offered on the marked . industrial pipes , suited for a large number of umbilical operations and high degrees of deformation without becoming oval , are offered for umbilical applications . such pipes are suitable for external pipeline applications . 12 meter long pipes , typically seamless pipes , are also delivered for butt welding from most of the larger steelworks . for pulling the center element 36 through the external pipe one can envisage a pipe section of limited length being rolled out on a flat surface , i . e . on shallow waters from a barge or from a vehicle on land , e . g . a shut down railway or airport , such that the pipe 31 rests perfectly straight and level . it will then be possible to pull a center element trough an external pipeline length 31 . typically , the external pipeline 31 is filled with inhibited water , while the internal pipelines 32 , 33 are filled with air in order to reduce frictional forces . the pulling wire 34 may be shot hydraulically through the external pipeline 31 with the aid of a plug , while the external pipeline 31 is filled with for example inhibited water . when the central element 36 is pulled though the external pipeline 31 , a production length is completed . the assembly of the external pipeline 31 and the central element 36 can be stored in a straight configuration or coiled on a carousel or reel . the internal friction in the coiled state will prevent large displacements of the central element 36 with respect to the external pipeline 31 . finally , the cable sections are joined together and the entire cable is coiled up on a carousel or reel for later unrolling to an installation carousel or reel on a laying vessel , alternatively the entire cable is coiled up directly on an installation reel , whereupon the latter is transferred to a laying vessel . it is also possible to guide the bundle of internal pipes 32 , 33 through a vertically positioned external pipeline 31 , e . g . on a barge . in this case , the pulling wire 34 probably may be omitted entirely . the joining of small pipes and metal clad , electric conductors is a standard practice in the industry . in an alternate embodiment , it would be advantageous to fabricate an external pipeline 31 around the central element 36 . this will cut down the number of operation steps , but will also require substantial capital investment for suitable equipment for the production of suitable pipes and their welding . the welding of pipes is known per se and will not be further elaborated . the described concept implies a risk for tensioning the central element 36 when the external pipeline is reeled , as it is impossible to control that the that all the smaller pipes are centered in the middle , even if the purpose of the shown radial spacers is to center the smaller pipelines . this may be solved by giving the central element 36 , i . e . the small pipes 32 and electric conductors 33 , an undulating — or spiral configuration in the lengthwise direction as compared to the middle point of the external pipeline 31 . thereby the pipelines 32 , 33 may be both compressed and tensioned without imposing unnecessary stress and strain . a horizontally oriented pulling operation will automatically result in some slack of the internal pipes 32 as a result of the catinary suspension between the spacers 35 (?). the central element 36 may be arranged with a number of parallel pipelines or as a spiral - configured bundle . the described configuration is cost saving in regard materials as compared to the established alternatives , shown in fig1 and 2 , in the following respects . hydrate inhibiting pipes of carbon steel without the need for expensive alloys are used . this is shown in fig2 . only one cable has to be laid . no strapping operations requiring stops are necessary . this is shown in fig1 . only a few small pipes and electric cables are necessary . this is described above in regard with the rationalization of the control system . robust outer surfaces on the cable are provided , typically 3 . 5 - 4 mm steel , that are well suited for the pulling in j - pipes . this feature , together with electric conductors that are designed for high temperatures , e . g . 150 ° c ., makes it possible to lay down the cable in the same trench as the flow line , thereby saving costs in regard to trenching , surveying and inspection , which are the same activities as for the flow line ( the laying time does however increase somewhat as a result of the strapping operation ). it is noted that it for conventional operations has not been possible to install flow lines and control cables in the same trench because the control cable has been prone to be damaged by the flow line as a result of temperature effects , e . g . buckling , and the fact that the outer surface of a conventional control cable has a far weaker structure than the presently proposed embodiment . also , the most usual material used for electric isolation ( polyethylene ) does not withstand high temperatures . however , several projects have installed umbilicals that are strapped to the flow line with good results . as described above , a main feature of the present invention is to keep the number of internal pipelines and their cross - sections down . this is achieved by means of a minor modification in the control module of each well , and is described in the following . in a conventional control system it is usual to have two supply lines ( see fig4 which shows one of them ), one for high pressure to the down - hole safety valve 47 and one for the 207 bar pressure supply to the actuators 55 on the wellhead christmas tree . the high - pressure system 40 is characterized by a near zero fluid flow . in principle , a high pressure may be generated by the low - pressure system by means of a booster , and a low pressure may be generated by the high - pressure system by means of a reduction valve 50 . boosters are known to have been installed in new fields , but are not very common . pressure reduction valves are usually avoided in the design of sub - sea control systems for hydrocarbon installations , because they are considered to be unreliable . however , a special valve 51 of the on / off - kind only used to control a flow between two accumulators 42 , 52 has been build and tested . the valve 51 is developed by others and does not constitute a part of the present invention . it comprises of a shear seal , which is common in this kind of system and has proven to be reliable , and two pilot steps for turning on and off the hydraulic flow in the main unit . this kind of valve 51 has not been implemented yet , probably because it requires a unusually large accumulator 42 on the high pressure side 40 if it is to provide a satisfactory control of the pressures in a larger installation , in addition to that a series of error modes makes it unsuited for larger installations . however , for marginal fields with small or no interaction between the pressure supplies of the various wells , this will not present large problems . a marginal field will probably be allowed to spill smaller amounts of water - based hydraulic fluids . this entails that the entire well may be controlled by only one hydraulic pipeline . it will therefore be possible to provide a supply system for a marginal field that comprises one pipeline 32 for chemicals ( there may be need for more than one ), one pipeline as a backup for the two first , and a quad 33 . a quad 33 provides a redundant control for one well , and depending on the configuration it may also provide some redundancy for more that one well . in addition , metal clad optical fibers withstanding high temperatures may be installed in the quad - unit 33 if real - time broadband instruments are required . optical fibers installed between the electric conductors 33 will not increase the cross - section . [ 0055 ] fig4 shows the principle of a conventional hydraulic control unit for a down - hole safety valve 47 . the supply line 41 ( innermost pipeline ) with a connected accumulator 42 , leads to a control valve 45 , which in turn is connected to the valve 49 . the circuit ( somewhat simplified ) is used by most suppliers . [ 0056 ] fig5 shows a schematic of the suggested hydraulic control system of the control system . a fixed restriction 50 reduces the flow between the high - pressure accumulator 42 and the low - pressure accumulator 52 to practical values . the valve 51 is the one referred to as two pilot steps controlled by the pressure in the accumulator 42 and the accumulator 52 in the off or on mode . a control valve 53 controls the valve 56 via the actuator 55 , the low - pressure accumulator 57 providing a stable pressure in the spring chamber of the actuator . a non - return valve 54 allows dumping of the used fluid to the sea . a pressure relief system 58 is similarly provided with a non - return valve 59 that dumps used fluid to the sea . the circuit functions in the following manner : the high - pressure accumulator loads the low - pressure accumulator 52 when it has the capacity to do so , i . e . almost always . the pilots in the valve 52 are loaded when the pressure falls bellow a certain value . the loading stops when the pressure reaches its highest allowed value , typically 207 bar . a circuit like this will not be accepted for larger installations , one of the reasons being that the high pressure may propagate into the low - pressure system and harm its components in case of accidents . this may be avoided by means of security measures , e . g . the pressure relief system 58 , but in larger installations this measure is probably not sufficient in total ( i . e . production regularity ). for 1 - 3 wells the risks may be accepted by the operators under certain production conditions if the capital cost is sufficiently reduced . conventional control cables often has a copper content that is significantly higher than required in regard to the electric losses in the system . this is due to the concerns like mechanic strength and line control , the latter often being connected to complex supply systems of both effect and control signals to wells that are geographically spread out . the electric conductors 33 according to the present invention are metal clad and exhibit extreme mechanic properties ( even if these features primarily are meant for protection against aggressive chemicals ). if the actual copper requirement ( for an electric system ) is to be the deciding factor for the dimensioning of the supply system for 1 - 3 satellites , a considerable reduction of the copper content in , and thereby also the cross - section of , the conductors will be achieved . | 5 |
the method and product described herein are intended to apply to acoustical panels used as building materials . more specifically , the panels can be used as acoustical ceiling or wall panels or tiles . the detailed description of the invention is one embodiment of the invention , and it should not be construed to limit the scope of the invention in any way . in accordance with embodiments of the present invention , base mats or substrates are made from a liquid slurry that contains a mixture of fibers , fillers , and binders employing methods known in the art . the fibers comprise mineral wool and cellulosic fibers ; the fillers comprise expanded perlite , calcium carbonate , or clay ; the binders comprise starch granules . as known in the art , a homogeneous slurry containing the above - mentioned ingredients transported using a hydraulic pump from a vat to a headbox , which is placed in an elevated position so that a steady and constant flow of slurry is supplied to a mat - forming machine . the slurry is then deposited onto a moving foraminous wire to form a wet base mat . water is drained from the wire by gravity . then additional water is removed by applying a low force vacuum ( vacuuming at a rate of about 1 to about 5 inches hg ) under the wire that carries the wet base mat . the base mat may be further dewatered by pressing the mat between two rolls . yet more water can optionally be removed by applying a relatively high vacuum ( vacuuming at a rate of about 8 to about 20 inches hg ) under the wire that carries the mat . the rest of the water in the wet base mat is evaporated in an oven or kiln . afterwards , the formed base mats are slit into various sizes . the surfaces of the base mats are ground relatively smooth before a primer coating is optionally applied to the surface . the purpose of the primer coating is to provide a good base on which glue can more easily adhere and to increase the light - reflectance of the mats . subsequently , the base mats are punched and fissured to achieve desired acoustic absorbency . the punching operation provides multiple perforations on the surface of the mat at a controlled depth , size , and density ( number of perforations per unit area ). as known in the art , punching operations are carried out by pressing a plate equipped with a predetermined number of needles onto a base mat . fissuring imparts indentations of unique shapes onto the surfaces of the base mats . fissuring operations are carried out with a roll device that has a circumference upon which the complementary features or patterns are placed . both punching and fissuring open the plane surface and the internal structure of the base mats , thereby allowing air and sound waves to move in and out of the base mat structure . the next step in the process is to deposit adhesives onto the base mats . the adhesive can be sprayed or coated with a gravure roll onto the base mats . the adhesives on the base mat must be in a discrete or perforate form , for example , in the form of droplets so that the mats do not have a continuous , imperforate sheet of adhesive film on them . a continuous film of adhesives on the base mat is undesirable as discussed above . the amount of adhesives must be optimized to reduce its impact on acoustic absorbency while providing sufficient bonding to base mats . even with an optimum amount of adhesives deposited in a discrete manner , a loss of 0 . 02 to 0 . 07 in enrc or nrc is expected . in accordance with embodiments of the present invention , the total amount of adhesives ( containing water or solvent ) applied to a base mat is in the range of about 0 . 5 to about 8 grams / ft 2 , and is preferably in the range of about 1 to about 4 grams / ft 2 . alternatively , adhesives can be applied to a non - woven scrim , such as fiberglass scrim , instead of on the base mats before lamination . the amount of the adhesives used and the manner that it is deposited on the scrim are similar to the methods described for base mats . after application of adhesive , the non - woven , porous , fiberglass scrim is laminated onto the base mats . the objectives of lamination are to improve the sag performance in humid environment and to reduce the loss in nrc and enrc caused by dense scrims . as mentioned previously , the specific air flow resistance of a scrim has a significant impact on the properties of a laminated acoustical panel . in general , the air flow resistance is dependent upon basis weight , fiber coarseness , and the amount of binder and filler applied in a scrim . scrims become dense and have a high specific air flow resistance when a scrim is composed of fine glass fibers and contains a relatively high amount of binder ; scrims become porous and have a low specific air flow resistance when a scrim is composed of coarse glass fibers and contains a relatively low amount of binder . in accordance with embodiments of the present invention , scrims of high porosity are required to render a laminated acoustical panel of high peel strength , high sag resistance and low loss in acoustical absorbency . although it appears counterintuitive , a scrim in and of itself does not significantly affect acoustical absorption . in fact , affixing any plain scrim to a base mat would increase enrc slightly . however , the application of glue and coating would reduce acoustical absorption considerably , although the extent of reduction varies with different scrims . with relatively porous scrims ( specific air flow resistance of between about 10 to about 25 rayls [ pa · s / m ]), the average loss in enrc or nrc due to glue and coating is about 0 . 03 to 0 . 06 . on the other hand , with relatively dense scrims ( specific air flow resistance of between about 25 to about 100 rayls ), the average loss in enrc or nrc due to glue and coating is about 0 . 05 to 0 . 10 . in order to minimize the loss in acoustical absorbency , a scrim with less than about 25 rayls of specific air flow resistance is desired . the application of coating or paint onto a porous scrim can significantly improve scrim peel strength . the increase in peel strength ranges from about 40 to about 400 %. however , this increase is dependent upon the scrim porosity . there is little or no improvement in peel strength when the specific air flow resistance of scrims is higher than 35 rayls . by examining photographs of peeled scrims through transmitted light , it is revealed that dense scrims have a great amount of coating retained on the scrim surfaces . porous scrims made with coarse fibers , on the other hand , retain much less amount of coatings on their surfaces . a substantial amount of coating deposits onto or wicks into the base mats . once the coating is transmitted into the base mat , the coating acts as a sealant to bond the scrim to the base mats , improving scrim peel strength . for dense scrims made with fine fibers , the coatings cannot penetrate the scrim surface as greatly so they cannot contribute to the improvement in peel strength . in accordance with embodiments of the present invention , a scrim with a specific air flow resistance less than 30 rayls is laminated onto base mats to develop a significant improvement in peel strength by coatings . the basic principle to improve sag resistance by laminating a rigid scrim made from a material such as fiberglass onto a base mat is that the face of the panel is under tension during sagging , and a rigid scrim would be able to sustain the tension and restrict sagging . however , as is unexpectedly revealed through experimentation with certain embodiments of this invention , how well a scrim is actually bonded to a base mat has a direct impact on the humidity sag performance of a laminated acoustical panel . surprisingly , there is actually an inversely linear relationship between the peel strength and humidity sag of a laminated panel until the coating no longer contributes to the peel strength as a result of impermeability of the scrim . if there is no coating or if the coating is mostly on the surface of a scrim due to low porosity , the bonding between a scrim and a base mat has to rely solely on adhesives . but the amount of adhesives that can be applied is limited in order to prevent plugging of perforations in base mats . in addition , most adhesives are visco - elastic , making the bonding stretchable . therefore , glue alone will not be able to restrict the relative movement between the scrim and base mat during sagging . even a slight relative movement between a scrim and base mat would result in a significant vertical movement from the panel plane , that is , sag . when coatings penetrate through a porous scrim , additional bonding between the scrim and base mat is formed . coatings or paint contain a high amount of pigment compared to glues . the bonding provided by coatings / paint is rigid . thus , the bonding can restrict the relative movement between scrim and base mat , making the scrim an integral part of a laminated ceiling panel . a firmly bonded scrim can improve the humidity sag performance of laminated panels . since a low amount of humidity sag is highly desirable , the use of a porous scrim would add a significant advantage to laminated acoustical panels . in order to have a total sag movement less than 0 . 3 inches ( for panels with 2 ft . width and 4 ft . length ) after three cycles in a humidity chamber alternated between 75 ° f ./ 50 % rh and 104 °/ 95 % rh , the scrim must possess a specific air flow resistance less than 30 rayls , and a tensile strength of at least 10 lbf per two - inch width in either direction . the novel use of scrims with low specific air flow resistance and high porosity claimed herein would reduce the loss in acoustical absorbency caused by adhesives and coatings . the laminated acoustical panel would have an enrc of at least about 0 . 45 and nrc of at least about 0 . 5 . a base mat comprising mineral wool , newsprint fibers , expanded perlite , starch , and clay was ground to have a relatively smooth surface and coated with a primer . the base mat was then perforated as described above , the perforations having a depth of about 0 . 4 inches . the perforated base mat had and enrc of 0 . 58 . a commercially available glue xr - 3025 manufactured by hb fuller of st . paul , minn . was sprayed onto said base mats at 4 . 5 grams / ft 2 . a fiberglass scrim was then laminated onto the base mats . the scrim was purchased from owens corning , toledo , ohio . the scrim had a specific air flow resistance of 41 . 4 rayls , a basis weight of 127 . 7 g / m 2 , a thickness of 0 . 020 inches ( 0 . 5 mm ), a tensile strength of 45 . 7 lbf / 2 - inch ( 200 n / 50 - mm ) in machine direction , and a tensile strength of 42 . 1 lbf / 2 - inch ( 184 n / 50 - mm ) in cross machine direction . after lamination , the surface was sprayed with a coating . the coating contained about 80 % pigments and 20 % latex based on total solids content . it had a solids content of about 50 %. the coating was applied at about 24 grams / ft 2 . after the coating was applied , the peel strength was measured to be 325 grams per 4 - inch width . the resultant laminated panel had an enrc of 0 . 49 and a humidity sag of 0 . 729 inches . the panel without scrim had a humidity sag of 0 . 719 inch . the loss in enrc was about 0 . 09 . the example shows that with a relatively dense scrim , there is no improvement in humidity sag and scrim peel strength is low . the enrc decreased significantly . a base mat comprising mineral wool , newsprint fibers , expanded perlite , starch , and clay was ground to have a relatively smooth surface and coated with a primer . the base mat was then perforated as described above , the perforations having a depth of about 0 . 4 inches . the perforated base mat had an enrc of 0 . 46 . the commercially available glue xr - 3025 mentioned above was sprayed onto said base mats at 4 . 8 grams / ft 2 . a fiberglass scrim was then laminated onto the base mats . the scrim ( sold under the product name ultra matt ®) was obtained from gaf - elk corp . of ennis , tex . the scrim had a specific air flow resistance of 15 . 3 rayls , basis weight of 76 . 7 g / m 2 , a thickness of 0 . 023 inch ( 0 . 58 mm ), a tensile strength of 29 . 8 lbf / 2 - inch ( 130 n / 50 - mm ) in machine direction , and a tensile strength of 26 . 7 lbf / 2 - inch ( 117 n / 50 - mm ) in cross machine direction . after lamination , the surface was sprayed with a coating . the coating contained about 80 % pigments and 20 % latex based on total solids content . it had a solids content of about 50 %. the coating was applied at about 24 grams / ft 2 . before coating , the peel strength was measured at 444 grams / 4 - inch width . after coating , the peel strength was 1598 grams per 4 - inch width . the resultant laminated panel had a humidity sag of 0 . 076 inch , an enrc of 0 . 40 , and a nrc of 0 . 48 . the panel without scrim had a humidity sag of 0 . 372 inch . this example shows that with a relatively porous scrim , the peel strength was increased by 3 . 6 times after coating is applied , the humidity sag was reduced drastically , and loss in enrc was reduced to 0 . 06 . a base mat comprising mineral wool , newsprint fibers , expanded perlite , starch , and clay was ground to have a relatively smooth surface and coated with a primer . the base mat was then perforated as described above , the perforations having a depth of about 0 . 4 inches . the perforated base mat had an enrc of 0 . 46 . the glue xr - 3025 was sprayed onto the said base mats at 4 . 8 grams / ft 2 . a fiberglass scrim was then laminated onto the base mats . the scrim ( sold under the product name dura - glass ® 7615 ) was obtained from johns manville corp ., denver , co . the scrim had a specific air flow resistance of 12 . 2 rayls , a basis weight of 60 . 9 g / m 2 , a thickness of 0 . 018 inch ( 0 . 46 mm ), a tensile strength of 41 . 4 lbf / 2 - inch ( 181 n / 50 - mm ) in machine direction , and a tensile strength of 35 . 2 lbf / 2 - inch ( 154 n / 50 - mm ) in cross machine direction . after lamination , the surface was sprayed with a coating containing about 80 % pigments and 20 % latex based on total solids content . it had a solids content of about 50 %. the coating was applied at about 24 grams / ft 2 . before coating , the peel strength was 412 grams / 4 - inch width . after coating , the peel strength was 1597 grams per 4 - inch width . the resultant laminated panel had a humidity sag of 0 . 053 inch , an enrc of 0 . 39 , and nrc of 0 . 47 . the panel without scrim had a humidity sag of 0 . 372 inches . this example shows that with a relatively porous scrim , the peel strength was increased by 3 . 9 times after coating is applied , the humidity sag was reduced drastically , and loss in enrc was reduced to 0 . 07 . a base mat comprising mineral wool , newsprint fibers , expanded perlite , starch , and clay was ground to have a relatively smooth surface and coated with a primer . the base mat was then perforated as described above , the perforations having a depth of about 0 . 4 inches . the perforated base mat had an enrc of 0 . 46 . the commercially available glue xr - 3025 was sprayed onto said base mats at 4 . 8 grams / ft 2 . a fiberglass scrim was then laminated onto the base mats . the scrim ( sold under the product name gft - 25 ) was obtained from ahlstrom corp . of kotka , finland . the scrim had a specific air flow resistance of 23 . 0 rayls , a basis weight of 50 . 8 g / m 2 , a thickness of 0 . 013 inch ( 0 . 33 mm ), a tensile strength of 22 . 6 lbf / 2 - inch ( 99 n / 50 - mm ) in machine direction , and a tensile strength of 15 . 3 lbf / 2 - inch ( 67 n / 50 - mm ) in cross machine direction . after lamination , the surface was sprayed with a coating containing about 80 % pigments and 20 % latex based on total solids content . it had a solids content of about 50 %. the coating was applied at about 24 grams / ft 2 . before coating , the peel strength was 329 grams / 4 - inch width . after coating , the peel strength was 1596 grams per 4 - inch width . the resultant laminated panel had a humidity sag of 0 . 102 inches , an enrc of 0 . 37 , and an nrc of 0 . 43 . the panel without scrim had a humidity sag of 0 . 372 inches . this example shows that with a medium porosity scrim , the peel strength was increased by 4 . 9 times after coating is applied , the humidity sag was reduced significantly , and loss in enrc was 0 . 09 , similar to the results from the dense scrim . the following table 1 illustrates comparative test results showing the relationship between peel strength , specific air flow resistance and humidity sag for the above examples . | 2 |
in the following descriptions , parts of the power module of the present invention which are similar to corresponding parts of the power module shown in fig5 have been given corresponding reference numerals and need not be further redescribed . in a first example of the present invention , aluminum of 99 . 99 % in purity was set in a crucible formed at an upper portion of a furnace 9 , and a plurality of ceramic substrate boards 2 of aluminum nitride were set on an inside bottom portion of the furnace 9 below the crucible . the crucible was closed by a piston 10 and the furnace 9 was filled with nitrogen gas . then , the furnace 9 was heated at 750 ° c . by a heater 11 to melt the aluminum in the crucible . the molten aluminum 13 was pushed out by the piston 10 through a narrow conduit 12 connecting between a center bottom portion of the crucible and the inside bottom portion of the furnace 9 , so that the molten aluminum 13 was poured on the ceramic substrate boards 2 until the hight of the molten aluminum 13 on the ceramic substrate boards 2 reached a predetermined value . then , the molten aluminum 13 on the ceramic substrate boards 2 was cooled and solidified gradually , to form an aluminum base plate 7 bonded directly on the ceramic substrate boards 2 . thus obtained aluminum base plate 7 had a thickness of 5 mm and a proof stress of 40 mpa . the value of the proof stress was measured along jis z2241 a test piece of jis z2201 . then , the base plate 7 with the ceramic substrate boards 2 was taken out from the furnace 9 in order to form a circuit portion on the ceramic substrate board 2 . a desired pattern of a brazing material consisting of al in an amount of 87 . 5 % by weight and si in an amount of 12 . 5 % by weight ( not shown ) was printed by using a screen printer , and dried at 80 ° c . an aluminum rolled plate of a desired pattern was placed as a metal layer 3 on the dried brazing material , and heated at 575 ° c . in a vacuum furnace . then , an electroless nickel plating layer 8 was formed on the metal layer 3 and a semiconductor tip 1 was fixed on the metal layer 3 through the plating layer 8 and a brazing material layer 4 to form a power module as shown in fig2 . a thermal cycle test was performed to evaluate the power module . after the thermal cycle of 4000 times , no change was recognized on the boundary surface between the ceramic substrate layer 2 and the base plate 7 . a power module having a metal - ceramic circuit substrate board as shown in fig2 was formed under the same conditions as in the example 1 except that the thickness of the aluminum base plate 7 was change from 5 mm to 1 mm . a thermal cycle test was performed to evaluate the power module . after the thermal cycle of 4000 times , no change was recognized on the boundary surface between the ceramic substrate layer 2 and the base plate 7 similar to the example 1 . a power module having a metal - ceramic circuit substrate board as shown in fig2 was formed under the same conditions as in the example 1 except that the thickness of the aluminum base plate was change from 5 mm to 10 mm . a thermal cycle test was performed to evaluate the power module . after the thermal cycle of 3000 times , no change was recognized on the boundary surface between the ceramic substrate layer 2 and the base plate 7 . a power module having a metal - ceramic circuit substrate board as shown in fig2 was formed under the same conditions as in the example 1 except that the thickness of the aluminum base plate was change from 5 mm to 30 mm . a thermal cycle test was performed to evaluate the power module . after the thermal cycle of 3000 times , no change was recognized on the boundary surface between the ceramic substrate layer 2 and the base plate 7 similar to the example 3 . a power module having a metal - ceramic circuit substrate board as shown in fig2 was formed under the same conditions as in the example 1 except that the material of the base plate 7 was changed from aluminum of 99 . 99 % in purity to aluminum alloy consisting of al in an amount of 95 . 5 % by weight and cu in an amount of 4 . 5 % by weight . the base plate 7 had a thickness of 5 mm and a proof stress of 95 mpa . a thermal cycle test was performed to evaluate the power module . after the thermal cycle of 3000 times , no change was recognized on the boundary surface between the ceramic substrate layer 2 and the base plate 7 similar to the example 3 . a power module having a metal - ceramic circuit substrate board as shown in fig2 was formed under the same conditions as in the example 1 except that the material of the base plate 7 is changed from aluminum of 99 . 99 % in purity to aluminum alloy consisting of al in an amount of 87 . 5 % by weight and si in an amount of 12 . 5 % by weight . the base plate 7 had a thickness of 5 mm and a proof stress of 320 mpa . a thermal cycle test was performed to evaluate the power module . after the thermal cycle of 3000 times , no change was recognized on the boundary surface between the ceramic substrate layer 2 and the base plate 7 similar to the example 3 . a power module having a metal - ceramic circuit substrate board as shown in fig2 was formed under the same conditions as in the example 1 except that the material of the ceramic substrate board 2 is changed from aluminum nitride to silicone nitride . a thermal cycle test was performed to evaluate the power module . after the thermal cycle of 4000 times , no change was recognized on the boundary surface between the ceramic substrate layer 2 and the base plate 7 similar to the example 1 . a power module having a metal - ceramic circuit substrate board as shown in fig2 was formed under the same conditions as in the example 1 except that fins were provided on the base plate 7 in order to improve the heat radiation . a thermal cycle test was performed to evaluate the power module . after the thermal cycle of 4000 times , no change was recognized on the boundary surface between the ceramic substrate layer 2 and the base plate 7 similar to the example 1 . in order to form a circuit portion on an upper surface of the ceramic substrate board 2 of aluminum nitride , an actuated metal brazing material consisting of ag in an amount of 90 % by weight , ti in an amount of 5 % by weight and cu in an amount of 5 % by weight was printed by using a screen printer , and dried at 80 ° c . a cupper rolled plate was placed as a metal layer 3 on the dried brazing material , and heated at 800 ° c . in a vacuum furnace , so that the metal layer 3 was bonded on the ceramic substrate board 2 . then , an etching resist was printed on the cupper portion by using the screen printer , uv dried and subjected to etching using a ferric chloride solution to form a desired pattern 14 . the ceramic substrate boards 2 with the metal layers 3 were placed on an inside bottom portion of a furnace 9 with a bottom surface of the ceramic substrate board 2 facing upward as shown in fig3 . aluminum of 99 . 99 % in purity was set in a crucible formed at an upper portion of the furnace 9 , and the crucible was closed by a piston 10 and the furnace 9 was filled with nitrogen gas . then , the furnace 9 was heated at 750 ° c . by a heater 11 to melt the aluminum in the crucible . the molten aluminum 13 was pushed out by the piston 10 through a narrow conduit 12 connecting between a center bottom portion of the crucible and the inside bottom portion of the furnace 9 , so that the molten aluminum 13 was poured on the ceramic substrate boards 2 until the bight of the molten aluminum 13 on the ceramic substrate boards 2 reached a predetermined value . then , the molten aluminum 13 on the ceramic substrate boards 2 was cooled and solidified gradually to form an aluminum base plate 7 bonded directly on the bottom surface of the ceramic substrate boards 2 . thus obtained aluminum base plate 7 had a thickness of 5 mm and a proof stress of 40 mpa . then , the base plate 7 with the ceramic substrate boards 2 and the metal layers 3 was taken out from the furnace 9 and a semiconductor tip 1 was fixed on the metal layer 3 through a brazing material layer 4 to form a power module as shown in fig2 . a thermal cycle test was performed to evaluate the power module . after the thermal cycle of 4000 times , no change was recognized on the boundary surface between the ceramic substrate layer 2 and the base plate 7 . a plurality of ceramic substrate boards 2 of aluminum nitride were bonded on a base plate 7 of aluminum under the same conditions as in the example 1 . as shown in fig4 , a furnace 15 is used and aluminum of 99 . 99 % in purity was set in a crucible formed at an upper portion of the furnace 15 . a plurality of ceramic substrate boards 2 of aluminum nitride bonded on the base plate 7 were set on an inside bottom portion of the furnace 15 below the crucible with the ceramic substrate board 2 facing upward . a mold 18 having a mortise of a desired circuit pattern was placed on each ceramic substrate board 2 . the crucible was closed by a piston 10 and the furnace 15 was filled with nitrogen gas . then , the furnace 15 was heated at 750 ° c . by a heater 11 to melt the aluminum in the crucible . the molten aluminum 13 was pushed out by the piston 10 through a narrow conduit 16 and narrow conduits 17 a , 17 b and 17 c connecting between a center bottom portion of the crucible and the molds 18 . a heat sink 19 was arranged at under side of the base plate 7 in order to cool and protect the base plate 7 . the pushed out molten aluminum 13 was poured on the ceramic substrate board 2 in the mold 18 until the hight of the molten aluminum 13 on the ceramic substrate board 2 reached a predetermined value . then , the molten aluminum 13 on the ceramic substrate board 2 was cooled and solidified gradually to form a metal layer 3 on the ceramic substrate board 2 . thus obtained aluminum base plate 7 had a thickness of 5 mm and a proof stress of 40 mpa . the base plate 7 with the ceramic substrate boards 2 and the metal layers 3 was taken out from the furnace 15 . a semiconductor tip 1 was fixed on the metal layer 3 through a brazing material layer 4 to form a power module as shown in fig2 . a thermal cycle test was performed to evaluate the power module . after the thermal cycle of 4000 times , no change was recognized on the boundary surface between the ceramic substrate layer 2 and the base plate 7 similar to the example 1 . a following sample was prepared for comparison . in order to form a circuit portion on an upper surface of a ceramic substrate board of aluminum nitride , a brazing material consisting of al in an amount of 87 . 5 % by weight and si in an amount of 12 . 5 % by weight was printed on the upper surface of the ceramic substrate board 2 by using a screen printer to form a desired pattern , and dried at 80 ° c . an aluminum rolled plate of a desired pattern was placed on the brazing material . the same brazing material was printed entirely on a lower surface of the ceramic substrate board , an aluminum rolled plate of a desired pattern was placed thereon , and heated at 575 ° c . in a vacuum furnace . then , the ceramic substrate board was subjected to an electroless nickel plating . three sheets of the ceramic substrate board thus obtained were fixed by brazing on an aluminum base plate having a thickness of 5 mm and a purity of 99 . 99 % which was subjected to an electroless nickel plating . a semiconductor tip was fixed on the aluminum layer formed on the ceramic substrate board to form a power module as shown in fig5 . a thermal cycle test was performed to evaluate the power module , as like as the examples . after the thermal cycle of 1000 times , cracks were recognized in the brazing material layer on the boundary surface between the ceramic substrate board and the base plate . a following sample was prepared for comparison . a power module as shown in fig5 was formed under the similar manner as in the comparative example 1 except that the material of the base plate was changed from aluminum to a cupper molybdenum alloy of 5 mm in thickness . a thermal cycle test was performed to evaluate the power module , as like as the examples . after the thermal cycle of 3000 times , cracks were recognized in the brazing material layer on the boundary surface between the ceramic substrate layer 2 and the base plate 7 . a following sample was prepared for comparison . a molten aluminum as shown in the example 1 was contacted directly to both surfaces of a ceramic substrate board of aluminum nitride , cooled and solidified to form aluminum layers . then , in order to form a circuit portion on one of the both surfaces of the ceramic substrate board , an etching resist was printed on the one surface by using a screen printer , uv dried and subjected to etching using a ferric chloride solution to form a desired circuit pattern . the ceramic substrate board with the circuit pattern was subjected to an electroless nickel plating . three sheets of the ceramic substrate board thus obtained were fixed by brazing on an aluminum base plate subjected to an electroless nickel plating and having a thickness of 5 mm and a purity of 99 . 99 %. further , a semiconductor tip was provided on each of the substrate boards to form a power module as shown in fig5 . a thermal cycle test was performed to evaluate the power module , as like as the examples . after the thermal cycle of 3000 times , cracks were recognized in the brazing material layer on the boundary surface between the ceramic substrate board and the base plate . a following sample was prepared for comparison . in order to bond three sheets of ceramic substrate board of aluminum nitride on one surface of a base plate of 99 . 99 % in purity having a thickness of 5 mm , a brazing material consisting of al in an amount of 87 . 5 % by weight and si in an amount of 12 . 5 % by weight was printed on the base plate by using a screen printer and dried at 80 ° c . a ceramic substrate board was placed on the brazing material and heated at 575 ° c . in a vacuum furnace . it was examined to form a circuit on the other side of the base plate by a brazing method similar to the above , however all of the ceramic substrate boards were cracked when the ceramic substrate boards were bonded on the base plate . a following sample was prepared for comparison . it was examined to form a power module having a metal - ceramic circuit substrate board as shown in fig2 under the same conditions as in the example 1 except that the thickness of the aluminum base plate was change from 5 mm to 0 . 5 mm . however , the base plate deformed easily because of the lack of proof stress . a following sample was prepared for comparison . it was examined to form a power module having a metal - ceramic circuit substrate board as shown in fig2 under the same conditions as in the example 1 except that the material of the base plate was changed from aluminum of 99 , 99 % in purity to aluminum alloy consisting of al in an amount of 88 % by weight , cu in an amount of 2 % by weight , mg in an amount of 3 % by weight and zn in an amount of 7 % by weight . the base plate had a thickness of 5 mm and a proof stress of 540 mpa . however , all of the ceramic substrate boards are cracked when the ceramic substrate boards were bonded on the base plate . ( 1 ) the reliability of the metal - ceramic circuit board when the cooling and heating are repeated , can be elevated remarkably , because the structure between the ceramic substrate board and the base plate is simple . specifically , aluminum or aluminum alloy is used as the material of the base plate and bonded directly on the ceramic substrate board , so that any irregularity in thermal expansion and contraction of the base plate when it is heated and cooled is eliminated , and the crack is prevented from being occurred in the contact portion of the ceramic substrate board by the softness of aluminum . ( 2 ) a high heat conductivity can be obtained because the structure between the ceramic substrate board and the base plate is simple , and the brazing material layer of low in heat conductivity can be omitted . ( 3 ) the cost can be reduced because the structure between the ceramic substrate board and the base plate is simple , so that any brazing for bonding the both can be omitted , and that any surface treatment such as plating or the brazing can be omitted . ( 4 ) cupper used conventionary as a base plate is cheap . however , the thermal expansion coefficient is larger than that of the ceramics , so that the reliability is low because a crack is formed easily on the bonding surface between the ceramic substrate board and the base plate when the heating and cooling are repeated . copper molybdenum alloy or aluminum silicon carbide composite material is low in heat conductivity and high in cost . on the contrary , aluminum is cheap and very small in proof stress , though the thermal expansion cofficient is high , so that the crack is hardly formed on the boundary surface between the ceramic substrate board and the base plate even if the heating and cooling are repeated and that high reliability can be obtained . ( 5 ) it is considered such a manufacturing method that a circuit substrate board is manufactured by bonding a base plate of aluminum , aluminum alloy , cupper , cupper molybdenum alloy , or aluminum silicon carbide composite material on a ceramic substrate board by using brazing material . however , the ceramic substrate board is deformed to a large extent and cracks are formed easily in the ceramic substrate board due to the difference in thermal expansion and reduction between the bonded base plate and the ceramic substrate board , because the thickness of the base plate is larger than the thickness of the ceramic substrate board , the bonding layer of brazing material low in flexibility is formed between the base plate and the ceramic substrate board . on the contrary , in the present invention , the above defects can be obviated , because the base plate of aluminum or aluminum alloy of less than 320 ( mpa ) in proof stress and more than 1 mm in thickness is bonded directly to the ceramic substrate board so as to have a bonding portion very high in flexibility . ( 6 ) the substrate board for the power module according to the present invention is suitable especially to control a large electric current of electric automobiles , electric cars , tooling machines or the like , because the reliability , and the yield are high and the cost is low . ( 7 ) the heat treatment is carried out in the inert gas , so that the oxidization of the material is prevented and the good bonding can be achived . further , the temperature in the furnace may be set to 550 ° c .˜ 850 ° c . while the invention has been particularly shown and described with reference to the preferred embodiments thereof , it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims . | 7 |
in accordance with the preferred process of the invention , a first titanium layer is sputter deposited from a ti target in argon onto a substrate , generally a silicon wafer having openings for the deposition of aluminum contacts , in a sputtering chamber fitted with a source of rf power connected to the substrate support . after sputter deposition of a second titanium nitride layer using an argon - nitrogen gas mixture , a small amount of oxygen is added to the argon used for sputter deposition , and the rf power is turned on , thereby forming a plasma of the oxygen adjacent to the substrate . the titanium target is simultaneously sputtered by continuing to apply a low level of dc power , about 500 watts , to the target . since only a small amount of oxygen is required to enhance the barrier properties of the titanium nitride layer , the flow of argon is continued in order to sustain the plasma . this plasma treatment forms a thin layer of tion at the surface of the titanium nitride layer , which is thick enough to provide an additional barrier against aluminum spiking , but not so thick as to reduce the resistivity of the contact . a tion layer about 20 - 100 å thick is preferred , and is formed in about 30 seconds . a final thin titanium top layer optionally can be deposited over the treated titanium nitride , also in the same sputtering chamber . this final sputter deposition provides a final metal layer over the barrier layer about 80 - 200 å thick . this step has the added advantage that the titanium target is cleaned , e . g ., any titanium nitride or titanium oxide deposited on the target during the prior tin deposition or the oxygen plasma treatment step is sputtered off , leaving a clean titanium target for deposition of the first titanium layer on the next substrate brought into the chamber . this final sputtering step eliminates the need to periodically clean the target . thus the throughput of the present process for continuous substrate processing is also improved . the substrate having the titanium - containing trilayer deposited thereon can then be transferred to an aluminum deposition chamber , also generally deposited by sputtering in argon in known manner , for forming the final aluminum contact . the initial titanium layer can be deposited over silicon , as when a contact opening is formed in the surface of a silicon wafer , or can be deposited over a dielectric silicon oxide layer . fig1 illustrates a sputtering chamber 10 suitable for carrying out the present process . the chamber 10 includes a titanium target 12 , connected to a dc power source 13 . a substrate 22 , such as a silicon wafer , having a plurality of exposed openings in which aluminum contacts are to be formed , is mounted on a substrate support 14 . the chamber 10 is also provided with a gas inlet 16 . a collimator 17 is optionally placed between the target 12 and the substrate support 14 . a source of rf power 18 is connected to the substrate support 14 . a flow of argon is started in the chamber and the electrodes powered from the dc power supply 13 , when a thin first layer of titanium is sputtered onto the substrate 22 . nitrogen is then added to the argon , sputter depositing a layer of titanium nitride onto the substrate 22 . the nitrogen flow is stopped and a mixture of oxygen and argon is added to the chamber 10 . the rf power 18 is turned on , forming an oxygen plasma in the chamber in a plasma region 20 that reacts with the titanium nitride surface to stuff the titanium nitride . the titanium target 12 is sputtered simultaneously by continuing to apply dc power to the target 12 , thus depositing a thin layer of tio 2 . after turning off the oxygen , a final layer of pure titanium is sputter deposited , e . g ., for about 3 seconds , which also cleans the titanium target 12 . the substrate 22 is then transferred to an aluminum deposition chamber . although the amount of rf power used to initiate the plasma in the chamber can vary from about 25 - 200 watts without changing the characteristics of the barrier layer obtained , high power levels increase the amount of bias seen by the substrate . thus preferably the rf power is maintained at a comparatively low level , for example about 25 - 200 watts at 400 khz . higher levels of dc power lead to formation of a thick layer of tio 2 . this is undesirable because tio 2 is an insulator that will adversely affect the resistance of the contact being made . the temperature during sputtering is also maintained on the low side , about 100 ° c ., but can be increased up to about 550 ° c . if necessary . thus the tri - part titanium - containing barrier layer and treatment thereof with oxygen plasma can all occur in the same chamber , increasing the throughput of the system . the properties of the resultant barrier layers are just as good as those made in accordance with prior art processes that require processing in more than one chamber , such as the system of liao et al which requires transfer to an rta chamber between sputtering steps . the invention will be further described in the following examples , but the invention is not meant to be limited to the details disclosed therein . a layer of titanium about 200 å thick and a layer of titanium nitride about 800 å was sputter deposited onto a silicon wafer in conventional manner using an argon gas flow of 140 sccm and applying 500 watts of dc power to the target in the chamber as in fig1 . the silicon wafer was provided with exposed contact openings less than 1 micron in diameter and having an aspect ratio greater than 2 : 1 . after deposition of the titanium and titanium nitride layers , the gas flow was changed to supply a mixture of 155 sccm of argon and 80 sccm of oxygen , and rf power of 400 khz at 25 - 50 watts was turned on . oxygen flow and rf power was continued for 30 seconds while applying 500 watts of dc power to the titanium target . a thin layer of tion was deposited . after shutting off the oxygen and rf power , a final titanium layer was sputter deposited for 3 seconds . the wafer was transferred to an aluminum sputtering chamber and a layer of aluminum 5000å thick was sputter deposited at 300 ° c . the resultant aluminum contact was heated at 550 ° c . in nitrogen for three hours . no aluminum spiking was observed , as shown in the attached fig2 . as a control , a conventional titanium / titanium nitride stack was sputter deposited onto a silicon wafer , with no post treatment of the layer . a 5000 å thick layer of aluminum was deposited on the ti / tin stack without exposure to air . after heating at 550 ° c . for one hour , severe spiking was observed , as can be seen in fig3 the resistance properties of both low pressure and high pressure titanium nitride layers were compared before treatment with oxygen and after treatment with oxygen . the sheet resistance , resistance uniformity and stress were measured . the results are summarized below : ______________________________________ r . sub . s r . sub . s unif . stress ohms / sq % 1 - σ dynes / cm . sup . 2 c______________________________________low pressure tin before o . sub . 2 treatment 21 . 02 1 . 7 - 9 . 0 e9 after o . sub . 2 treatment 20 . 99 1 . 3 - 6 . 6 e9 high pressure tin before o . sub . 2 treatment 100 . 6 2 . 7 - 1 . 8 e9 after o . sub . 2 treatment 139 . 5 2 . 7 - 7 . 0 e8______________________________________ thus the change in film properties is minimal and the present process permits easy integration with standard integrated circuit processing . a tin barrier layer 1000 å thick was sputter deposited and plasma treated in an argon - oxygen atmosphere for 30 seconds in a single wafer chamber as in example 1 onto over 700 silicon wafers sequentially . after 425 wafers had been processed , a 1 micron thick layer of titanium was deposited to completely remove contaminants from the titanium target . deposition onto the remaining wafers was then continued . a particle count was performed on the wafers no . 0 , 75 , 425 and 720 . the results are given below as particles added per wafer . the tests were done on the deposited films after processing . ______________________________________number of wafer particles added______________________________________0 0 50 3 . 5 425 0 720 0 . 33______________________________________ this shows that very few particles are generated during the process of the invention . thus the present process is eminently suitable for mass production . although the invention has been described in terms of particular embodiments , one skilled in the art would know how to vary deposition conditions and times and equipment without departing from the spirit of the invention , and these variations are meant to be included herein . the invention is only to be limited by the scope of the appended claims . | 2 |
the complicated lithography required to connect the electrodes of the philips mim capacitor restricts that capacitor to just a few layers ( e . g ., three metal layers ). the present inventors have devised a method to form a mim capacitor (“ mimcap ”) having up to fifteen plates , or any number of plates , constrained only by the thicknesses of the deposited layers and the dimension of the cavity within which the mimcap is formed . referring now to fig2 , an opening such as cavity 210 is formed in a substrate 201 , according to a patterned mask . the mask may be , for example , oxide hardmask 203 on top of pad nitride 202 . the substrate may be a semiconductor wafer , which may be , for example , a silicon or gallium nitride substrate , and can be a semiconductor - on - insulator ( soi ) substrate . the substrate can be heavily doped to serve as a capacitor plate , for example , silicon with arsenic ( as ) dopant at 1e19 to 5e21 , or the capacitor plates can be formed with the metal layers only and the substrate can be undoped . the invention is not limited to particular dimensions of cavity 210 , but it can be about 1 . 5 micron across and 30 micron depth . the opening of cavity 210 can be the critical dimension ( the minimum dimension patternable by the lithography used to form devices ( not shown ) in or on substrate 201 ). cavity 210 can be a trench ( formed according to a generally rectilinear pattern with a length and width ), a pore ( formed according to a circular pattern ), an annulus , or an opening formed according to a pattern of any other shape . dielectric layer 221 can be formed over the sidewalls and bottom of cavity 210 . as shown in fig3 a , dielectric layer 221 can be a conformal layer having substantially uniform thickness on all surfaces . layer 221 can be thermally grown , or formed by conventional deposition such as plasma - enhanced chemical vapor deposition ( pecvd ) or atomic layer deposition ( ald ). in embodiments , layer 221 is high - k dielectric having dielectric constant greater than 2 . 5 , and can have dielectric constant in the range of 15 to 20 , or even greater than 20 . layer 221 can be any interlayer dielectric material ( ild ), which can be an high k material such as hafnium oxide ( hfo2 ), hafnium silicate , zirconium oxide , aluminum oxide or zirconium silicate . layer 221 can also be any other dielectric compound , and can be a combination of dielectric materials . dielectric layer 221 can range in thickness from about 20 angstroms to about 50 angstroms , and is preferably at least 15 angstrom thick . conformality of +/− 20 % is desirable , but can be more relaxed as long as no substantially weak spots exist in the dielectric film which could cause premature breakdown in operation . fig3 b illustrates a cross section at cut ‘ 3 b ’, if cavity 210 is a pore . fig4 a shows first conductive layer 231 formed over dielectric layer 221 . first conductive layer 231 is preferably a conformal layer , which can be a metal layer and can be formed by known processing such as ald . second dielectric layer 222 is formed over first metal layer 231 . a second conductive layer 241 can be formed over second dielectric layer 222 . like the first conductive layer , the second conductive layer 241 can be formed of metal . reference throughout the following description to ‘ metal ’ refers to any conductive material . the sequence of dielectric , first metal , dielectric , and second metal can be repeated numerous times . for example , repeating n = four times would produce a structure with n + 1 = 5 first metal layers interleaved with 5 second metal layers , with dielectric separating adjacent metal layers . the stack can be completed , after repeating the first four layers as desired ( or not repeating even once ), by depositing a final dielectric layer that fills any remaining space within cavity 210 . such a final stack would have an equal number of first and second metal layers . alternatively , after forming just the first four layers , or after repeating the four - layer sequence ‘ n ’ times , the stack can be completed by depositing another dielectric layer ( 223 in fig4 a if n = 0 ), then a final first metal layer ( 232 if n = 0 ), and finally a final dielectric layer ( 224 if n = 0 ) that fills any remaining space within cavity 210 . the stack in such an embodiment would have 1 + n second metal layers and would have 2 + n first metal layers . fig4 b is a cross section at cut 4 b for a pore - type embodiment at an intermediate stage after depositing dielectric 223 onto second metal layer 241 . the thickness of the metal is determined by structural integrity of the metal and the conductivity requirement as well as the number of layers desired and the dimension of the cavity . typical thickness ranges between 50 angstroms and 500 angstroms with 100 a to 200 a being the preferred thickness . the metal layers can be deposited with typical conformal thin film deposition techniques . for cavities with high aspect ratios , ald can be the preferred technique . conformality of +/− 50 % is desirable but the metal layers do not necessarily need to be free of thin spots . fig5 a illustrates just three metal layers ( i . e ., n = 0 ), but the mim capacitor according to the present invention can have many more metal layers . the simple mim capacitor of fig5 a has two first - type metal layers 231 and 232 , one second metal layer 241 , and four dielectric layers 221 , 222 , 223 , and 224 . all dielectric layers of the present mimcap can be the same dielectric material , or some or each dielectric layer could comprise different dielectric materials . similarly , all dielectric layers can be formed according to the same process , but the invention is not so limited . all first - type metal layers can be , but are not necessarily , the same material , so long as all of the first - type metal layers can be selectively etched relative to all the second - type metal layers . similarly , all second - type metal layers can be , but are not necessarily , the same material , so long as all of the second - type metal layers can be selectively etched relative to all the first - type metal layers . fig5 b illustrates a cross section at cut ‘ 5 b ’ of a pore embodiment having four metal layers , two being first - type metal layers 231 and 232 and two being second - type metal layers 241 and 242 . five dielectric layers 221 , 222 , 223 , 224 , and 225 isolate each metal layer from the next adjacent metal layer or from the substrate 201 . the last dielectric layer 225 fills the cavity inner core . as noted , the materials of the first - type and second - type metal layers are selected such that a first selective etch recesses just one set ( ie , all the first - type or all the second - type metal layers ) and a second selective etch recesses just the other set . some selective etch rates are listed in hussein , et al ., metal wet etch process development for dual metal gate cmos , electrochemical and solid - state letters , 8 ( 12 ) g333 - g336 ( 2005 ). as one example , the first - type metal layers could be formed of pvd tin and the second - type metal layers could be formed of pvd tasin ( si - 30 %), and the first and second etches could be sc2 and hf . sc2 chemistry ( di : h2o2 : hcl at a ratio of 10 : 1 . 1 : 1 ) at 60 c can etch tin at 10 a / min while only etching tasin at 0 . 01 a / min , whereas hf chemistry ( h2o : hf ) at a ratio of 50 : 1 at 60 c only etches tin at 1 . 32 a / min while etching tasin at 33 . 6 a / min . an alternative hf etch could be h2o : hf at a ratio of 10 : 1 at 25 c , which only etches tin at 2 . 47 a / min while etching tasin at 50 . 3 a / min . the metal materials and etch chemistries can be selected according to design requirements . in preferred embodiments , all first - type metal layers ( whether or not formed of the same metal composition ) be selectively etched by a single etch step ( a “ first etch ”) that substantially does not etch the second - type metal layers , and all second - type metal layers ( whether or not formed of the same metal composition ) be selectively etched by a single etch step ( a “ second etch ”) that substantially does not etch the first - type metal layers . after depositing the complete sequence of layers , the structure can be planarized and polished as per fig6 . this step can be achieved using chemical mechanical polish ( cmp ). each layer of the mim stack can have a portion extending generally parallel to the sidewalls of cavity 210 . thus removing all overburden down to the substrate surface can expose a cross section of the stack , exposing an edge of every layer of the mimcap stack . a mask layer 250 can be deposited and patterned to expose a first electrode region 251 of the planarized surface , which region can extend from the cavity sidewall to the last ( innermost ) dielectric layer . so long as the first electrode region extends in a first direction to expose an edge segment of each metal layer of the first type ( or each metal layer of the second type ), then a selective etch can recess all the first - type ( 23 x ) metal layers ( or all the second - type metal layers ), without significantly effecting the other set . fig7 a illustrates a first selective etch to recess the edge of first - type metal layers 23 x exposed within region 251 . a cross section of the structure of a pore embodiment of fig7 a at cut ‘ 7 b ’ is shown in fig7 b . after removing first mask 250 , which can be by a conventional resist strip process , a second mask 260 can be deposited and patterned to expose a second electrode region 262 of the planarized surface . like the first electrode region , the second electrode rejoin can encompass the full set of second - type metal layers and can be patterned by a single mask . so long as it extends to expose an edge segment of each layer of the heretofore not - etched metal layer set , e . g ., the second electrode region can extend from the cavity sidewall to the last ( innermost ) dielectric layer , then a second selective etch can recess those metal layers 24 x not etched by the first selective etch . as shown in fig8 b , the second electrode region can be opposite the first electrode region , but this relative position is not required . the second electrode region can be located per convenience of the process integration . it can , e . g ., be adjacent the first electrode region . in preferred embodiments there is no overlap of the first and second electrode regions . fig8 a shows second metal layer 241 recessed by the second selective etch , and a cross section of the structure of a pore embodiment of fig8 a at cut ‘ 8 b ’ is shown in fig8 b . note that if the mim stack had more layers , for example , with three second metal layers , then all three could be exposed by a single ‘ second electrode mask ’, and all three could be recessed simultaneously by a single ‘ second selective etch ’ step . in some embodiments , the substrate can constitute a plate of the mimcap . if the substrate constituted part of the ‘ second - type ’ plate of the ultimate capacitor structure , one option would be to recess the substrate within the second electrode region , but another option would be to pattern the second electrode ( as described in conjunction with fig1 a and 10b ) such that it did not extend over the substrate . as illustrated in fig9 a , a dielectric material 270 can backfill the recesses formed by the two selective etch steps . appropriate dielectric materials include oxide , nitride , or amorphous carbon . after removing excess dielectric 270 , such as by cmp , the mimcap electrodes can be formed . according to one embodiment , a conductive film 280 can be formed over the wafer , such film in conductive contact with the exposed metal layers of the mimcap and extending over the substrate surface . fig9 b illustrates that conductive film 280 can extend over dielectric regions 270 to avoid conductive contact with corresponding metal layers . a patterning step can form a first electrode 281 that is in contact with all second - type metal layers 24 x ( and no first - type metal layers ) and a second electrode 282 that is in contact with all first - type metal layers 23 x ( and no second - type metal layers ) as illustrated in fig1 a and fig1 b . for example , continuing with the embodiment illustrated by fig7 and 8 , the first electrode 281 can contact the mimcap stack only within the first exposed region 251 so that electrode 281 connects all second metal layers but is insulated from all first metal layers by the dielectric that backfilled the recesses formed by the first selective etch . and the second electrode 282 can contact the mimcap stack only within the second exposed region , whereby electrode 282 connects all first - type metal layers but is insulated from all second - type metal layers by the dielectric backfill in the recesses formed by the second selective etch . if the substrate constituted a plate of this mimcap , then electrode 281 could be formed to connect all second - type metal layers with the substrate plate , and electrode 282 could be trimmed such that it contacts all first - type metal layers and does not contact the substrate plate . although the invention has been shown and described with respect to a certain preferred embodiment or embodiments , certain equivalent alterations and modifications will occur to others skilled in the art upon the reading and understanding of this specification and the annexed drawings . in particular regard to the various functions performed by the above described components ( assemblies , devices , circuits , etc .) the terms ( including a reference to a “ means ”) used to describe such components are intended to correspond , unless otherwise indicated , to any component which performs the specified function of the described component ( i . e ., that is functionally equivalent ), even though not structurally equivalent to the disclosed structure which performs the function in the herein illustrated exemplary embodiments of the invention . in addition , while a particular feature of the invention may have been disclosed with respect to only one of several embodiments , such feature may be combined with one or more features of the other embodiments as may be desired and advantageous for any given or particular application . | 7 |
the present invention is particularly suited for the rapid production and isolation of cdna libraries from small amounts of poly a + rna or mrna in a high - throughout manner . in a preferred aspect of the invention , a population of single - stranded poly a + rna or mrna is hybridized in solution with a ligand - coupled primer adapter ( non - specific or gene - specific ). as used herein , the term “ primer - adapter ” refers to a nucleic acid molecule which is capable of specifically binding ( e . g ., hybridizing ) to a template nucleic acid molecule ( e . g ., a mrna or polya + rna molecule ). in a particularly preferred embodiment of the invention , the primer - adapter allows priming of the transcription , reverse transcription , polymerization or elongation of a nucleic acid molecule complementary to all or a portion of the template nucleic acid molecule . according to the invention , the first and second strand cdna reactions are preferably performed in one tube , introducing the ligand at or near the 3 ′ end of the double - stranded cdna produced . the ligand - coupled cdna may then be isolated by binding to a solid support coupled with a hapten to which the cdna will bind through ligand - hapten interactions , thereby allowing the concentration of the cdna and exchange of the buffer without organic extraction and precipitation . subsequently , the bound cdna is released from the solid phase support by restriction enzyme digestion . this asymmetric cdna is then cloned directionally into a vector that contains the appropriate termini ( one terminus matches the restriction site used to release the cdna and the other terminus is blunt ended ). subsequent or prior to cloning into a vector , specific cdna sequences ( e . g ., genes or gene fragments ) may be selectively isolated using target - specific primer - adapters of the invention . in addition to the elimination of multiple time - consuming extractions and precipitations , the methods of the invention eliminate the need for dna adapters and cdna fractionation ( normally a necessary step to remove excess unligated adapters ). the invention thus facilitates rapid production and isolation of larger amounts of cdna and the construction of cdna libraries from nanogram amounts of poly a + rna or mrna without the need for pcr amplification . the invention also provides a simple selection technique which allows isolation of desired genes or gene fragments from the constructed cdna library . using the methods of the invention , nucleic acid molecules and in particular cdna molecules may be prepared from a variety of nucleic acid template molecules . preferred nucleic acid molecules for use in the present invention include single - stranded or double - stranded rna . more preferred nucleic acid molecules include polyadenylated rna ( polya + rna ), messenger rna ( mrna ), transfer rna ( trna ) and ribosomal rna ( rrna ) molecules , and most preferred are mrna and polya + rna molecules . the nucleic acid template molecules that are used to prepare nucleic acid or cdna molecules according to the methods of the present invention may be prepared synthetically according to standard organic chemical synthesis methods that will be familiar to one of ordinary skill . more preferably , the nucleic acid template molecules may be obtained from natural sources , such as a variety of cells , tissues , organs or organisms . cells that may be used as sources of nucleic acid molecules may be prokaryotic ( bacterial cells , including those of species of the genera escherichia , bacillus , serratia , salmonella , staphylococcus , streptococcus , clostridium , chlamydia , neisseria , treponema , mycoplasma , borrelia , legionella , pseudomonas , mycobacterium , helicobacter , erwinia , agrobacterium , rhizobium , and streptomyces ) or eukaryotic ( including fungi ( especially yeasts ), plants , protozoans and other parasites , and animals including insects ( particularly drosophila spp . cells ), nematodes ( particularly caenorhabditis elegans cells ), and mammals ( particularly human cells )): mammalian somatic cells that may be used as sources of nucleic acids include blood cells ( reticulocytes and leukocytes ), endothelial cells , epithelial cells , neuronal cells ( from the central or peripheral nervous systems ), muscle cells ( including myocytes and myoblasts from skeletal , smooth or cardiac muscle ), connective tissue cells ( including fibroblasts , adipocytes , chondrocytes , chondroblasts , osteocytes and osteoblasts ) and other stromal cells ( e . g ., macrophages , dendritic cells , schwann cells ). mammalian germ cells ( spermatocytes and oocytes ) may also be used as sources of nucleic acids for use in the invention , as may the progenitors , precursors and stem cells that give rise to the above somatic and germ cells . also suitable for use as nucleic acid sources are mammalian tissues or organs such as those derived from brain , kidney , liver , pancreas , blood , bone marrow , muscle , nervous , skin , genitourinary , circulatory , lymphoid , gastrointestinal and connective tissue sources , as well as those derived from a mammalian ( including human ) embryo or fetus . any of the above prokaryotic or eukaryotic cells , tissues and organs may be normal , diseased , transformed , established , progenitors , precursors , fetal or embryonic . diseased cells may , for example , include those involved in infectious diseases ( caused by bacteria , fungi or yeast , viruses ( including aids ) or parasites ), in genetic or biochemical pathologies ( e . g ., cystic fibrosis , hemophilia , alzheimer &# 39 ; s disease , muscular dystrophy or multiple sclerosis ) or in cancerous processes . transformed or established animal cell lines may include , for example , cos cells , cho cells , vero cells , bhk cells , hela cells , hepg2 cells , k562 cells , f9 cells and the like . other cells , cell lines , tissues , organs and organisms suitable as sources of nucleic acids for use in the present invention will be apparent to one of ordinary skill in the art . once the starting cells , tissues , organs or other samples are obtained , nucleic acid molecules ( such as mrna ) may be isolated therefrom by methods that are well - known in the art ( see , e . g ., maniatis , t ., et al ., cell 15 : 687 - 701 ( 1978 ); okayama , h ., and berg , p ., mol . cell . biol . 2 : 161 - 170 ( 1982 ); gubler , u ., and hoffman , b . j ., gene 25 : 263 - 269 ( 1983 )). as discussed , the invention provides an improvement in isolating mrna and / or polya + rna from samples . the use of the primer - adapters of the invention , which specifically recognize and bind polya + rna or mrna , allows for such selection . preferably , the primer - adapter recognizes and hybridizes to the polya tail of the mrna or polya + rna . such primer - adapters may include an primer - adapters comprising oligo ( dt ). once bound , use of the ligand portion of the primer - adapter allows isolation of the desired rna molecule . the polya + rna or mrna molecules thus isolated may then be used to prepare cdna molecules and cdna libraries using the methods of the present invention . in the practice of the invention , nucleic acid molecules and in particular cdna molecules or cdna libraries comprising one or more ligand molecules are produced by mixing a nucleic acid template obtained as described above , which is preferably a mrna molecule or a polya + rna molecule , with one or more polypeptides having polymerase activity and / or reverse transcriptase activity and with a one or more primer - adapters of the invention . under conditions favoring the reverse transcription and / or polymerization of the input nucleic acid molecule , synthesis of a nucleic acid molecule complementary to all or a portion of the template is accomplished . preferred polypeptides ( e . g ., enzymes ) having reverse transcriptase and / or polymerase activity to be used in the present invention include , but are not limited to , moloney murine leukemia virus ( m - mlv ) reverse transcriptase , rous sarcoma virus ( rsv ) reverse transcriptase , avian myeloblastosis virus ( amv ) reverse transcriptase , rous associated virus ( rav ) reverse transcriptase , myeloblastosis associated virus ( mav ) reverse transcriptase , human immunodeficiency virus ( hiv ) reverse transcriptase , retroviral reverse transcriptase , retrotransposon reverse transcriptase , hepatitis b reverse transcriptase , cauliflower mosaic virus reverse transcriptase , bacterial reverse transcriptase , thermus thermophilus ( tth ) dna polymerase , thermus aquaticus ( taq ) dna polymerase , thermotoga neopolitana ( tne ) dna polymerase , thermotoga maritima ( tma ) dna polymerase , thermococcus litoralis ( tli or vent ™) dna polymerase , pyrococcus furiosus ( pfu or deepvent ™) dna polymerase , pyrococcus woosii ( pwo ) dna polymerase , bacillus sterothermophilus ( bst ) dna polymerase , sulfolobus acidocaldarius ( sac ) dna polymerase , thermoplasma acidophilum ( tac ) dna polymerase , thermus flavus ( tfl / tub ) dna polymerase , thermus ruber ( tru ) dna polymerase , thermus brockianus ( dynazyme ™) dna polymerase , methanobacterium thermoautotrophicum ( mth ) dna polymerase , and mutants , variants and derivatives thereof . particularly preferred for use in the invention are the variants of these enzymes that are substantially reduced in rnase h activity . by an enzyme “ substantially reduced in rnase h activity ” is meant that the enzyme has less than about 20 %, more preferably less than about 15 %, 10 % or 5 %, and most preferably less than about 2 %, of the rnase h activity of a wildtype or “ rnase h + ” enzyme such as wildtype m - mlv or amv reverse transcriptases . the rnase h activity of any enzyme may be determined by a variety of assays , such as those described , for example , in u . s . pat . no . 5 , 244 , 797 , in kotewicz , m . l ., et al ., nucl . acids res . 16 : 265 ( 1988 ) and in gerard , g . f ., et al ., focus 14 ( 5 ): 91 ( 1992 ), the disclosures of all of which are fully incorporated herein by reference . any ligand to which a hapten molecule will bind may be used to form the ligand - coupled primer - adapter molecule used in the present methods . suitable ligands for this purpose include , but are not limited to : ( i ) biotin ; ( ii ) an antibody ; ( iii ) an enzyme ; ( iv ) lipopolysaccharide ; ( v ) apotransferrin ; ( vi ) ferrotransferrin ; ( vii ) insulin ; ( viii ) cytokines ( growth factors , interleukins or colony - stimulating factors ); ( ix ) gp120 ; ( x ) β - actin ; ( xi ) lfa - 1 ; ( xii ) mac - 1 ; ( xiii ) glycophorin ; ( xiv ) laminin ; ( xv ) collagen ; ( xvi ) fibronectin ; ( xvii ) vitronectin ; ( xviii ) integrins α v β 1 and α v β 3 ; ( xix ) integrins α 3 β 1 , α 4 β 1 , α 4 β 7 , α 5 β 1 , α v β 1 , α iib β 3 , α v β 3 and α v β 6 ; ( xx ) integrins α 1 β 1 , α 2 β 1 , α 3 β 1 and α v β 3 ; ( xxi ) integrins α 1 β 1 , α 2 β 1 , α 3 β 1 , α 6 β 1 , α 7 β 1 and α 6 β 5 ; ( xxii ) ankyrin ; ( xxiii ) c3bi , fibrinogen or factor x ; ( xxiv ) icam - 1 or icam - 2 ; ( xxv ) spectrin or fodrin ; ( xxvi ) cd4 ; ( xxvii ) a cytokine ( e . g ., growth factor , interleukin or colony - stimulating factor ) receptor ; ( xxviii ) an insulin receptor ; ( xxix ) a transferrin receptor ; ( xxx ) fe +++ ; ( xxxi ) polymyxin b or endotoxin - neutralizing protein ( enp ); ( xxxii ) an enzyme - specific substrate ; ( xxxiii ) protein a , protein g , a cell - surface fc receptor or an antibody - specific antigen ; and ( xxxiv ) avidin and streptavidin . most preferred for use in the methods of the invention is biotin . the ligand - coupled primer - adapter nucleic acid molecules , in which one or more ligand molecules are attached ( preferably covalently ) to one or more nucleotides of the primer - adapter molecule ( see , for example , fig1 ), may be produced using conventional organic synthesis methods that are familiar to one of ordinary skill in the art . for example , the oligonucleotide may be biotinylated at the 5 ′ terminus by first producing 5 ′ amino ( nh 2 ) groups followed by cab - nhs ester addition ( langer , p . r ., et al ., proc . natl . acad . sci . usa 78 : 6633 ( 1981 )). in a particularly preferred aspect of the invention , a primer - adapter molecule comprising one or more , two or more ; three or more or four or more ligand molecules , most preferably biotin molecules , is prepared . in addition to the ligand molecules , the primer - adapter molecule also preferably comprises one or more endonuclease cleavage sites , preferably restriction endonuclease cleavage sites . these sites facilitate the release of the newly synthesized nucleic acid molecule comprising the primer - adapter from the hapten - coupled solid support . examples of endonucleases which can be used in accordance with the invention include , but are not limited to , geneii . examples of restriction endonucleases which can be used in accordance with the invention include , but are not limited to , alui , eco47 iii , ecorv , fspi , hpai , msci , nrui , pvuii , rsai , scai , smai , sspi , stui , thai , avai , bamhi , bannii , bglii , clai , ecori , hindiii , hpaii , kpni , msei , ncoi , ndei , noti , psti , pvui , saci / ssti , sali , xbai , xhoi and i - ceui . the restriction endonuclease sites engineered into the primer - adapter molecule are preferably chosen to result in either blunt ends or sticky ends . examples of blunt - end restriction enzymes , the recognition sites for which may be engineered into the primer - adapter molecules of the invention , include without limitation alui , eco47 iii , ecorv , fspi , hpai , msci , nrui , pvuii , rsai , scai , smai , sspi , stui and thai . examples of sticky - end restriction enzymes , the recognition sites for which may be engineered into the primer - adapter molecules of the invention , include without limitation avai , bamhi , banii , bglii , clai , ecori , hindiii , hpaii , kpni , msei , ncoi , ndei , noti , psti , pvui , sacii / ssti , sali , xba , xhoi and i - ceui . in a particularly preferred aspect of the invention , the primer - adapter molecule is engineered to contain a site recognized by rare cutting restriction endonucleases , for example , those recognizing 8 or more bases ( e . g ., a 8 - basepair cutter , etc .). such restriction sites may include a noti restriction site , i - ceui restriction site , a pi - pspi restriction site , an i - ppoi restriction site , a pi - tlii restriction site and a pi - fcei restriction site . the above - mentioned restriction enzymes , and others that may be equivalently used in the methods of the present invention , are available commercially , for example from life technologies , inc . ( rockville , md .). see also roberts , r . j ., nucl . acids res . 17 ( suppl . ): r347 - r387 ( 1989 ), for other examples of restriction enzymes and their cleavage sites . once the ligand - coupled primer - adapter molecule has been obtained , it is used to produce nucleic acid molecules from the input nucleic acid using any of a number of well - known techniques . such synthetic techniques involve hybridization of the primer - adapter to the nucleic acid template and extending the primer - adapter to make a nucleic acid molecule complementary to all or a portion of the template . such synthesis is accomplished in the presence of nucleotides ( e . g ., deoxyribonucleoside triphosphates ( dntps ), dideoxyribonucleoside triphosphates ( ddntps ) or derivatives thereof ) and one or more polypeptides having polymerase and / or reverse transcriptase activity . the primer - adapters of the invention may be used in any nucleic acid synthesis reaction including cdna synthesis , nucleic acid amplification and nucleic acid sequencing , using well - known techniques . for synthesis of cdna , the primer - adapter molecules of the invention may be used in conjunction with methods of cdna synthesis such as those described in example 1 below , or others that are well - known in the art ( see , e . g ., gubler , u ., and hoffman , b . j ., gene 25 : 263 - 269 ( 1983 ); krug , m . s ., and berger , s . l ., meth . enzymol . 152 : 316 - 325 ( 1987 ); sambrook , j ., et al ., molecular cloning : a laboratory manual , 2nd ed ., cold spring harbor , n . y . : cold spring harbor laboratory press , pp . 8 . 60 - 8 . 63 ( 1987 )), to produce cdna molecules or libraries . alternatively , the primer adapter molecules of the invention may be used in single - tube synthesis of cdna molecules according to the invention . in this approach , the input nucleic acid molecule ( preferably a mrna or polya + rna molecule ) is hybridized in solution with the primer - adapter molecule of the invention , and the hybridized complex is contacted with a polypeptide ( e . g ., an enzyme ) having reverse transcriptase activity ( which is preferably any of those described above ) in the presence of dntps and cofactors needed for cdna synthesis . following first strand synthesis , the second cdna strand may then be synthesized in the same reaction vessel by a modified gubler - hoffman reaction ( d &# 39 ; alessio , j . m ., et al ., focus 9 : 1 ( 1987 )). other techniques of cdna synthesis in which the methods of the invention may be advantageously used will be readily apparent to one of ordinary skill in the art . according to the present methods , single - stranded or double - stranded nucleic acid molecules ( e . g ., cdna molecules or cdna libraries ) comprising one or more primer - adapters will be produced . such nucleic acid molecules or libraries may then be rapidly isolated from solution by binding the nucleic acid molecules to a solid support comprising one or more hapten molecules that will bind the ligands . in the practice of the invention , any solid support to which a ligand - specific hapten molecule can be bound may be used . preferred such solid phase supports include , but are not limited to , nitrocellulose , diazocellulose , glass , polystyrene , polyvinylchloride , polypropylene , polyethylene , dextran , sepharose , agar , starch , nylon , beads and microtitre plates . preferred are beads made of glass , latex or a magnetic material , and particularly preferred are magnetic , paramagnetic or superparamagnetic beads . linkage of the hapten molecule to the solid support can be accomplished by any method of hapten coupling such as covalent , hydrophobic or ionic coupling ( including coating ) that will be familiar to one of ordinary skill in the art . according to the invention , any hapten molecule having the capability of binding the ligand molecule that is coupled to the primer - adapter molecule ( and that therefore is contained in the nucleic acid molecules produced by the present methods ) may be used . particularly preferred hapten molecules for use in the invention ( which correspond in order to the ligand molecules listed above ) include without limitation : ( i ) avidin and streptavidin ; ( ii ) protein a , protein g , a cell - surface fc receptor or an antibody - specific antigen ; ( iii ) an enzyme - specific substrate ; ( iv ) polymyxin b or endotoxin - neutralizing protein ( enp ); ( v ) f +++ ; ( vi ) a transferrin receptor ; ( vii ) an insulin receptor ; ( viii ) a cytokine ( e . g ., growth factor , interleukin or colony - stimulating factor ) receptor ; ( ix ) cd4 ; ( x ) spectrin or fodrin ; ( xi ) icam - 1 or icam - 2 ; ( xii ) c3bi , fibrinogen or factor x ; ( xiii ) ankyrin ; ( xiv ) integrins α 1 β 1 , α 2 β 1 , α 3 β 1 , α 6 β 1 , α 7 β 1 and α 6 β 5 ; ( xv ) integrins α 1 β 1 , α 2 β 1 , α 3 β 1 and α v β 3 ; ( xvi ) integrins α 3 β 1 , α 4 β 1 , α 4 β 7 , α 5 β 1 , α v β 1 , α iib β 3 α v β 3 and α v β 6 ; ( xvii ) integrins α v β 1 and α v β 3 ; ( xviii ) vitronectin ; ( xix ) fibronectin ; ( xx ) collagen ; ( xxi ) laminin ; ( xxii ) glycophorin ; mac - 1 ; ( xxiv ) lfa - 1 ; ( xxv ) β - actin ; ( xxvi ) gp120 ; ( xxvii ) cytokines ( growth factors , interleukins or colony - stimulating factors ); ( xxviii ) insulin ; ( xxix ) ferrotransferrin ; ( xxx ) apotransferrin ; ( xxxi ) lipopolysaccharide ; ( xxii ) an enzyme ; ( xxviii ) an antibody ; and ( xxxiv ) biotin . for example , in a preferred aspect of the invention where the primer - adapter molecule and the newly synthesized nucleic acid molecules comprise biotin , a biotin - binding hapten such as avidin or streptavidin may be linked to the solid support . in a particularly preferred such aspect , the solid support used is avidin - or streptavidin - coupled magnetic , paramagnetic or superparamagnetic beads which are commercially available , for example , from dynal a . s . ( oslo , norway ) or from sigma ( st . louis , mo .). of course , the choice of hapten will depend upon the choice of ligand used in the production of the primer - adapter molecule ; appropriate haptens for use in the methods of the invention will thus be familiar to one of ordinary skill in the art . to isolate the nucleic acid molecules produced by the methods of the invention , the solution comprising the nucleic acid molecules which comprise the primer - adapters of the invention is contacted with the hapten - coupled solid support under conditions favoring binding of the ligand by the hapten . typically , these conditions include incubation in a buffered salt solution , preferably a tris -, phosphate -, hepes - or carbonate - buffered sodium chloride solution , more - preferably a tris - buffered sodium chloride solution , still more preferably a solution comprising about 10 - 100 mm tris - hcl and about 300 - 2000 mm nacl , and most preferably a solution comprising about 10 mm tris - hcl and about 1 m nacl , at a ph of about 6 - 9 , more preferably a ph of about 7 - 8 , still more preferably a ph of about 7 . 2 - 7 . 6 , and most preferably a ph of about 7 . 5 . incubation is preferably conducted at 0 ° c . to about 25 ° c ., and most preferably at about 25 ° c ., for about 30 - 120 minutes , preferably about 45 - 90 minutes , and most preferably about 60 minutes , to allow the binding of the ligand - coupled nucleic acid molecules to the hapten - coupled solid support . once the nucleic acid molecules have been bound to the solid phase support , unwanted or contaminant materials ( such as buffers and enzymes from first and second strand synthesis reactions , untranscribed input rna molecules , etc .) may be eliminated by simply removing them in the supernatants . for example , in a preferred aspect in which biotinylated cdna molecules are bound to a avidin - or streptavidin - coupled solid phase , the contaminants may be removed by gently aspirating and discarding the supernatants . in a particularly preferred such aspect in which avidin - or streptavidin - coupled magnetic , paramagnetic or superparamagnetic beads are used as the solid support , the nucleic acid ( e . g ., cdna )- containing beads are segregated from the supernatants using a magnet ( such as a magna - sep magnetic particle separator ; life technologies , inc .) and the supernatants are withdrawn using a pipette . prior to their release from the solid support , the immobilized nucleic acid molecules are preferably washed one or more times , for example with one of the buffered salt solutions described above , to more fully remove unwanted materials . once the contaminants have been fully removed , the nucleic acid ( e . g ., cdna ) molecules may be released from the solid support by contacting the support with an endonuclease , which may be a restriction endonuclease , that specifically recognizes the sequence engineered into the primer - adapter molecule as described above , under conditions favoring the cleavage of the recognition sequence . in a particularly preferred such aspect of the invention in which a noti and / or i - ceui recognition sequence is engineered into the primer - adapter molecule ( and is thus contained in the newly synthesized nucleic acid ( e . g ., cdna ) molecules ), the solid support is contacted with a solution comprising noti and / or i - ceui . of course , the choice of restriction enzyme used to release the nucleic acid molecules from the solid support will depend upon the specific recognition site engineered into the primer - adapter molecule and the possibility of that recognition site being present in the nucleic acid molecules . preferred conditions for release of the nucleic acid molecules ( e . g ., cdna or cdna libraries ) from the solid support include incubation at about 20 ° c . to about 40 ° c ., preferably at about 25 ° c . to about 39 ° c ., more preferably about 30 ° c . to about 37 ° c ., and most preferably about 37 ° c ., for about 30 - 180 minutes , preferably about 60 - 150 minutes , and most preferably about 120 minutes . following their release from the solid support , the nucleic acid molecules ( e . g ., cdna molecules or cdna libraries ) may be processed and further purified in accordance with the invention , or by techniques that are well - known in the literature ( see , e . g ., gubler , u ., and hoffman , b . j ., gene 25 : 263 - 269 ( 1983 ); krug , m . s ., and berger , s . l ., meth . enzymol . 152 : 316 - 325 ( 1987 ); sambrook , j ., et al ., molecular cloning : a laboratory manual , 2nd ed ., cold spring harbor , n . y . : cold spring harbor laboratory press , pp . 8 . 60 - 8 . 63 ( 1987 )), and others that will be familiar to one of ordinary skill in the art . the present invention also provides kits for use in production and isolation of nucleic acid molecules ( e . g ., cdna molecules or libraries ). kits according to this aspect of the invention comprise a carrier means , such as a box , carton , tube or the like , having in close confinement therein one or more containers , such as vials , tubes , ampules , bottles and the like , wherein a first container contains one or more primer - adapter nucleic acid molecules , which are preferably biotinylated primer - adapter nucleic acid molecules . in other aspects , the kits of the invention may further comprise one or more additional containers containing a hapten - coupled solid support , which may be any of the above - described solid supports and which is most preferably avidin - or streptavidin - coupled magnetic , paramagnetic or superparamagnetic beads . in additional aspects , the kits of the invention may further comprise one or more additional containers containing , for example , one or more nucleotides ( e . g ., dntps , ddntps or derivatives thereof ) or one or more polypeptides ( e . g ., enzymes ) having reverse transcriptase activity and / or polymerase activity , preferably any of those enzymes described above . such nucleotides or derivatives thereof may include , but are not limited to , dutp , datp , dttp , dctp , dgtp , ditp , 7 - deaza - dgtp , α - thio - datp , α - thio - dttp , α - thio - dgtp , α - thio - dctp , ddutp , ddatp , ddttp , ddctp , ddgtp , dditp , 7 - deaza - ddgtp , α - thio - ddatp , α - thio - ddttp , α - thio - ddgtp , α - thio - ddctp or derivatives thereof , all of which are available commercially from sources including life technologies , inc . ( rockville , md . ), new england biolabs ( beverly , mass .) and sigma chemical company ( saint louis , mo .). additional kits according to the invention may comprise one or more additional containers containing one or more endonucleases or restriction enzymes used for release of the nucleic acid molecules ( e . g ., cdna molecules or cdna libraries ) from the solid support . the kits encompassed by this aspect of the present invention may further comprise additional reagents ( e . g ., suitable buffers ) and compounds necessary for carrying out nucleic acid reverse transcription and / or polymerization protocols . the present invention can be used in a variety of applications requiring rapid production and isolation of nucleic acid molecules . the invention is particularly suited for isolation of mrna or polya + rna molecules , for isolation of desired nucleic acid molecules from a population of nucleic acid molecules , and for production of nucleic acid molecules ( particularly full - length cdna molecules from small amounts of mrna ). the invention is also directed to methods for the amplification of a nucleic acid molecule , and to nucleic acid molecules amplified by to these methods . according to this aspect of the invention , a nucleic acid molecule may be amplified ( i . e ., additional copies of the nucleic acid molecule prepared ) by amplifying the nucleic acid molecule ( e . g ., a cdna molecules ) of the invention according to any amplification method that is known in the art . particularly preferred amplification methods according to this aspect of the invention include pcr ( u . s . pat . nos . 4 , 683 , 195 and 4 , 683 , 202 ), strand displacement amplification ( sda ; u . s . pat . no . 5 , 455 , 166 ; ep 0 684 315 ), and nucleic acid sequence - based amplification ( nasba ; u . s . pat . no . 5 , 409 , 818 ; ep 0 329 822 ). most preferred are those methods comprising one or more pcr amplifications . the invention is also directed to methods that may be used to prepare recombinant vectors which comprise the nucleic acid molecules or amplified nucleic acid molecules of the present invention , to host cells which comprise these recombinant vectors , to methods for the production of a recombinant polypeptide using these vectors and host cells , and to recombinant polypeptides produced using these methods . recombinant vectors may be produced according to this aspect of the invention by inserting , using methods that are well - known in the art , one or more of the nucleic acid molecules or amplified nucleic acid molecules prepared according to the present methods into a vector ( see fig1 ). the vector used in this aspect of the invention may be , for example , a phage or a plasmid , and is preferably a plasmid . preferred are vectors comprising cis - acting control regions to the nucleic acid encoding the polypeptide of interest . appropriate trans - acting factors may be supplied by the host , supplied by a complementing vector or supplied by the vector itself upon introduction into the host . in certain preferred embodiments in this regard , the vectors are expression vectors that provide for specific expression of the cdna molecule or nucleic acid molecule of the invention , which vectors may be inducible and / or cell type - specific . particularly preferred among such vectors are those inducible by environmental factors that are easy to manipulate , such as temperature and nutrient additives . expression vectors useful in the present invention include chromosomal -, episomal - and virus - derived vectors , e . g ., vectors derived from bacterial plasmids or bacteriophages , and vectors derived from combinations thereof , such as cosmids and phagemids , and will preferably include at least one selectable marker such as a tetracycline or ampicillin resistance gene for culturing in a bacterial host cell . prior to insertion into such an expression vector , the nucleic acid molecules ( e . g ., cdna molecules ) or amplified nucleic acid molecules of the invention should be operatively linked to an appropriate promoter , such as the phage lambda pl promoter , the e . coli lac , trp and tac promoters . other suitable promoters will be known to the skilled artisan . among vectors preferred for use in the present invention include pqe70 , pqe60 and pqe - 9 , available from qiagen ; pbs vectors , phagescript vectors , bluescript vectors , pnh8a , pnh16a , pnh18a , pnh46a , available from stratagene ; pcdna3 available from invitrogen ; pgex , ptrxfus , ptrc99a , pet - 5 , pet - 9 , pkk223 - 3 , pkk233 - 3 , pdr540 , prit5 available from pharmacia ; and psport1 , psport2 and psv • sport1 , available from life technologies , inc . other suitable vectors will be readily apparent to the skilled artisan . representative host cells that may be used according to the invention include , but are not limited to , bacterial cells , yeast cells , plant cells and animal cells . preferred bacterial host cells include escherichia spp . cells ( particularly e . coli cells and most particularly e . coli strains dh10b and stb12 ), bacillus spp . cells ( particularly b . subtilis and b . megaterium cells ), streptomyces spp . cells , erwinia spp . cells , klebsiella spp . cells and salmonella spp . cells ( particularly s . typhimurium cells ). preferred animal host cells include insect cells ( most particularly spodoptera frugiperda sf and sf21 cells and trichoplusa high - five cells ) and mammalian cells ( most particularly cho , cos , vero , bhk and human cells ). these and other suitable host cells are available commercially , for example from life technologies , inc ., american type culture collection and invitrogen . in addition , the invention provides methods for producing a recombinant polypeptide , and polypeptides produced by these methods . according to this aspect of the invention , a recombinant polypeptide may be produced by culturing any of the above recombinant host cells under conditions favoring production of a polypeptide therefrom , and isolation of the polypeptide . methods for culturing recombinant host cells , and for production and isolation of polypeptides therefrom , are well - known to one of ordinary skill in the art . in other applications , the methods of the invention may be used to generate a gene - specific cdna library from a complex population of poly a + rna . the methods of the invention , in combination with polymorphism analysis methods such as aflp , also facilitate rapid and direct identification of transcriptional differences between two different dna populations . additionally , the primer - adapter used in the invention can be designed to contain a regulatory sequence , such as a promoter , enhancer or other regulatory region . in one such aspect , a promoter for t7 or sp6 rna polymerase may be engineered into the primer - adapter , thereby enabling the production of additional copies of the original mrna for use in amplification or subtraction . furthermore , the methods of the invention can be used to isolate poly a + rna from total rna , such as from cells , tissues , organs or organisms , or to generate a cdna library directly from total rna . in the latter application , the invention is particularly useful when the mrna of interest represents only a minute fraction of the total rna ; by the invention , this low - level mrna may be rapidly and efficiently isolated from the background of total rna and may then be rapidly and efficiently reverse transcribed into single - stranded or double - stranded cdna molecules for a variety of purposes such as cloning and / or amplification . it will be readily apparent to one of ordinary skill in the relevant arts that other suitable modifications and adaptations to the methods and applications described herein are obvious and may be made without departing from the scope of the invention or any embodiment thereof . having now described the present invention in detail , the same will be more clearly understood by reference to the following examples , which are included herewith for purposes of illustration only and are not intended to be limiting of the invention . first and second strand cdna synthesis reactions were conducted as described in the instruction manual for the superscript plasmid system ( life technologies , inc ., rockville , md . ), except that 50 - 5000 ng of mrna was used as starting material to produce a library of & gt ; 10 6 clones . the primer - adapter used in cdna synthesis contained four biotin ( b ) residues : briefly , 1 μg of the biotinylated primer - adapter was used to prime first strand synthesis for 60 minutes , in a solution containing 50 mm tris - hcl ( ph 8 . 3 ), 75 mm kcl , 3 mm mgcl 2 , 10 mm dtt , 500 μm each of datp , dctp , dgtp and dttp , 50 μm / ml bio - p - a and 10 , 000 to 50 , 000 units / ml superscript ii reverse transcriptase ( life technologies , inc .). second strand synthesis was performed for two hours at 16 ° c . using methods described previously ( okayama , h ., and berg , p ., mol . cell . biol . 2 : 161 ( 1982 ); gubler , u ., and hoffman , b . j ., gene 25 : 263 ( 1983 ); d &# 39 ; alessio , j . m ., et al ., focus 9 : 1 ( 1987 )), in a solution containing 25 mm tris - hcl ( ph 7 . 5 ), 100 mm kcl , 5 mm mgcl 2 , 10 mm ( nh 4 ) 2 so 4 , 0 . 15 mm b - nad +, 250 μm each of datp , dctp , dgtp and dttp , 1 . 2 mm dtt , 65 units / ml dna ligase , 250 units / ml dna polymerase i and 13 units / ml rnase h . during the final 30 min of the two - hour second strand cdna synthesis reaction , streptavidin paramagnetic beads were prepared . briefly , paramagnetic beads ( life technologies , inc .) were resuspended and 150 μl of bead suspension was placed into a microcentrifuge tube for each reaction . the tubes were the placed into a magna - sep magnetic particle separator ( magnet ) for two minutes , and supernatant removed by aspiration . the beads were then washed by adding 100 μl of te buffer ( 10 mm tris - hcl ( ph 7 . 5 ), 1 mm edta ) to each tube , resuspending beads , and removing supernatant after two minutes as described above . following washing , the beads were resuspended in 160 μl of binding buffer ( 10 mm tris - hcl ( ph 7 . 5 ), 1 mm edta , 1 m nacl ) and held at 25 ° c . until use in isolating cdna . after incubating the second strand cdna synthesis reaction mixtures with t4 dna polymerase , the tubes were placed on ice and the reaction terminated by the addition to each tube of 10 μl of 0 . 5 m edta . the biotinylated cdna molecules were then isolated by contacting the solution with the streptavidin - coupled paramagnetic beads . briefly , 160 μl of the beads prepared as described above were added to the cdna reaction mixture tubes , and the tubes gently mixed and incubated for 60 minutes at room temperature . tubes were then inserted into the magnet for two minutes , after which supernatants were removed and discarded . the beads were then washed by gentle resuspension with 100 μl of wash buffer ( 10 mm tris - hcl ( ph 7 . 5 ), 1 mm edta , 500 mm nacl ), followed by re - insertion into the magnet . after two minutes , supernatants were removed and discarded and the washing step repeated . following the second wash , beads were resuspended in 100 μl of wash buffer , transferred into fresh tubes , and washed twice as above ( with five minute exposures to the magnet ). following the second five - minute wash , supernatant was removed and discarded and cdna molecules were removed from the beads by incubation with noti . briefly , 50 μl of noti solution ( 41 μl of autoclaved distilled water , 5 μl of react 3 buffer ( 500 mm tris - hcl ( ph 8 . 0 ), 100 mm mgcl 2 , 1 m nacl ) and 4 μl of not i ) were added to each reaction tube and tubes mixed by gentle pipetting . tubes were incubated for two hours at 37 ° c ., then inserted into the magnet for two minutes . supernatants containing the cdna molecules were withdrawn into a fresh tube , and the beads gently resuspended in 20 μl of te buffer , re - inserted into the magnet for two minutes , and supernatants from this wash combined with those containing the cdna molecules from above . to each tube containing pooled supernatants , 70 μl of phenol : chloroform : isoamyl alcohol ( 25 : 24 : 1 ) was added and the tubes vortexed thoroughly and centrifuged at room temperature for five minutes at 14 , 000 × g . following centrifugation , 65 μl of the upper , aqueous layer were removed from each tube and transferred into fresh microcentrifiige tubes , and 32 μl of 7 . 5 m ammonium acetate , 1 μl ( 20 μg ) of glycogen and 250 μl of cold (− 20 ° c .) absolute ethanol were added to each tube . tubes were then mixed and stored on dry ice or at − 70 ° c . for 15 minutes , then centrifuged for 30 minutes at 14 , 000 × g at 4 ° c . supernatants were removed and discarded , 100 μl of 70 % ethanol were added to the pellets and the tubes were centrifuged for two minutes at 14 , 000 × g at room temperature . supernatants were removed and discarded , and the pellets were dried in a speed - vac and then dissolved in te buffer ( 10 μl for 50 - 200 ng of input mrna , or 100 μl for 200 - 5000 ng of input mrna ). final cdna yields were determined by cerenkov counting . from 10 to 50 ng of the cdna was ligated into a vector ( e . g ., pcmvsport ) and this ligation introduced into e . coli by transformation as described in the superscript plasmid system manual ( life technologies , inc . ), except the cloning vector was pre - digested with noti and smai . in one such ligation , 50 ng of vector was ligated to the cdna in a 1 . 5 ml microcentrifuge tube with 4 μl of 5 × t4 dna ligase buffer ( 250 mm tris - hcl ( ph 7 . 6 ), 50 mm mgcl 2 , 5 mm atp , 5 mm dtt , 25 % ( w / v ) peg - 8000 ) and 1 μl of t4 ligase ( 1 unit ) at 4 ° c . for 16 hours . to examine the efficiency and yield of cdna synthesis by the methods of the invention , cdna was produced as described above and the amounts produced were compared to those obtained using an alternative commercially available system ( superscript plasmid system ; life technologies , inc ., rockville , md .). briefly , after introducing the pcmv • sport - cdna ligations into max e fficiency dh5α ™ and e lectro max ® dh10b cells , the cells were plated onto ampicillin - containing plates to determine transformation efficiencies . the cdna inserts were sized by using the sp6 and t7 promoter primers and 40 cycles of pcr on 48 randomly chosen colonies for each experiment . table 1 shows a comparison of the cdna yields obtained by the methods of the present invention to those obtained using the superscript plasmid system . these results demonstrate that the present invention produces about three - to four - fold greater yields of cdna than the superscript plasmid system . furthermore , the present invention demonstrates approximately equivalent transformation efficiencies and average insert sizes to those obtained with the superscript plasmid system . thus , the present invention provides methods for the rapid and efficient production of full - length cdna molecules without the use of time - consuming and yield - reducing cdna size fractionation steps . having demonstrated that the methods of the invention produce cdna rapidly and efficiently , the efficacy of the invention in producing cdna from varying amounts of input mrna was examined . in these studies , the amount of input mrna was varied from 5 ng to 1 μg and the cdna yield , transformation efficiency and average insert size determined as above . results are shown in table 2 . these results demonstrate that the present invention is capable of producing large cdna libraries ( i . e ., & gt ; 10 5 clones ) from as little as 5 ng of input mrna . previously , pcr ( a process that biases the cdna library ) was the only method that would have enabled the production of cdna libraries from this small amount of rna . together with those above , these results indicate that the invention is capable of rapidly and efficiently producing high - quality , full - length cdna molecules from varying quantities of input mrna , including those that show a low level of expression and thus represent only a small fraction of the polya + or total rna pools . having now fully described the present invention in some detail by way of illustration and example for purposes of clarity of understanding , it will be obvious to one of ordinary skill in the art that the same can be performed by modifying or changing the invention within a wide and equivalent range of conditions , formulations and other parameters without affecting the scope of the invention or any specific embodiment thereof , and that such modifications or changes are intended to be encompassed within the scope of the appended claims . all publications , patents and patent applications mentioned in this specification are indicative of the level of skill of those skilled in the art to which this invention pertains , and are herein incorporated by reference to the same extent as if each individual publication , patent or patent application was specifically and individually indicated to be incorporated by reference . | 2 |
a method 200 for upgrading an os in accordance with the present invention is shown in fig2 . the method 200 begins by installing a temporary os file ( i . e ., the upgrade ) to a system disk ( step 202 ). the system &# 39 ; s boot pointers are updated to point to a memory location that points to the temporary os ( step 204 ) and the system is booted into the temporary os ( step 206 ). as an optional step , the user can be informed that the temporary os is running , rather than the permanent os ( step 208 ). with the temporary os operating , it is ready to accept system commands ( step 210 ). if the system command is not to make the temporary os permanent ( step 212 ), then the system processes the command as it would with any other system command ( step 214 ) and continues to accept commands ( step 210 ). if the system command is to make the temporary os permanent ( step 212 ), then the temporary os file is verified to ensure that it is not corrupted ( step 216 ). it is noted that the verification step ( step 216 ) is performed as a “ sanity check ” of the os file , and can be skipped . the boot pointers stored in the bsa on disk for the permanent os are updated to point to the current / temporary os , since the temporary os is now the permanent os ( step 218 ), and the method terminates ( step 220 ). the bsa maintains a pointer to the os file to load , and the bsa is stored in a particular area on the disk . when the temporary os is installed , a soft boot pointer is set to point to the temporary os file such that when the soft boot is initiated , the temporary os is loaded . while the temporary os is running , any type of system reboot will look to the bsa stored on disk to locate the permanent os file . essentially , making the temporary os the permanent os requires updating the boot pointer on disk to point to the temporary os . in an alternate embodiment of the present invention , the temporary os can be automatically hardened by the system , without further intervention by the user . the criteria to be applied for the automatic hardening can be supplied by the user when the os upgrade is installed , or can be supplied at a later time . for example , the user could specify that if the system runs for a predetermined period of time ( e . g ., three days ) without any errors , then the os upgrade should be made permanent . the criteria to be evaluated can be open - ended , including , but not limited to , the length of runtime without errors , a certain number errors over a given period of time , or the types of errors that can be permitted to occur . in addition , the criteria selected can be combined or performance thresholds can be established , such that the user can customize the determination whether to automatically harden the os upgrade . if the selected criteria are not met , or if a certain trigger condition is met ( e . g ., a fatal error occurs ), then the automatic hardening process is deactivated , and the user can manually harden the os upgrade , as described above . regardless of the criteria selected for the automatic hardening , the user is also able to deactivate the automatic hardening , such that a manually initiated hardening process would be required . the reason for this escape process is that the system may be running close to the threshold criteria specified by the user , but not sufficiently above the threshold to satisfy the user . for system integrity , it is better to provide the user with a way out of the automatic hardening process , than to force the user to accept a hardening he or she may be uncomfortable with . an example of the present invention as applied to the mcp os is shown as a method 300 in fig3 a and 3 b . however , the inventive principles disclosed herein can be applied to any os upgrades . the method 300 begins with a halt / load ( step 302 ). a determination is made whether the mcp currently running is a temporary mcp or a permanent mcp ( step 304 ). if the current mcp is permanent , then there is nothing further to do and the method terminates ( step 306 ). if the current mcp is temporary , then a task is created to display a message to the user indicating that the current mcp is temporary ( step 310 ) and the system then waits for system commands ( step 312 ). each system command is evaluated ( step 314 ) and if the system command is not “ cm : perm ” ( to make the current mcp permanent ), then the system command is processed as normal ( step 316 ) and the system continues to accept other commands ( step 312 ). if the “ cm : perm ” command is entered ( step 314 ), then the mcp code file is verified ( step 318 ). it is noted that the verification step is performed as a “ sanity check ” of the code file , and can be skipped . the mcpinfo array and the bsa are updated with the permanent mcp information ( step 320 ) and are saved to disk ( step 322 ). the current mcp becomes the permanent mcp and the method terminates ( step 324 ). when the display task is created ( step 310 ), it is forked off as a separate process . a message is displayed to the user indicating that the current mcp is a temporary mcp ( step 330 ). the system then waits for a response from the user or for a time limit to expire ( step 332 ). in a preferred embodiment , the time limit is 20 seconds . a determination is then made whether the user entered a response or whether the time limit expired ( step 334 ). if there was no response from the user ( meaning that the time limit expired ), then a determination is made whether the current mcp is still the temporary mcp ( step 336 ). if the mcp is still temporary , then the method waits for another response from the user or for another time limit ( step 332 ), as described above . if the user did enter a response , a determination is made whether the user entered an “ ax perm ” ( harden the soft mcp ) command ( step 338 ). if so , then the method continues by verifying the mcp code file ( step 318 ), as described above . if the user does not enter an “ ax perm ” command ( step 338 ), a check is made whether the user has entered a “ ds ” ( discontinue ) command to terminate the message display ( step 340 ). if the user has not entered a “ ds ” command , then a determination is made whether the current mcp is still the temporary mcp ( step 336 ), as described above . if the user has entered a “ ds ” command ( step 340 ) or if the temporary mcp has been hardened ( step 336 ), then the displayed message is removed because the problem has been addressed and the process ( i . e ., the waiting stack ) terminates ( step 342 ). although steps 310 - 324 and 330 - 342 are separate processes within the system , they do interact with each other . in mcp , steps 310 - 324 are referred to as a control stack and steps 330 - 342 are referred to as a waiting stack . under mcp , a screen display is divided into a number of different areas , with each area being capable of displaying information relating to different processes running under the os . when a waiting message is displayed , it is done so in a separate area of the screen from the main control area . as described above , there are two different ways for a user to harden the temporary mcp : ( 1 ) via the control stack and entering the “ cm : perm ” command ( step 314 ); and ( 2 ) via the waiting stack and entering the “ ax perm ” command ( step 338 ). if either of these methods are used to harden the mcp , the other is not needed ; this is the reason for the check made in step 336 . one mechanism of tracking when a temporary os change is performed is to set a bit in a reserved section of memory that indicates the presence of the temporary os . when this bit is encountered , a message is displayed to the user that informs them that the current os is a temporary os ( steps 310 , 330 ). when the message is acknowledged with the “ perm ” parameter ( step 338 ), the process of updating the permanent os information ( steps 318 - 324 ) is started . once completed , the reserved bit is reset and the system is considered to be running on the permanent os . a system 400 constructed in accordance with the present invention is shown in fig4 a and 4 b . the system 400 includes a disk 402 , a memory 404 , and a boot process 406 . the disk 402 includes a boot pointer 408 , a permanent os 410 , and a temporary os 412 . as shown in fig4 a , the boot pointer 408 points to the permanent os 410 and the memory 404 is loaded with the location of the temporary os 412 . when the temporary os 412 is loaded , the boot process 406 is invoked and looks to the memory 404 to determine the location of the temporary os 412 on the disk 402 . on a subsequent reboot , the memory 404 is erased , and the boot process 406 looks to the boot pointer 408 stored on the disk 402 to load the permanent os 410 . when the temporary os 412 is made the permanent os 410 , the pointer stored in the memory 404 is copied to the boot pointer 408 , such that the boot pointer 408 now points to the temporary os 412 , as shown in fig4 b . this changing of the boot pointer 408 makes the temporary os 412 permanent . it is noted that the present invention may be implemented in a variety of systems and that the various techniques described herein may be implemented in hardware or software , or a combination of both . although the features and elements of the present invention are described in the preferred embodiments in particular combinations , each feature or element can be used alone ( without the other features and elements of the preferred embodiments ) or in various combinations with or without other features and elements of the present invention . while specific embodiments of the present invention have been shown and described , many modifications and variations could be made by one skilled in the art without departing from the scope of the invention . the above description serves to illustrate and not limit the particular invention in any way . | 6 |
on fig1 is shown a working storage mv and also an associated device called &# 34 ; fault vector &# 34 ; fv for eventually locating the faults of said storage . the working storage is mounted on a wiring carrier co , such as a printed circuit board or a thin or thick film module . the storage has a plurality of identical components cll ... cmn , each of which is made up of a large scale integrated circuit chip either mounted bare and uncovered on the wiring carrier co or enclosed in a protective and terminal case joined to the carrier . both mountings permit the individual replacement of components . as shown by fig1 components cll ... cmn are laid out on the wiring carrier co in a matrix array formed by rows and columns , the two indices attached to each component identifying respectively the column ( 1 .... m ) and the row ( 1 .... n ) to which it belongs . each of the components cll ... cmn is a large scale integrated circuit , preferably mos ( metal oxide silicon ) for well known reasons . each of these components has several addresses al ... ap , each corresponding to at least one store cell capable of storing one data bit ; for ease of description , it will be assumed here that each component has p = 2 addresses ( 1024 for example ) each corresponding to a store cell . consequently , each component has x addressing inputs , one data input and one data output , as well as the usual connections for supply , validation , inhibiting and read / write selection . in these conditions , access to a given store location of any one of components cll .... cmn can be achieved by means of an addressing bunch a comprising x conductors , each one of which is connected to the addressing inputs of the same rank of every component . this access , however , is effective only for the specified address of the components of a same column whose validation inputs are connected to one of the m conductors of a validation bunch b . this is , the components of a same column constitute a block , of which each one of the p addresses has n positions and can have written in or read out a word of n bits , respectively loaded or read in parallel by means of data input and output bunches d having n conductors . the selection write / read is carried out by means of a writing validation conductor e connected to the corresponding input of each of components cll ... cmn . the operation of the working storage mv which has just been described is as follows : access to a given address aj of a given block bk is obtained on the one hand by putting the x conductors of addressing bunch a into respective logic states whose combination corresponds to the said address and on the other hand by energizing the validation conductor of bunch b corresponding to the block . hence if a word must be written into the selected address of the working storage mv , the writing validation circuit e is energized and the n bits of the word to be written are loaded in parallel to the corresponding locations of the specified address by the n conductors of the input data bunch d ; inversely , to read out a word that had first been loaded in the selected address , the validation circuit is left in the quiescent state and the n bits of the word to be read are extracted in parallel by the n conductors of the data output bunch d . of course these operations are carried out under the control of a control unit ( not shown ) connected to the addressing bunch a and validation bunch b , as well as the writing selecting circuit e . the data input and output bunches d are connected to external registers ( not shown ). before describing the fault locating device or fault vector fv , it is advisable to analyze the defects or faults that could arise in working store mv and to establish the procedure enabling them to be located . a defective store cell or circuit can either remain permanently in one or the other of the logic states 0 , 1 , or it could be &# 34 ; tied &# 34 ; to another variable , for example , because of a spurious coupling . during the operation of the store , any internal fault of a component or any fault which affects that component alone ( for example a circuit interrupted on one of its terminals ) results in anomalies in the data circuits di corresponding to the row to which the faulty component belongs when block b k corresponds to the column to which that same component belongs is brought into play . depending on the nature of the fault , these anomalies can occur when data is read out of one , several or all of the addresses aj . similarly , if each component had at each of its addresses not one but several ( y ) store cells , the anomalies could appear on one of several of the y rows of corresponding bits . however , these considerations are unimportant as far as the implementation of the invention is concerned , for which it is sufficient to determine the row and column of the matrix to which the defective components to be changed belong . if the number of store cells or of faulty circuits in a component is thus immaterial , it is important on the other hand to check that each of these cells can correctly store and give back a data bit for both binary logic states ; the necessity for this double check has consequences that will be described hereafter . apart from individual component faults , the working store mv can display wiring faults either internal or external to the component matrix , but which all give rise during operation to anomalies affecting several components : thus when anomalies affect one specific bit on all the blocks , the fault concerns the corresponding data row dl .... dn ; inversely , if the anomalies affect all the bits of a single block , the fault concerns the validation row bl ... bm of that block ; finally , anomalies affecting all the bits of all the blocks give rise to a fault concerning either the addressing bunch or else the validation circuit for writing . as already mentioned , satisfactory location of faults of the working storage mv implies that each store cell must be checked for both logic states 0 and 1 . for so doing , in accordance with the invention , one writes successively in each address of the store several test words each one of which has as many bits as a store word and between which the two logic states 0 and 1 are distributed in such a way that each bit has assumed at least once each state when all the test words have been written . after anyone test word is written in a specific address , the contents of that address is read and compared bit for bit to the original test word . any discrepancy between the bit written in and the bit read out is detected to indicate a fault of the corresponding store cell ; when this procedure has been repeated for each of the test words , it is certain that all the store cells of the address in question have been checked for both logic states and therefore that all the defective cells of that address have been brought to light . the implementation of this process raises two problems , namely on the one hand the definition of the set of test words satisfying the criteria mentioned above and on the other hand the definition of a procedure to detect and locate addressing faults by means given in the detailed description that follows . in accordance with the preferred embodiment of the invention , these two problems will be jointly resolved on the one hand through the use of a sequence of test words put in a specific order satisfying the criteria mentioned above and on the other hand through the use of a test procedure which essentially consists of : writing the sequence , repeated as many times as necessary , into the successive addresses of a same block ; starting again that operation for the same block with a cyclic permutation of the test words in the sequence until they return to their initial order ; and reproducing the whole of this process for each of the storage blocks . each writing in of test words at all the addresses is followed by the reading out of the content of each of these addresses for its comparison with the corresponding test word . the test words format corresponds to the format of the store words . in the case shown in fig2 in which the data words md processed by the working storage mv have two bytes each , with a parity bit , that is a total of 18 bits , the test words mt also have 18 bits . for each of these bits to assume at least once each logic state , it would appear that the use of whatever test word and of its complement would suffice ; however , since the inversion of a word having an even number of bits does not alter its parity bit , three test words mtl - 3 are , in fact , necessary . except for having to satisfy the above condition , these test words could have several structures and could be arranged in arbitrary order ; however , their structure and their sequence are chosen so that after they are written in consecutive addresses , the sequence s of the three test words mtl - 3 on the table of fig2 meets these various conditions . the number of test words , at least equal to three for reasons mentioned above , must satisfy an extra condition in order to be able to detact addressing faults . in case of a fault affecting addressing circuit , those addresses being effectively reached differ from the prescribed addresses by a value equal to a power of 2 , i . e . to the &# 34 ; weight &# 34 ; of the corresponding address position ; it is therefore necessary to write different test words in addresses distant from each other by whatever power of 2 , but , of course , smaller than the total number of addresses . because of the cyclic writing of the test words ( repetition of the sequence ) in the successive addresses of the block tested and taking into account the subsequent circular permutation of these test words , the last mentioned condition is satisfied if the number of test words of the sequence is different from all powers of 2 smaller than the total number of addresses . it means that for these reasons also , the sequence must have at least three test words . finally , to avoid any interference on the circuits of the store data locations belonging to all the blocks other than the one tested , it is preferable to load all the addresses of all these blocks with a neutral word mto corresponding to the combination of the logic state of the data output circuits when quiescent , namely , 18 bits in the 0 state , in the example shown in fig2 . after having briefly described the proposed test procedure , an example will now be described of the means used to implement it , that is the fault locating device or fault vector shown in fig1 . this device comprises essentially one auxiliary storage , advantageously made up of a permanent storage mp holding the test words sequence mtl ... mts . associated circuitary including gate , pl as well as shift and buffer registers ( not shown ) enable the cyclic reading of these words from any predetermined rank and their dispatch on the one hand to the data input circuits d of the working storage mv for writing in said storage and on the other hand to one of the sets of inputs of a comparison operator φ . an other set of inputs to operator φ is connected to the data output circuits d of the working storage mv . operator φ ensures the bit for bit comparison of each test word previously written in a specific address of the working storage mv with the word thereafter read at that same store address . operator φ generates an output signal having as many bits as the test words , normally all held in a normal logic state . however , if a bit of a word read in the permanent storage mp differs from the corresponding bit of the same word as previously written and then read in the working storage mv , the bit of like rank in the output signal of comparison operator 0 is switched to the state opposite the normal state . this output signal is applied to the inputs of a register n whose state identifies the rank of the differing or clashing bits and therefore the rank of the corresponding row of components . the output signal also is applied to a multiple or gate which operates gate circuits p2 that respectively control the connection of each of and thereby the column conductors bl ... bm to a corresponding position of a register m . consequently , the state of register m identifies the block and thereby the column containing a component recognized as defective by operator . registers m and n are linked with locating circuits l ( including for instance a sequential printer ) which establish the list of components found defective in the course of the test procedure . the said auxiliary storage and related devices and circuitry for carrying out the test procedure are operated either by the control unit of the data processing system adequately programmed for this purpose or else by a special , e . g . microprogrammed instruction generator g put into operation by a special triggering or enable signal f . under the control of clock signals h , said control unit or generator g supplies all the instructions required for the sequential access to successive addresses of each of the blocks of the working storage mv , the cyclic reading of the test words in the permanent auxilliary storage mp , the selection of write or read operations of the working storage and the operation of the gate circuits p1 and other devices associated with the permanent storage , as well as the comparison operator 0 , the registers m , n , the gate circuits p2 and the locating circuits l . the set of instructions required therefor will appear clearly from the following description of the flow - chart of fig3 : the combined operation of the working storage mv and of the fault locating device fv is shown in the flow - chart of fig3 . in that flow chart , a test word is designated by mti , i varying from l to s , the total number of words in the sequence ; similarly aj designates any of the addresses al ... p of a block bk corresponding to any one of the m columns of components , whereas di designates a data bit or group of data bits corresponding to any one of the n rows of components . as shown at the start of the test procedure , it will be assumed that indices i , j , k have initial values i o = 1 , j o = 1 , k o = 1 . under these conditions the reading of the flow - chart shows that during a first , preliminary step , the test word mt1 read in the permanent storage mp is simultaneously written in the first address a1 of first block b1 of the working storage mv . then indices i and j are increased simultaneously by one ( loop i ) which triggers the reading of the second test word mt2 in the permanent storage mp and its writing in the second address a2 of the first block b1 of the working storage . this procedure is repeated by simultaneously increasing indices i and j ( in loop i ) until the sequence of test words mt1 - mts is exhausted ; each of these test words is then written in the address with rank a1 - as corresponding to the first block b1 of the working storage . when the sequence of test words is thus exhausted , ( i = s ), this index is brought back to its initial value i o = 1 whereas index j is increased by one ( loop ii ). so , the test words sequence mt1 - mts is read again in the permanent storage mp and written in the consecutive addresses as + 1 - a2s of the first block b1 of the working storage mv by loop i . the preliminary stage is pursued by repetition of these procedures through the interplay of loops i and ii , which ensures the writing of sequences of test words mt1 - mts in the consecutive addresses of the first block b1 of the working storage mv repeated as many times as necessary to exhaust all the addresses of said block ( j = p ). the preliminary stage is ended by writing in the other blocks of the neutral word mto . at the end of this preliminary stage starts a procedural stage , with indices i and j being brought back to their initial values , i o and j o = 1 respectively . during this procedural stage , by the interplay of loops iii and iv , which operate respectively which operate like the loops i and ii , the content of each of consecutive addresses a1 - ap of block b1 of the working storage mv is read and compared by operator to φ corresonding test word mti written at this same address during the preliminary stage and which is read again in the permanent storage mp . when there are two clashing or differing bits of the same rank in a word read in working storage and in the corresponding test word as pointed out by the operator φ , the rank i of these bits is marked off by register n and the rank k of the block concerned is marked off simultaneously by register m , that is to say the first block rank , at this stage in the test procedure . when all the addresses of the first block have been tested ( j = p ), the preliminary stage is restarted , by the loop v . the beginning initial conditions are restored , except that the initial value i o is incremented by 1 . during a second preliminary stage , the sequence of test words read from the second word , i . e ., mt2 ... mts - mt1 , is cyclically written at the consecutive addresses a1 - ap of the same block b1 as before . then , during a second procedural stage , the content of each address is compared to the corresponding test word by the operator φ , any variance being indicated by registers m and n as before . at the end of this second procedural stage , loop v restarts a new preliminary stage - procedural stage cycle after a new incrementation by one of the initial value io of indice i , causing a new cyclic permutation of the test words . the sequence now become mt3 .... mts - mt1 - mt2 . the whole of the procedure described is repeated through the intervention of loop v until all the test words have taken the first position in the sequence ( io = s ) successively . in this way , each of the addresses a1 - ap of the first block b1 have been tested successively by each of the test words , and it is possible to detect all the eventual faults of the block components . then , the following block can be tested , with the indices i and j brought back to their initial values and indice k increased by one through the intervention of loop vi . when all the blocks have been tested in this way ( k = m ), the test procedure has ended , and it is possible to set up the diagnostic of the eventual faults of the working storage mv from the listing set up by the locating circuits l linked to registers m and n . this diagnostic can be carried out very simply as shown symbolically by the diagrams of fig4 to 7 . as shown in fig4 if only one component ck1 of the working storage is faulty , registers m and n , respectively , display the rank k of the column and the rank l of the row to which the defective component ck1 belongs . in order to take into account the possibility of internal faults individually concerning several components , the listing must be carried out block by block . in the case shown in fig5 in which all the components of a single block of rank k behave abnormally , the cause of the fail lies in the corresponding block validation circuit bk . inversely , as shown in fig6 if all components of a single row l behave abnormally , the cause of the fault lies in the data input or output circuits corresponding to row d l . finally , if all the components of the matrix show an abnormal behavior , as shown in fig7 the fault is due either to the addressing circuits a or to the write / read selecting circuit e . apparatus made in accordance with the invention facilitates the location of eventual faults in a working storage using equipment of little complexity which is easy to operate . the equipment will work either independently or under the control of the operating units of the processing system which incorporates the store being tested . the invention is in no way limited to the methods of implementation and apparatus described and shown which were only given as an example ; on the contrary , the invention includes all the means forming technical equivalents to those described and illustrated taken separately or in combination and implemented within the framework of the claims that follow . | 6 |
referring now to fig1 and 3 , there is shown various sections fragmentarily of the pipe system and expansion joint configuration comprising the present invention . for purposes of this discussion , reference will be made only to two adjacent pipe sections . it should be clearly understood , however , that the expansion joint configuration comprising the present invention may be applied between any two consecutive pipe sections of a pipe line whether in line or parallel to each other . there is shown two adjacent pipe sections 10 and 12 that are coupled to each other by an expansion joint generally designated by the reference character 14 . the configuration includes a first pipe section 16 joined to the pipe 10 by means of joint 18 . a right angle exists between the sections 10 and 16 . a second pipe section 20 is joined at a right angle to section 16 by means of joint 22 . a third pipe section 24 is joined at a right angle to section 12 by means of joint 26 . a fourth pipe section 28 is joined to pipe section 24 at right angles thereto by means of joint 26 . pipe section 30 interconnects pipe sections 20 at a right angle thereto by means of joint 32 and to pipe section 28 at right angles thereto by means of joint 34 . pipe sections 16 , 20 and 30 lay in a single plane . similarly , pipe sections 24 , 28 and 30 lay in a second plane intersecting the first plane . the joints are so arranged that the two planes formed by the two halves of the configuration and intersecting with pipe section 30 can be moved relative to each other . this is shown by the arrows in fig2 . when the two adjacent lengths of pipe 10 , 12 are extended in an outward direction away from each other , the angle between the two plane sections will increase as the sections 20 and 28 move away from each other with section 30 moving in a downward direction . conversely , when sections 10 and 12 expand thereby moving towards each other , the angle α between the two plane sections decreases as sections 28 and 20 move towards each other with pipe section 30 moving upward until at its extreme position the angle between the two plane sections approaches zero . if the line sections 10 and 12 are not in line the angle α can become negative . it is , therefore , seen that in one extreme position , where most planes lay adjacent to each other and sections 20 and 28 lay in a same plane , the distance between the pipes 10 and 12 will be equal to the total lengths of pipe sections 20 and 28 plus the additional length provided by the pipe joints therebetween . on the other hand , in its opposite extreme position , the ends of pipe sections 10 and 12 will be almost touching each other with the pipe sections 20 and 28 lined up parallel to each other . thus , the total amount of expansion permitted with the expansion joint configuration of this invention is equal to the combined lengths of sections 20 and 28 plus the additional lengths provided by the joints therebetween . if the incoming line and the outgoing line are not aligned , the angle α can become negative thereby increasing the total amount of expansion . in order to provide the rotation within the expansion joint configuration shown in the drawing , swivel type joints and / or ball type joints must be used at various locations . thus , it is necessary to have pipe sections 20 rotate around the longitudinal axis of pipe section 16 . this can be provided by using a fixed joint 18 and a swivel type joint 22 which is fixedly connected to section 16 and permits section 20 to rotate thereabout . similarly , joint 26 could be fixed and joint 27 could be of the swivel type permitting section 28 to rotate about the longitudinal axis of section 24 . alternatively , joints 22 and 27 could be fixed joints and joints 18 and 26 could be ball type joints . in this manner the entire pipe section 16 and 24 would rotate axially within respective ball joints 18 and 26 . however , since pipe sections 20 and 28 are fixedly connected to their respective joints 22 , 26 , as pipe sections 16 and 24 axially rotate , pipe sections 20 and 28 will rotate about the longitudinal axis of sections 16 and 24 , respectively . sections 20 and 28 must also have relative rotation with respect to pipe section 30 . this can be provided by having one of the joints 32 , 34 a swivel type joint with the other joint being fixed . in this way , either section 20 or 28 , depending upon which joint is the swivel joint , can swivel about the longitudinal axis of section 30 with the other section fixed to section 30 . alternatively , both sections 32 and 34 could be swivel type joints . still further , one or both of the joints 32 and 34 could be ball type joints permitting the section 30 to axially rotate within the joint 32 or 34 or both . it is , therefore , seen that numerous type of joints could be used to obtain the required relative rotation of the various sections with respect to each other . the objective to be reached , however , is that the plane formed by section 16 , 20 and 30 can be moved relative to the plane formed by sections 24 , 28 and 30 with the longitudinal axis of section 30 being the intersection between the two planes . the configuration as shown in the figures indicates that the two adjacent lengths of pipe 10 , 12 lay in a same plane and , in fact , are in a common or adjacent axis . this can be achieved by making the length of section 16 equal to the length of section 24 and making the length of section 30 equal to the combination of the length of sections 16 and 24 . however , it is understood that sections 10 and 12 need not lay along the same axis , nor , in fact , need they lay in the same plane . thus , the lengths of the various sections can be adjusted and varied to interconnect two adjacent lengths of pipe regardless of the axial relationship between them and regardless of the different planes that they may be in . furthermore , while the configuration as shown have the section 16 in opposite direction to section 24 , it is understood that this need not be the case . section 30 could , in fact , be located in opposite direction to that shown in the drawing wherein it would be 180 ° opposed to that shown in the figures . similarly , sections 16 and 24 could also be 180 ° out of that position shown in the figures . in addition , the lengths of pipe in the expansion joint configuration shown could be varied such that section 24 be longer or shorter than section 16 ; section 28 could be longer or shorter than section 20 , etc . in this manner , the expansion joint configuration can be modified to particular requirements of the input and output pipes . although in the configuration shown the expansion joint comprised three pipe sections 16 , 20 and 30 , as well as 24 , 28 and 30 for each of the planes , it is understood that there need not be three such pipes forming each plane section but more or less could be used . the only requirement in accordance with this invention is that two planes be formed which intersect along a single line of intersection and the planes are mutually rotatable about this line of intersection . in addition , the planes should be relatively rotatable with respect to the input and output pipe to which the expansion joints are connected . as heretofore described , the joints that can be used to connect adjacent pipe sections could be fixed joints , swivel joints , or ball type joints , depending upon the particular configuration and method of rotation used . although numerous types of swivel joints and ball type joints are available in the art , by way of example , fig4 and 5 show one swivel joint with locking means for adjacent pipe sections , the locking means being as described by u . s . pat . no . 3 , 606 , 402 , granted on sept . 20 , 1971 , to jonas medney . referring now to fig4 and 5 , wherein like reference numerals identify like parts , there is shown adjacent pipes 40 and 42 which are interconnected by means of the swivel joints shown generally at 44 . the swivel joint as shown is fixedly connected to the pipe 40 by means of joint section 46 while joint section 48 , which is fixedly secured to pipe section 42 , can rotate relative to pipe section 40 in a clockwise direction as shown by line 40 - 50 and in a counterclockwise direction as shown by line 52 . a sleeve 54 is tightly positioned onto the end of the pipe section 40 forming the male ends of the junction , the end of the joint 56 forming the female part of the junction . the male and female sections are respectively provided with confronting circumferential grooves 58 and 60 in order to receive a key member 62 . slots 64 , spaced circumferentially around the perimeter of the joint , are at the same axial position as the confronting grooves 56 and 58 as to permit tangential insertion of the key member 62 . it will be seen in fig5 that a typical key member 62 defines a hexagonal polygon in cross section . in addition to the key section 62 , the male section includes angular groove 66 , arranged to receive an o - ring 70 in order to provide a position fluid tight seal . in operating the device shown in fig4 and 5 , the female joint is placed over the male joint with the o - ring in place , thereby providing a fluid tight seal . the hexagonal key is then inserted through the groove 64 into the confronting grooves 58 and 60 to retain the joint in a tight fixed connection onto the end of the pipe . however , as is well known in the art , the elbow section of the swivel joint permits relative motion of the two halves of the joint such that the two pipe sections 40 and 42 can swivel relative to each other . there has been disclosed heretofore the best embodiment of the invention presently contemplated . however , it is to be understood that various changes and modifications may be made thereto without departing from the spirit of the invention . | 5 |
a first embodiment of the door drive 1 in accordance with the invention is shown in fig1 . the door drive 1 shown includes a door movement element 2 which is designed as a door shaft in the embodiments of fig1 to 4 . the door shaft 2 is rotatable about is longitudinal axis , whereby a door , not shown here , in particular a sectional door , door grille / roller door , arranged at the door shaft 2 , can be rolled up and down . in accordance with the invention , the door drive 1 has two electric motors 3 , 4 whose rectified drive torques complement one another to form a greater total torque overall . the use of an individual , powerful motor unit can thereby be dispensed with and costs can be saved by the use of two smaller motor units . both electric motors transfer their output forces via a connection means in the form of a drive pinion 5 , 6 to a connection means arranged at the door shaft , but not shown in any more detail in fig1 to 4 , and thereby to the door shaft . the connection means , which is not shown in any more detail , can in this connection be a further gear which is seated on the door shaft and whose toothed arrangement engages into the teeth of the drive pinion of the two electric motors . a chain or other means for the force transfer to the door shaft is , however , likewise also conceivable . the two electric motors 3 , 4 used are two identical dc geared motors which are fed in each case via a transfer 7 with a predefined supply voltage . the transformers 7 are likewise models of the same type with identical performance properties . it can be seen from fig1 that separate supply systems are defined for the two electric motors 3 , 4 . a door control signal can be detected by a suitable measurement apparatus and it can be evaluated by a control . the control outputs a control variable 8 which serves for the regulation of the supply voltage of the two electric motors 3 , 4 from fig1 . the speed at which the two electric motors 3 , 4 rotate can be varied with reference to the supply voltage . in simplified terms , the control variable output by the control is defined from a function which calculates a required output voltage for the feeding of the electric motors 3 , 4 in dependence on the path , i . e . in dependence on the set position of the door s : in the embodiment of the door drive 1 in accordance with the invention in fig1 , both the supply voltages feeding the electric motors 3 , 4 are regulated by means of the control variable 8 . since minimal differences in the performance properties also result in the use of identical electric motors 3 , 4 and transformers 7 and since this results in a slightly asynchronous operation of the two electric motors , an electric motor 4 is arranged via springs 9 at the door drive . the springs in this connection help compensate growing strains and friction points of the gears by pressure relief of the electric motor 4 in the direction of the door shaft 2 by means of the springs 9 . in a further embodiment ( fig2 ) of the door drive 1 in accordance with the invention , in addition to the compensation of the transformer and motor differences by means of springs 9 , a respective incremental encoder 10 is arranged in direct proximity to the electric motors 3 , 4 such that the movement path covered by the drive pinions 5 , 6 can be detected in a technical measurement . the outputs are in this respect connected to a suitable evaluation apparatus 11 which either compares the two signal inputs with one another or adds them to one another . the use of a comparator for the comparison or of an operational amplifier for the addition of the two output signals of the incremental encoders 10 is conceivable . the output of the evaluation apparatus 11 is in this respect connected to the feedback loop of the electric motor 4 . a regulation value 12 is generated in dependence on the applied signal at the output of the evaluation apparatus 11 which triggers a regulation of the rotational speed of the electric motor 4 to counter an advancing or a lagging of the electric motor 4 in comparison with the electric motor 3 . it becomes clear in this respect that two separately regulatable regulation control circuits are present in the embodiment of the door drive 1 in accordance with the invention in fig2 . it must additionally be noted that all further components or properties of the embodiment of fig2 coincide with those of fig1 . a third embodiment possibility of the door drive 1 in accordance with the invention is shown in fig3 . the door drive 1 in turn comprises a door shaft 2 which is driven via two drive pinions 5 , 6 flanged to the motor output of the electric motors 3 , 4 . both electric motors 3 , 4 of the same construction are fed with a predefined supply voltage via transformers 7 of identical constructional types . a regulation value 8 is determined by a suitable door setting measurement unit for the regulation of the rotational speed of the first electric motor 3 . for the regulation of the separately regulatable second regulation circuit by the second electric motor 4 , the angular position of the electric motor 4 is detected in a technical measurement and a regulation value 12 can be generated by means of the value detected . minimal malpositions in the mutual engagement of the teeth of the drive pinion 5 into the teeth of the gear arranged on the door shaft and thus increasing friction points can be compensated by the resilient arrangement of the electric motor 4 by means of the springs 9 . a changed angular position of the motor 4 can thereby occur which is recognized by the measurement apparatus 13 in a technical measurement and which is compensated by the regulation value 12 . in this respect , the regulation value 12 regulates the supply voltage of the electric motor 4 such that its rotational speed is matched to that of the electric motor 3 and a precise mutual engaging of the named gears is again made possible . fig4 shows a further embodiment of the door drive 12 in accordance with the invention . the design of the door drive is identical to the design of fig3 with the exception of the measuring apparatus 13 and the regulation value 12 . instead of the named measurement apparatus 13 , a rheostat 14 is used which is arranged at the electric motor 4 such that the electrical ohmic resistance of the rheostat changes on minimal positional changes or delay angle changes of the electric motor 4 due to the running apart of the teeth of the drive pinion 5 and of the gear arranged on the door shaft 2 . the supply voltage is changed directly at the input of the electric motor 4 by the rheostat 14 by the connection of the rheostat 14 in the regulation circuit of the electric motor 4 and the generated change in the electrical ohmic resistance . the tracking electric motor 4 can be influenced by a suitable dimensioning of the rheostat to the extent that a synchronous operation of the two electric motors 3 , 4 is ensured . | 4 |
with reference to fig1 , the clamping cord 2 of the present invention includes a core portion 4 and a clamping portion 6 . optionally , the clamping cord 2 may have a section of core portion 4 extending from both ends of the clamping portion 6 , thereby permitting introduction of the clamping cord 2 between multiple sets of teeth . fig2 depicts the clamping cord 2 in cross - section , showing the core portion 4 in the depicted embodiment having longitudinally arranged fibers 12 , which extend the length of the clamping cord 2 . the longitudinally arranged fibers 12 may be round or flat , natural or synthetic , and may be coated with a wax , polytetrafluoroethylene ( ptfe ), or other suitable lubricant commonly known in the art , unless the treatment process for the clamping portion 6 , as described below , would be adversely affected by such a coating . the fibers 12 may include nylon , polyester , polypropylene , natural fibers like cotton , or other materials capable to impart tensile strength . the core portion 4 of the clamping cord 2 is shown as being circular , or round , in shape but also may include other configurations , such as polygonal , and preferably includes a diameter , or width , of about 0 . 1 to 0 . 5 mm . the clamping portion 6 transitions from the core portion 4 at point a and increases in diameter to a generally maximum diameter at point b thereon . the clamping portion 6 similarly is shown as being circular , or round , in shape but also may include other configurations , such as polygonal , and preferably includes a diameter , or width , of about 0 . 5 mm up to a maximum of about 5 mm . alternatively , the clamping portion 6 may present some variability in maximum diameter along its length . the clamping portion 6 includes longitudinally arranged fibers 12 disposed outwardly of the core portion 4 . in an exemplary embodiment , the longitudinally arranged fibers 12 are originally part of the core portion 4 prior to treatment involving an air jet or brush . this treatment opens the original tightly arranged fibers to create a fibrous portion outward of an untreated core portion 4 with fibers 12 having expanded volume interstices therebetween longitudinally arranged outward of the core portion 4 but still physically connected to the core portion 4 . alternatively , longitudinally arranged fibers 12 can be arranged over a section of the core portion 4 in a separate procedure , for example , as a sleeve ( not shown ). in this alternative embodiment , it is preferred that some type of anchoring be effected between this outwardly applied sleeve of longitudinally arranged fibers 12 and the core portion 4 to minimize axially resiliency . the remainder of the clamping portion 6 is comprised of a polymeric elastic material 16 such as silicones , thermoplastic elastomers , or polyurethanes ( pur ) that is applied onto the longitudinally arranged fibers 12 disposed outwardly of the core portion 4 to substantially impregnate the interstices thereof , following by a curing or other setting step . the polymeric elastic material 16 exhibits relatively low axially resiliency due to the existence of a plurality of axial anchoring points 20 which serve to substantially prevent movement of the polymeric elastic material 16 relative to the longitudinally arranged fibers 12 . the clamping portion 6 of the clamping cord 2 preferably includes a hardness of about 10 to 90 shore a . the polymeric elastic material 16 in one embodiment is medical grade silicone . alternatively , other polymeric materials can be used , such as but not limited to thermoplastic elastomers like santoprene ® available from exxonmobil chemical , dynaflex ® available from gls corporation , pebax ® available from arkema , or polyurethane pellethane ® available from dow chemcial , etc . in addition , the polymeric material may be colored and / or contain one or more additives to reduce friction . in an alternative embodiment , the clamping cord 2 incorporates a palatinal shaper 22 , as depicted in fig5 a and 5b . the clamping cord 2 , at an end of the clamping portion 6 , has affixed thereto a palatinal stopper 22 , comprised in turn of a net component 25 and a polymeric - shaped component 26 . the net component 25 is fibrous and preferably of the same or compatible composition to the fibers 12 of the core portion 4 . as an alternative , ductile metallic or plastic fibers can be utilized to produce the net component 25 such as by being inserted between the polymeric - shaped component 26 and the end of the clamping portion 6 . to minimize radial resiliency , the fibers of the net component 25 preferably are anchored to fibers 12 either in the core portion 4 , the clamping portion 6 , or both , prior to the incorporation of the polymeric elastic material 16 . the polymeric - shaped component 26 is preferably of the same or compatible composition to the polymeric elastic material 16 . as indicated above , the clamping portion 6 , as shown in fig5 a and 5b , may present some variability in diameter along its length , i . e . is at a lesser diameter proximal the core portion 4 than proximal the palatinal stopper 22 , for use with class iii cavity application , as further explained below . referring to fig3 a - 3e , dental dam 30 is depicted being fitted over teeth 32 by use of the core portion 4 of the clamping cord 2 , and thereafter secured about the teeth 32 by use of the clamping portion 6 of the clamping cord 2 . in practice , as best shown in fig3 a , a rubber dam frame holder 34 is arranged outward of the opened mouth , and receives the outer dimension of the dental dam 30 over retaining points 36 . the core portion 4 of the clamping cord 2 can be inserted between any adjacent teeth in the mouth , and against the dental dam 30 , which has openings 33 adapted to fit around the teeth 32 . the core portion 6 can then be forced upwards against the dental dam 30 so that the teeth 32 may be received through the openings 33 . as best shown in fig3 b and 3c , to prevent movement of the dental dam 30 downward over the teeth 32 after the dental dam 30 is in place , the core portion 4 of clamping cord 2 is brought into position , such as between two teeth 32 a and 32 b . the teeth 32 a , 32 b through which the core portion 4 of the clamping cord 2 is passed are upper molars 32 a , 32 b , i . e . the second premolar and first molar . after the core portion 4 has been inserted between the adjacent teeth 32 a , 32 b , the core portion 4 is pulled through the space between the two teeth 32 a , 32 b to eventually provide a wedging effect facilitated by the clamping portion 6 as shown in fig3 d . the selection of which teeth to pass the clamping cord 2 therebetween is at the discretion of the dentist or oral surgeon , and is a function of the particular tooth or teeth subject to treatment , as well as the ease in maintaining the stability of the dental dam relative to the treatment area . because of the low axial resiliency of clamping cord 2 , the clamping portion 6 can be drawn as far as desired by the dentist or oral surgeon through the space between teeth 32 a , 32 b as is necessary to effectively stabilize the dental dam 30 . with further reference to fig3 e , that portion of the clamping cord 2 located more than a few millimeters outward of the space between teeth 32 a , 32 b is cut . the resultant wedge created by the clamping portion 6 is minimally obtrusive to the dentist or oral surgeon performing a treatment procedure , and the relatively high radial resiliency of the polymeric elastic material 16 allows for a secure wedging operation , thereby preventing movement of the remaining portion of the clamping cord 2 during the treatment procedure . fig4 depicts a tooth 40 a fitted with a class iii matrix 42 , i . e . a mylar foil , for use with a class iii cavity application , and the clamping portion 6 of the clamping cord 2 having been inserted and pulled between the class iii matrix 42 and adjacent tooth 40 b with the larger diameter clamping portion 6 wedging the class iii matrix 42 into position . as indicated above , it should be understood that the clamping portion 6 may present some variability in diameter along its length ( see fig5 a and 5b ), which may permit easier initial wedging of the clamping portion 6 between teeth 40 a and 40 b as well as minimize patient discomfort in the instance an anesthetic is not permitted or utilized , such as for class iii cavity application , as represented by fig4 . in an alternative embodiment , fig6 a - 6c depict the tooth 40 a fitted with the class iii matrix 42 , i . e . the mylar foil , and the clamping cord 2 having incorporated therein the palatinal shaper 22 , as depicted in fig5 a and 5b . in this series , clamping portion 6 of the clamping cord 2 is pulled between the class iii matrix 42 and adjacent tooth 40 b until the palatinal stopper 22 abuts against the class iii matrix 42 , wherein the stopper 22 is pressed and adapted anatomically against the palatinal teeth surfaces with the larger diameter clamping portion 6 wedging the class iii matrix 42 into position . in addition , the clamping portion 6 of the clamping cord 2 further is wedged , in a manner as above described , between another set of adjacent teeth 43 a and 43 b so that the pressure of the palatinal stopper 22 is prevented from slackening against the class iii matrix 42 , thereby providing an ideal condition for filling the tooth 40 a . as above mentioned , the optional variability in diameter of the clamping portion 6 , as shown in fig6 a - 6c , may permit easier initial wedging between teeth 40 a and 40 b may minimize patient discomfort in the instance an anesthetic is not permitted or utilized for class iii cavity application . accordingly , there is provided the improved dental or clamping cord 2 that may be inserted through or between at least two adjacent teeth 32 a , 32 b , 40 a , 40 b , 43 a , 43 b and thereby , after wedging between the teeth 32 , serves to effectively stabilize a dental dam 30 or class iii matrix 42 position . while the invention has been illustrated by a description of various embodiments and while these embodiments have been described in considerable detail , it is not the intention of the applicant to restrict or in any way limit the scope of the appended claims to such detail . additional advantages and modifications will readily appear to those skilled in the art . thus , the invention in its broader aspects is therefore not limited to the specific details , representative apparatus and method , and illustrative examples shown and described . accordingly , departures may be made from such details without departing from the spirit or scope of applicant &# 39 ; s general inventive concept . | 0 |
the present invention is described in further detail below with reference to examples . 4 , 4 ′- dimercaptodiphenyl sulfone ( 9 . 88 g , 35 . 0 mmol ), lithium chloride ( 0 . 07 g , 1 . 8 mmol ), toluene ( 20 . 00 g ), and methanol ( 10 . 00 g ) were placed in a 100 ml - flask equipped with a stirrer , a thermometer , a condenser , and a gas inlet tube . subsequently , the temperature of the solution was raised to 50 ° c ., and epichlorohydrin ( 6 . 70 g , 72 . 0 mmol ) was added thereto . the reaction was carried out under stirring at 50 ° c . for 2 hours . after the reaction was completed , the temperature of the solution was cooled to 30 ° c ., and water ( 9 . 8 g ), 50 % by weight of tetrabutylammonium bromide ( 1 . 0 g ), and 30 % by weight aqueous solution of sodium hydroxide ( 9 . 70 g , 72 . 8 mmol ) were added thereto . the reaction was carried out under stirring at 35 ° c . for 1 hour . after the reaction was completed , the oil layer was separated by liquid - liquid separation and the solvent was distilled off , thereby obtaining bis ( 4 - oxiranylmethyl sulfanylphenyl ) sulfone ( 11 . 05 g ). the yield relative to bis [( 4 - glycidylthio ) phenyl ] sulfone was 80 %. 1 h nmr d 2 . 65 ( dd , j = 2 . 4 hz , 4 . 8 hz , 2h ), 2 . 83 ( dd , j = 3 . 6 hz , 4 . 4 hz , 2h ), 3 . 15 - 3 . 21 ( m , 6h ), 7 . 41 ( d , j = 8 . 8 hz , 4h ), 7 . 80 ( d , j = 8 . 8 hz , 4h ); elemental analysis ( as c 18 h 18 o 4 s 3 ); bis [( 4 - glycidylthio ) phenyl ] sulfone ( 6 . 00 g , 15 . 0 mmol ), methylene chloride ( 23 . 40 g ), and methanol ( 31 . 00 g ) were placed in a 100 ml - flask equipped with a stirrer , a thermometer , a condenser , and a gas inlet tube . subsequently , the temperature of the solution was raised to 45 ° c ., and thiourea ( 9 . 10 g , 120 . 0 mmol ) was added thereto . the reaction was carried out under stirring at 45 ° c . for 4 hours . after the reaction was completed , water ( 37 . 00 g ) was added to separate the oil layer by liquid - liquid separation , and the solvent was distilled off , thereby obtaining bis [( 4 - thioglycidylthio ) phenyl ] sulfone ( 5 . 79 g ). the yield relative to bis [( 4 - glycidylthio ) phenyl ] sulfone was 89 %. 1 h nmr d 2 . 23 ( dd , j = 1 . 2 hz , 5 . 2 hz , 2h ), 2 . 83 ( m , 2h ), 2 . 94 - 3 . 21 ( m , 6h ), 7 . 41 ( d , j = 8 . 8 hz , 4h ), 7 . 82 ( d , j = 8 . 4 hz , 4h ); elemental analysis ( as c 18 h 18 o 2 s 5 ); 4 , 4 ′- dimercaptodiphenyl sulfone ( 1 . 95 g , 6 . 9 mmol ) and 10 % by weight aqueous solution of sodium hydroxide ( 6 . 00 g , 15 . 0 mmol ) were placed in a 10 ml - flask equipped with a stirrer , a thermometer , a condenser , and a gas inlet tube . subsequently , the temperature of the solution was cooled to 10 ° c . ( reaction solution a ). meanwhile , acryloyl chloride ( 1 . 31 g , 14 . 5 mmol ), cyclohexane ( 5 . 00 g ), and toluene ( 2 . 00 g ) were placed in a 25 ml - flask equipped with a stirrer , a thermometer , a condenser , and a gas inlet tube . the temperature of the solution was subsequently cooled to 10 ° c ., and the reaction solution a was added dropwise thereto over a period of 30 seconds . the reaction was carried out under stirring at 20 ° c . for 1 hour . after the reaction was completed , the reaction solution was filtered , thereby obtaining bis ( 4 - acryloylthiophenyl ) sulfone ( 1 . 08 g ) as a white powder . the yield relative to 4 , 4 ′- dimercaptodiphenyl sulfone was 40 %. 1 h nmr d 5 . 70 ( d , j = 9 . 2 hz , 2h ), 6 . 34 - 6 . 49 ( m , 4h ), 7 . 55 ( d , j = 6 . 8 hz , 4h ), 7 . 88 ( d , j = 6 . 8 hz , 4h ); elemental analysis ( as c 18 h 14 o 4 s 3 ); 4 , 4 ′- dimercaptodiphenyl sulfone ( 1 . 95 g , 6 . 9 mmol ) and 10 % by weight aqueous solution of sodium hydroxide ( 6 . 00 g , 15 . 0 mmol ) were placed in a 10 ml - flask equipped with a stirrer , a thermometer , a condenser , and a gas inlet tube , and the temperature of the solution was cooled to 10 ° c . subsequently , acryloyl chloride ( 1 . 31 g , 14 . 5 mmol ) was added dropwise thereto over a period of 30 seconds . the reaction was carried out under stirring at 20 ° c . for 1 hour . after the reaction was completed , the reaction solution was filtered , thereby obtaining bis ( 4 - acryloylthiophenyl ) sulfone ( 0 . 95 g ) as a white powder . the yield relative to 4 , 4 ′- dimercaptodiphenyl sulfone was 35 %. 4 , 4 ′- dimercaptodiphenyl sulfone ( 1 . 95 g , 6 . 9 mmol ) and 10 % by weight aqueous solution sodium hydroxide ( 6 . 00 g , 15 . 0 mmol ) were placed in a 10 ml - flask equipped with a stirrer , a thermometer , a condenser , and a gas inlet tube . subsequently , the temperature of the solution was cooled to 10 ° c . ( reaction solution a ). meanwhile , methacryloyl chloride ( 1 . 52 g , 14 . 5 mmol ), cyclohexane ( 5 . 00 g ), and toluene ( 3 . 00 g ) were placed in a 25 ml - flask equipped with a stirrer , a thermometer , a condenser , and a gas inlet tube . the temperature of the solution was subsequently cooled to 10 ° c ., and the reaction solution a was added dropwise thereto over a period of 30 seconds . the reaction was carried out under stirring at 20 ° c . for 1 hour . after the reaction was completed , the reaction solution was filtered , thereby obtaining bis ( 4 - methacryloylthiophenyl ) sulfone ( 2 . 58 g ) as a white powder . the yield relative to 4 , 4 ′- dimercaptodiphenyl sulfone was 90 %. 1 h nmr d 2 . 00 ( s , 6h ), 5 . 77 ( s , 2h ), 6 . 21 ( s , 2h ), 7 . 60 ( d , j = 6 . 8 hz , 4h ), 7 . 98 ( d , j = 6 . 8 hz , 4h ); elemental analysis ( as c 20 h 18 o 4 s 3 ); 4 , 4 ′- dimercaptodiphenyl sulfone ( 1 . 95 g , 6 . 9 mmol ), sodium hydride ( 0 . 36 g , 15 . 2 mmol ), and n - methylpyrrolidone ( 6 . 00 g ) were placed in a 10 ml - flask equipped with a stirrer , a thermometer , a condenser , and a gas inlet tube , and the temperature of the solution was then cooled to 10 ° c . subsequently , methacryloyl chloride ( 1 . 52 g , 14 . 5 mmol ) was added dropwise thereto over a period of 30 seconds . the reaction was carried out under stirring at 20 ° c . for 1 hour . after the reaction was completed , water ( 5 . 0 g ) was added to the reaction solution , and filtration was then performed , thereby obtaining bis ( 4 - methacryloylthiophenyl ) sulfone ( 2 . 44 g ) as a white powder . the yield relative to 4 , 4 ′- dimercaptodiphenyl sulfone was 85 %. 4 , 4 ′- dimethylthiodiphenyl sulfone ( 8 . 4 g , 27 mmol ) and toluene ( 50 . 0 g ) were placed in a 100 ml - flask equipped with a stirrer , a thermometer , a condenser , and a gas inlet tube , and the temperature was raised . while the temperature of the solution was maintained at 75 ° c ., chlorine gas ( 4 . 8 g , 68 mmol ) was bubbled into the solution , and the reaction was carried out for 1 hour under stirring . as a result , bis ( 4 - chloromethylsulfanylphenyl ) sulfone was produced in the system . subsequently , water ( 20 . 0 g ) was added thereto , the temperature of the solution was raised to 110 ° c . under stirring , and a hydrolysis reaction was carried out for 12 hours . after the reaction was completed , the temperature of the solution was cooled , and precipitated crystals were filtered , thereby obtaining 4 , 4 ′- dimercaptodiphenyl sulfone ( 6 . 9 g ). the yield relative to 4 , 4 ′- dimethylthiodiphenyl sulfone was 90 %. 4 , 4 ′- dichlorodiphenyl sulfone ( 61 . 0 g , 212 mmol ), toluene ( 75 . 0 g ) and 50 % by weight aqueous solution of tetra - n - butylammonium bromide ( 1 . 0 g ) were placed in a 300 ml - flask equipped with a stirrer , a thermometer , a condenser , and a gas inlet tube ; and the temperature was raised . while the temperature of the solution was maintained at 60 ° c ., 32 % by weight aqueous solution of sodium methanethiolate ( 97 . 5 g , 445 mmol ) was added dropwise to carry out the reaction for 5 hours under stirring . after the reaction was completed , the temperature of the solution was cooled to 25 ° c ., and filtration was performed , thereby obtaining 4 , 4 ′- di ( methylthio ) diphenyl sulfone . next , the obtained crude 4 , 4 ′- di ( methylthio ) diphenyl sulfone and acetonitrile ( 150 . 0 g ) were placed in a 300 ml - flask equipped with a stirrer , a thermometer , a condenser , and a gas inlet tube , and dissolved by increasing the temperature of the solution to 80 ° c . after dissolution , the temperature of the solution was cooled to 10 ° c ., and filtration was performed , thereby obtaining 4 , 4 ′- di ( methylthio ) diphenyl sulfone ( 62 . 5 g ). the yield relative to 4 , 4 ′- dichlorodiphenyl sulfone was 95 %. 1 h nmr d 2 . 48 ( s , 6h ), 7 . 27 ( d , j = 8 . 4 hz , 4h ), 7 . 79 ( d , j = 8 . 8 hz , 4h ); elemental analysis ( as c 14 h 14 o 2 s 3 ); | 2 |
killing orthotopic melanoma in vivo , maintaining body leukocyte number , and improving living states of tumor - bearing mice , by rlz - 8 male kunming mice of 6 - 8 weeks , weighed 18 - 22 g , were purchased from laboratory animal center of norman bethune university of medical science , and reared at a specific pathogen - free ( spf ) condition in northeast normal university , at a temperature controlled at ( 20 ± 2 )° c . and a humidity of 48 %, and in 12 hours alternating lighting . the mice were transplanted with a melanoma cells line b16 - f10 . dulbecco &# 39 ; s modified eagle medium ( dmem ), fetal bovine serum , phosphate buffer saline ( pbs ), trypsin - edta , dimethyl sulfoxide ( dmso ), 0 . 9 % nacl solution , tris - hcl buffer with ph 7 . 6 for rinsing , 0 . 05 % trypsin , rlz - 8 , and dtic ( positive contrast drug ). co 2 thermostat incubator , inverted microscope , pipette , tweezers , clean bench , hematology analyzer , low - speed centrifuge , ultra - low temperature freezing storage cabinet , electronic balance , fresh - keeping cabinet , refrigerator , sterilized pot , water bath pot ; mouse raising boxes , water containers ; disposable medical sterilized gloves , medical sterilized cotton , 50 ml centrifugal tube , pipette tip , cryogenic vial , 10 cm cell culture plate , culture flask , 1 . 5 ml ep tube , and cell counting camber ; disposable 1 ml syringe , mouse bedding , and mouse food . the mice melanoma cells b16 - f10 were cultured in the dmem containing 10 % fetal bovine serum , at 37 ° c . in the co 2 thermostat incubator . 200 μl of b16 - f10 cell suspension ( containing 1 × 10 7 cells ) was slowly subcutaneously injected into a dorsal - ventral side of the mouse through 1 ml syringe , so as to establish a model of mice transplanted with tumors . after 24 hours , the mice were tail - intravenously injected with the rlz - 8 ( 123 μg / kg , 246 μg / kg and 492 μg / kg ), the dtic ( 2 . 5 mg / kg ) and the physiological saline respectively . the rlz - 8 was injected once per day ; the dtic was continuously tail - intravenously injected for 5 days and injected for a second time after 3 weeks . during the experiment , living states of the mice were observed ; the mice were weighed once every 7 days ; blood samples were taken from tail veins of the mice every 2 weeks ; volumes of the tumors , subcutaneously injected into the mice , were measured every 2 days ; for each group , the tumors were dissected at an end of the experiment and weighed on the balance , with weights recorded . according to a formula that a tumor growth inhibition rate =( an average weight of the tumors of the physiological saline group − an average weight of the tumors of the drug administrated groups )/ the average weight of the tumors of the physiological saline group , the inhibition rate of the rlz - 8 upon the growth of the orthotopic tumor was calculated . after the 28 days of continuously administrating the rlz - 8 to the tumor - bearing mice , no significant difference was observed in aspects of hair glossiness , basic feeding and excrement among the rlz - 8 groups ( three dosages ), the dtic group , the physiological saline group and a normal group ; the physiological group had poorer movement and agility than the rlz - 8 groups and the dtic group , and especially the rlz - 8 high dosage group had significantly higher agility than the physiological saline group . after the 56 days of continuously administrating the rlz - 8 , it was observed that the rlz - 8 administrated groups had better hair glossiness than the negative contrast group and the dtic group . ( 2 ) analysis result about impact of treatment drug on mice weights after the 28 days of continuously administrating the rlz - 8 to the tumor - bearing mice , no significant difference existed among the weight of each group before the experiment ; after the experiment , the rlz - 8 high dosage group had the slightly smaller weight than the other groups , as showed in fig1 . after the 56 days of continuously administrating the rlz - 8 , the rlz - 8 groups and the dtic group had larger weights than the negative contrast group , while the five experiment groups all had the smaller weights than the normal group , as showed in fig2 . after the 28 days of continuously administrating and then 28 days of raising without drug administration , for the weights of the finally survived mice , the dtic group and the rlz - 8 low dosage group had smaller weights than the negative contrast group , and the five experiment groups had the smaller weight than the normal group , which indicated that the rlz - 8 is able to adjust body states of the mice . the tumors were dissected and weighed , and then an average weight of the tumors of each group was calculated . as showed in table 1 and table 2 , after the 28 days of administrating the rlz - 8 , the rlz - 8 high dosage group had the smaller tumor weight than the dtic group ; for the three rlz - 8 groups , with a concentration of the rlz - 8 gradually increased , the weight of the tumor gradually decreased . the rlz - 8 groups had significant difference over the negative contrast group , while the rlz - 8 low dosage group , the rlz - 8 medium dosage group and the rlz - 8 high dosage group had significant difference ( n = 10 , p & lt ; 0 . 05 ). when the drug administration days reach 56 days , by weighing the tumors of the survival mice , the rlz - 8 groups had better tumor inhibition effect than the dtic group , and especially the rlz - 8 high dosage group had significant difference over the dtic group ( n = 10 , p & lt ; 0 . 05 ). therefore , after the 28 days of administrating the rlz - 8 , the rlz - 8 high dosage group had smaller tumor weight than the dtic group ; among the three rlz - 8 groups , with the concentration of the rlz - 8 gradually increased , the weight of the subcutaneous tumor gradually decreased ; when the days of administration elongated to 56 days , the tumor weights of the survival mice indicated that the rlz - 8 groups had significant tumor inhibition effect over the dtic group . for the 28 days of drug administration , with the rlz - 8 concentration gradually increased , the volume of the subcutaneous tumor gradually decreased ; the rlz - 8 groups had significantly smaller tumor volumes than the dtic group , and especially the rlz - 8 groups had significant inhibition on the growth of the tumor compared with the contrast group ( n = 10 ). analyzed from the volumes of the tumors , as showed in table 1 , for the 28 days of the drug administration , the rlz - 8 high dosage group had higher tumor inhibition rate than the dtic group ; among the rlz - 8 groups , with the drug dosage gradually increased , the inhibition rate gradually enhanced . when the days of the drug administration elongated to 56 days , the rlz - 8 groups had particularly significant tumor inhibition rates compared with the dtic group . ( 4 ) test result of drug tolerance reaction of body against dtic and rlz - 8 while inhibiting the weight of the body tumor , the dtic and the rlz - 8 had a certain impact on the drug tolerance of the body . as showed in table 1 and table 2 , after administrating the dtic for 28 days and for 56 days , the inhibition rate greatly decreased , and the tumor growth rate greatly increased , which indicated that the body gradually generated tolerance against the dtic along with an elongation of a dtic administration time , so that the tumor inhibition weakened ; however , after administrating the rlz - 8 for 28 days and for 56 days , the inhibition rate greatly increased , which indicated that the body tolerance did not increase with an elongation of a rlz - 8 administration time and further proved that the rlz - 8 had healing effect far better than the dtic . by administrating for 28 days , with the gradually increased rlz - 8 concentration , the body leukocyte number of the mice slightly increased , while the body leukocyte number of the positive drug group ( dtic ) evidently decreased ; especially each rlz - 8 group had particularly significant impact on the body leukocyte number compared with the contrast group ( n = 10 ). by elongating the administration time to 56 days , the leukocyte number of each rlz - 8 group showed significance over the dtic group ( n = 10 ), as showed in fig3 ; the body leukocyte number of the dtic group reached a minimal value . by administrating the drug for 28 days and continuing raising without drug administration , the body leukocyte number of the rlz - 8 group slightly decreased ; the body leukocyte number of the dtic group continuously decreased and then showed a stable state for a while . analyzed from the body leukocyte number , it was showed that the rlz - 8 group exhibited small impact on the body leukocyte number in the anti - tumor treatment experiment , while the positive drug group ( dtic ) greatly decreased the body leukocyte number in the anti - tumor treatment experiment , and damaged and weakened the body immune function , causing a hidden danger of immune deficiency in the anti - tumor treatment process . furthermore , in the anti - tumor experiment , the rlz - 8 not only was able to effectively inhibit the growth of the tumor , but also had functions of maintaining and protecting body immunity . the rlz - 8 had better safety than the positive drug group ( dtic ). after continuously administrating the drug for 28 days , no mice died in the experiment period . after continuously administrating the drug for 56 days , death emerged in the negative contrast group and the positive drug group ( dtic ), wherein massive death emerged in the positive drug group ( dtic ). however , no mice died in each rlz - 8 dosage group , as showed in table 3 . therefore , the rlz - 8 showed significant difference in maintaining the life elongation rate of the tumor - bearing mice over the dtic , with significant advantage . male kunming mice of 6 - 8 weeks , weighed 18 - 22 g , were purchased from laboratory animal center of norman bethune university of medical science , and reared at an spf condition in northeast normal university , at a temperature controlled at ( 20 ± 2 )° c . and a humidity of 48 %, and in 12 hours alternating lighting . the mice were transplanted with a melanoma cells line b16 - f10 . dmem , fetal bovine serum , pbs , trypsin - edta , dmso , tris - hcl buffer with ph 7 . 6 for rinsing , 0 . 05 % trypsin , rlz - 8 , and dtic . the mice melanoma cells b16 - f10 were cultured in the dmem containing 10 % fetal bovine serum , at 37 ° c . in the co 2 thermostat incubator . 200 μl of b16 - f10 melanoma cell suspension ( containing 1 × 10 7 cells ) was slowly intravenously injected into a tail vein of the mouse through 1 ml syringe , so as to establish a model of mice transplanted with tumors . after 24 hours , the mice were tail - intravenously injected with the rlz - 8 ( 123 μg / kg , 246 μg / kg and 492 μg / kg ), the dtic ( 2 . 5 mg / kg ) and the physiological saline respectively . the rlz - 8 was injected once per day ; the dtic was continuously tail - intravenously injected for 5 days and injected for a second time after 3 weeks . after the mice were put to death , lungs of the dead mice were dissected out and the number of black spots on surfaces of the lungs , formed by an aggregation of metastasis cell , was counted , so as to calculate the inhibition rate of the drug against the growth of the lung metastasis as : inhibition rate =( an average metastasis number of the negative contrast group − an average metastasis number of the drug administrated group )/ the average metastasis number of the negative contrast group × 100 %. a time and the number of the dead mouse in each experiment group were recorded in detail , especially during administrating the drug continuously , until the negative contrast group was completely dead ; and then , the survival states of the mice in the experiment groups and the contrast groups were analyzed . a survival rate was calculated according to the number of the dead mice in the other groups when all the mice of the negative contrast group were dead , based on a formula that survival rate =( a total number of the mice − the number of the dead mice )/ the total number of the mice . based on an analysis about the statistics of the melanoma lung metastases , each rlz - 8 dosage group had the smaller number of the tumor metastases than the negative contrast group and the positive contrast group ; the positive contrast group had evidently fewer metastases than the negative contrast group . according to the formula of the inhibition rate , the tumor metastasis inhibition rate of the drug in each group was calculated . as showed in fig4 , for the 28 days of administrating the drug , the rlz - 8 low dosage group had the inhibition rate of 62 . 13 ± 1 . 88 % compared with the contrast group ; the rlz - 8 medium dosage group had the inhibition rate of 67 . 65 ± 2 . 1 % compared with the contrast group ; and , the rlz - 8 high dosage group had the inhibition rate of 71 . 17 ± 2 . 43 % compared with the contrast group . therefore , the rlz - 8 evidently inhibited the formation and the growth of the b16 - f10 lung metastases which were intravenously injected into the tail vein of the mice . the positive contrast group had the inhibition rate of 32 . 04 ± 1 . 27 %, lower than the three experiment drug groups , which indicated that the rlz - 8 had better inhibition effect on the b16 - f10 lung metastases which were intravenously injected into the tail vein of the mice , than the positive drug dtic , as showed in table 4 . as showed in table 4 , by recording the time and the number of the dead mouse in each group in detail , the survival states of the mice in the experiment groups and the contrast groups were analyzed . when all the mice of the negative contrast group were dead ( respectively on the 87 th day and on the 95 th day after injecting the tumors , in two repeated tests ), the survival rate of the mice remained in the positive drug dtic group was 10 %, namely that 10 % of the initial total number of the mice were still alive ; the survival rates of the three experiment groups with different concentrations of the experiment drug were respectively 25 %, 30 % and 10 %. concluded from the results , the positive drug and the experiment drug were effective for an elongation of the survival time of the mice to some extent . generally speaking , the experiment drug elongated the survival time of the mice and improved the life elongation rate better than the positive drug dtic . generation of antibody and neutralizing antibody after continuous multiple administration in vivo of rlz - 8 to macaca fascicularis as a fungal recombinant genetic engineering drug , it is crucial to track generation of antibody of the rlz - 8 for a preclinical evaluation . blood serum of normal monkeys , macaca fascicularis , after being continuously administrated , was selected for testing antibody of the rlz - 8 by elisa and for testing a neutralization activity of anti - rlz - 8 antibody by a biological activity method . on the 9 th - 11 th days of administrating the drug , three monkeys were tested to have low titer ( 1 : 5 ) of the anti - rlz - 8 antibody ; after the 28 th day of administrating , the titer of the antibody maintained low , within a range of 1 : 25 to 1 : 125 . no anti - rlz - 8 antibody was tested from the monkeys of the contrast group . based on a study about impacts of culture media , with the anti - rlz - 8 antibody positive ( 1 : 125 ) monkey blood serum ( diluted 10 times ) and without the monkey blood serum , on ifn - γ secreting expression stimulated by different concentrations of the rlz - 8 , in a cell proliferation curve of the culture medium with the monkey blood serum , a maximum expression value ( emax ) of value a decreased to 0 . 78 ± 0 . 09 ; a half maximal inhibitory concentration ic 50 increased ; and a slope of the curve decreased to 0 . 77 ± 0 . 20 . therefore , the inhibition effect of the monkey blood serum was not the property of the competitive neutralizing antibody . conclusion : the rlz - 8 does not generate the neutralizing antibody in the monkeys and is not neutralized by the antibody during the whole melanoma treatment process . 98 sd rats ( 49 male and 49 female ), weighed 100 - 120 g , were purchased from laboratory animal center of norman bethune university of medical science , and reared at an spf condition in northeast normal university , at a temperature controlled at ( 20 ± 2 )° c . and a humidity of 48 %, and in 12 hours alternating lighting . the administration dosages for the rats were calculated based on the administration dosage for the mice ; the rats were divided into a contrast group ( physiological saline ), a low dosage group ( 15 μl / kg weight ), a medium dosage group ( 30 μl / kg weight ) and a high dosage group ( 60 μl / kg weight ). the administration manner was an intraperitoneal injection . feeding amount , weight ; serology : liver function and kidney function ; immunity : thymus index and spleen index ; serum complements igm , igg , c3 and c4 ; pathology examination : heart , liver , spleen , lung , kidney , pancreas , thymus , gonad etc . as showed in table 5 , the rlz - 8 protein medium dosage group and the rlz - 8 protein high dosage group evidently increased the weights of the male rats ; the rlz - 8 protein low dosage group evidently increased the weights o the female rats . the rlz - 8 protein had no adverse impact on a general growth state of the sd rats , such as the feeding . moreover , the rlz - 8 protein medium dosage group and the rlz - 8 protein high dosage group significantly increased the weights of the male rats ; the rlz - 8 protein low dosage group significantly increased the weights of the female rats . as showed in table 6 , the rlz - 8 protein had no obvious adverse impact on the liver function and the kidney function of the rats . the rlz - 8 low dosage group significantly increased a content of alb ; the rlz - 8 high dosage group had lower content of ast than the rlz - 8 medium dosage group ; the rlz - 8 protein groups had lower content of bun than the contrast group , wherein the rlz - 8 medium dosage group and the rlz - 8 high dosage group had the significantly low content of bun . the cbe levels of the rlz - 8 low dosage group and the rlz - 8 medium dosage group significantly increased ; the cre level of each rlz - 8 protein group significantly increased . in the rlz - 8 medium dosage group , the tba level and the ua level significantly increased ; in the rlz - 8 low dosage group , the tp level significantly increased . for the female rats , the alb content and the ast content of the rlz - 8 high dosage group significantly decreased ; the tp content of the rlz - 8 high dosage group decreased ; and the ua content of each rlz - 8 group significantly increased . referring to table 7 , immunity examination results showed that the spleen index ( except the low dosage group ) and the thymus index of each rlz - 8 group increased compared with the contrast group , but not significantly . with regard to igg and igm , each dosage group slightly increased compared to the contrast group , without significance . with regard to c3 and c4 , no significant difference existed between each dosage group and the contrast group , and thus , the rlz - 8 had no impact on c3 and c4 of the rats . pathology examination : by comparing tested organs with the organs of the to contrast group , no obvious morphological change was observed . the rlz - 8 protein facilitates the growth of the rats ; the rlz - 8 protein has no adverse impact on the liver function and the kidney function of the rats . the ua is beneficial and harmful to the body , wherein the former one refers to an anti - oxidation property and the latter one refers to stimulation to blood vessel smooth muscle cell proliferation and an injury to functions of endothelial cells . in the example 4 , the significant increase of ua may play an important role in anti - oxidant capacity ; the rlz - 8 protein significantly enhances the immunity of the rats , especially humoral immunity ; and , the rlz - 8 protein has no significant adverse impact on major organs of the rats . 1 . the above pharmacology tests indicate that the anti - tumor effect of the rlz - 8 is significant in maintaining the leukocyte level of the body without toxicity . therefore , the rlz - 8 is suitable and safe as a drug . 2 . as an anti - tumor drug , the rlz - 8 can be administrated orally and parenterally . the administration dosage depends on the symptom , the age , the weight etc . for adults , the oral administration is executed as 10 - 1000 mg per dosage / per person , several times per day ; the parenteral administration is executed as 10 - 100 mg , several times per day . 3 . a drug for the oral administration of the present invention can be tablets , pills and capsules ( hard capsules and soft capsules ). the drug for the oral administration comprises the rlz - 8 and at least one inert diluent , such as lactose , mannitol , glucose , starch and polyvinyl pyrrolidone ; and further comprises a pharmaceutically acceptable additive , except the inert diluent , such as lubricant , disintegrant and stabilizer . if necessary , the tablets or the pills can be coated with at least one layer of film made of gastric - soluble material or enteric - soluble material . an injection for the parenteral administration of the present invention comprises the rlz - 8 and at least one inert liquid diluent , such as distilled water for injection and physiological saline . the rlz - 8 can be made into lyophilized powder and dissolve into the inert liquid diluent to be injected . 1000 mg of rlz - 8 were dissolved into 100 ml of sterilized physiological saline , uniformly mixed , separated into each injection with a concentration of rlz - 8 10 mg / ml / per injection to be stored into each bottle , sealed , and sterilized into products . other items accorded to requirements of the injection under pharmacopoeia of the people &# 39 ; s republic of china , 2010 edition . 100 g of rlz - 8 and 0 . 5 kg of pharmaceutical starch were prepared into capsules according to known capsule preparation techniques and devices , rlz - 8 10 mg / per capsule . other items accorded to requirements of the capsule under pharmacopoeia of the people &# 39 ; s republic of china , 2010 edition . 100 g of rlz - 8 , 560 g of microcrystalline cellulose , 380 g of anhydrous lactose , and 200 g of magnesium stearate were prepared into tablets according to known tablet preparation techniques and devices , rlz - 8 10 mg / per tablet . other items accorded to requirements of the capsule under pharmacopoeia of the people &# 39 ; s republic of china , 2010 edition . a certain amount of the rlz - 8 , according to requirements of oral fluid under pharmacopoeia of the people &# 39 ; s republic of china , 2010 edition , was prepared into the oral fluid through known oral fluid preparation techniques and devices . one skilled in the art will understand that the embodiment of the present invention as shown in the drawings and described above is exemplary only and not intended to be limiting . it will thus be seen that the objects of the present invention have been fully and effectively accomplished . its embodiments have been shown and described for the purposes of illustrating the functional and structural principles of the present invention and is subject to change without departure from such principles . therefore , this invention includes all modifications encompassed within the spirit and scope of the following claims . | 0 |
the role played by floating surface states in the function of emitters of the invention can be understood with reference to the special case of an electron in vacuum near a flat surface having a negative electron affinity . with reference to fig1 an electron 100 in vacuum 120 is attracted to an electrically neutral material 130 by its image charge 140 in the material 130 . the potential energy of the electron 100 falls from its value at infinity as it approaches the surface 150 of the material 130 , varying as the reciprocal of its distance from the surface 150 , as shown by curve 160 . since the surface 150 has a negative electron affinity , the conduction band edge 170 of the material 130 near the surface 150 is , by definition , at a higher energy than the vacuum level ; an energetic barrier prevents the electron &# 39 ; s entering the bulk of the material 130 . however , no barrier guards the electron from entering floating surface states over the surface 150 . such floating surface states have been observed over some vacuum - metal and vacuum - nea interfaces . the electron wave functions of these states approach zero at the surface 150 . the average displacement d of the electron from the interface in the lowest of the floating surface states is d = 2α 0 , ## equ1 ## in which α 0 is the bohr radius , and ε is the dielectric constant of the material 130 . in the case of diamond , which has a dielectric constant of about 5 . 7 , an electron in a free surface state resides about 0 . 3 nm above the surface 150 . the magnitude of the corresponding one - dimensional hydrogenic quantum binding energy e is approximated by , ## equ2 ## in which r is the rydberg constant . in the case of diamond , this energy is 0 . 42 electron volts , indicated by dashed line 180 . thus the injection of an elcctron from a metal contact to a floating surface state is more favorable than its emission to vacuum by about half an electron volt . the enhancement of device operation due to convolution of the interface between the contact and the free surface can be understood with reference to fig2 . the respective floating surface states of two flat , parallel nea surfaces 150 &# 39 ;, separated by a sufficiently small distance d , interact to gives rise to composite floating surface states . the interaction of the respective states effectively reduces the vacuum level at &# 34 ; infinity &# 34 ; between the surfaces 150 &# 39 ;, which tends to reduce the magnitude of the composite - state energy compared to the rydberg term calculated above for a floating state associated with a single surface . however , a particle - in - a - box term due to the confinement between the surfaces 150 &# 39 ; of an electron 100 &# 39 ; in such a composite state increases the energy level of the state . the e min of the lowest energy composite state , represented by the curve 190 , is then approximated by ## equ3 ## in which e is the electronic charge , ε 0 is the permittivity of vacuum , and m is the mass of the electron . the energy profile of the electron 100 &# 39 ; in a composite floating surface state , plotted in fig3 shows that the electron energy is lower than the work function , i . e ., the energy increment separating a metal fermi level from the vacuum level at infinity , in the case of many metals . even for separations up to 10 å , the energy of the composite surface state is significantly lower than the level of a floating single - surface state , signified by d =∞. ( according to the model , the composite state energy increases for very small values , around 0 . 2 nm , of the wall separation d . since this value is smaller than the crystallographic unit cell of most materials -- for example , the diamond unit cell is 0 . 36 nm on a side -- the model is probably overly simplistic in this regime .) thus , the interaction of the two surfaces 150 &# 39 ; in the vicinity of the junction of a metallic contact significantly improves the energetics of electron injection from a metallic contact into floating states over a free surface without altering the work function of the metallic contact material . the increased energy gap between the floating surface states and the vacuum level at infinity that must be traversed in order to enable emission to vacuum is easily overcome by the high kinetic energies that the electrons attain during acceleration over the free surface . the interacting surfaces 150 &# 39 ; need not belong to distinct bodies in order to produce the energetic benefit . for example , they may be noncoplaniar portions of a single surface that has a sufficiently small radius of curvature to allow the portions to interact . entire free surface of the invention may have a convoluted profile , for example may be circular - or rectangular - cylindrical ; or the free surface may include a convoluted section comprising locally curved portions of a macroscopically flat region . the operation and fabrication of surface - emission cathodes of the invention are demonstrated by the following examples . with reference to fig4 a , a region 210 of a type - ib diamond 230 , about 3 mm on a side , was ion - implanted with carbon cations to serve as a first conductive contact to the diamond 230 . the implanted region 210 was joined to a metal support 240 . the diamond was exposed to an oxygen discharge , treated with cesium , and the reexposed to oxygen in order to enhance the nea of the surfaces 245a and 245b of the diamond 230 . a voltage source 250 imposed a potential between the metal support 240 and an anode 260 , biased to a dc potential of 0 to 10 kv and separated from the diamond 230 by an expanse 270 of vacuum of 0 to 0 . 8 mm . electrons left the top surface 245a and traveled to the anode 260 , apparently following the path from the implanted region 210 indicated by the arrow a , along which the surfaces 245a and 245b of the diamond 230 glowed green yellow . then a phosphorescent screen 260 &# 39 ; having a 1 - kev - luminescence threshold was used as the anode , placed directly on the top surface 245a of the diamond 230 , as indicated in fig4 b . when 1 to 7 kilovolts was applied between the metal support 240 and the screen 260 &# 39 ;, the screen fluoresced in regions 265 near its intersection with the perimeter 270 of the diamond 230 , as shown in fig4 c . the electrons evidently leave the surface 245a or 245b with kinetic energies equal to or greater than 1 kev . with reference to fig5 a , a 100 - μm - thick diamond plate 310 was coated on one side with a nickel layer 320 , which was joined to a metallic substrate 325 . the opposite side of the diamond plate 310 was graphitizcd to form a conductive layer 330 . the diamond was then cleaved and a portion removed to expose a clean , undamaged surface 340 . when a voltage source 345 applied a few kilovolts between the nickel layer 320 and the graphitized layer 330 , electrons were emitted into vacuum and collected by a collector 350 ; some current to the top electrode 330 was also detected through circuit 360 . in fig5 b , curves 370 and 380 respectively show the i - v characteristics of the emitted current and of the electrode current . by using a movable phosphor screen ( not shown ), it was determined that these electrons originated from the cleaved free surface 340 and that they were nearly monoenergetic , with kinetic energies nearly equivalent to the applied potential , sometimes within 50 ev of the applied potential . with reference to fig6 a , an emitter was formed in a slab 410 of type - ib diamond . the emitter features a raised portion 415 in the slab 410 . the top surface of the raised portion and the lower surfaces of the slab 410 are covered by a 50 - nm film of nickel metal . the lower nickel film 440 serves as the first conductive contact ; the upper nickel film 450 serves as the second conductive contact . the uncoated free surfaces 460 are about 1 . 5 μm long . this device was fabricated by forming array of raised squares in a flat slab by depositing an aluminum layer , patterning the aluminum layer , and etching away diamond around the patterned squares by etching in a flux of no 2 while impinging the surface with 1200 - ev xenon cations . after removal of the aluminum mask , the structure was cleaned in molten sodium nitrate at about 400 ° c . to remove insoluble nondiamond carbon compounds from the diamond surfaces . then the nickel films 440 and 450 were deposited by electron - beam evaporation . it was found that 5 - to - 50 - nm - thick nickel layers formed good contacts . depositing thicker films usually caused some undesired deposition on the cleaned free surfaces 460 . a slab of cvd diamond suitable for making this structure could be made by growing cvd diamond on a sacrificial substrate and then removing the substrate to expose the smooth cvd surface . fig6 b shows the emission current from the free surfaces 460 of this device as a function of the gate voltage applied across the first and second conductive contacts . the current to the film 450 was on the order of 10 2 to 10 4 times the emitted current . measurable emission occurs at applied potentials substantially less than 4 v . adequate currents for use in flat - panel displays are obtained at voltages less than 10 v . a 1 - μm layer 510 of nitrogen - doped diamond is deposited by chemical vapor deposition over a conductive substrate 520 of metal or heavily doped silicon to form the structure shown in fig7 a . the top diamond surface 525 is then subjected to a current of uranium ions having ion energies greater than 10 7 ev , sufficient to damage the diamond layer 510 . the resulting graphite traces 530 , shown in fig7 b , each correspond to the pathway of a heavy ion through the thickness of the layer 510 . the traces 530 are removed using an oxygen plasma , thereby forming an array of tunnels 540 . with reference to fig7 c , the interior surfaces 550 of the array of tunnels 540 , each having diameter from 0 . 5 to 10 nm , provide a convoluted free surface joined at the bottom 560 of each tunnel 540 to the conductive substrate 520 . treating the diamond surface 525 with a higher flux of argon ions having energies from 10 3 to 10 5 ev provides a damaged layer 570 serving as the second conductive contact , as shown in fig7 d . with reference to fig8 a flat - panel light - emitting device of the invention , generally designated at 610 , includes a cathode body 620 of cesiated diamond having a front surface 624 and a back surface 628 . the free surface 630 of the body 620 is in contact with a first conductive contact 638 at the back surface 628 and with a second conductive contact 634 at the front surface 624 . the second contact 634 is a thin conductive layer , no thicker than several nanometers , preferably of metal or graphite . the device 610 is optionally housed in an evacuated chamber . a voltage source imposes a potential difference between the first and second conductive contacts 638 and 634 . a layer 650 of phosphor material , such as , for example , zinc oxide , is disposed over the second contact 634 . in operation , electrons are injected from the first contact 638 onto the free surface 630 , are accelerated over the free surface 630 toward the second contact 634 , and leave the free surface 630 and enter the layer 650 , without emission to vacuum , thereby exciting the phosphor material to luminescence . it will therefore be seen that the foregoing represents a highly advantageous approach to the construction of field - emission devices , especially those incorporating diamond and other wide - bandgap materials . the terms and expressions employed herein 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 invention claimed . for example , the free surface of the emitter may be coplanar with one or both of the conductive contacts , the extent of each of the features being lithographically defined . | 7 |
fig3 a and 3b illustrate the use of an opaque film adjacent another layer or an air gap to absorb shunting light . fig3 a shows the opaque film 34 , before assembly being placed over layers 36 , 36 ′ separated by an air gap 38 . layers 36 , 36 ′ may be mounted on a common substrate ( not shown ). holes 40 and 42 are shown for the emitter and detector . alternately , these can be windows or simply a solid portion of a transparent layer . fig3 b shows the assembled lower layer and opaque film layer 34 . as light attempts to shunt from emitter area 40 to detector area 42 , either passing through the air gap 38 or through layers 36 and 36 ′, it will bounce back and forth between the boundaries of the layer and through the air gap . some of the light that would normally hit the top end of layer 36 or 36 ′ and bounce back into the middle of the layer , will instead pass into and be absorbed by opaque layer 34 , which is tightly coupled to the layers 36 and 36 ′. fig4 illustrates the use of a woven or fiber material 44 on layers 36 and 36 ′, and filling the air gap 38 of fig3 a . fibers in the material will absorb light , thus attenuating light attempting to shunt from emitter area 40 to detector area 42 . an additional cover layer 46 may be placed over the assembly , and which will need to be at least partially transparent for light to escape and be detected . layer 46 can function as another shunting layer . by abutting up against the woven or fiber material 44 , light will be absorbed out of that layer in the same manner as the opaque film 34 of fig3 a and b . alternately , the fiber and woven material can be inserted into layer 46 between the emitter and detector . fig5 shows an alternate embodiment in which a layer 50 is used with an emitter 52 placed on top of it . alternately , layer 50 could have holes 54 and 56 over the emitter and detector , with the emitter 52 being placed through hole 54 onto an underlying layer . a partially opaque layer 58 is placed above emitter 52 in the embodiment shown . layer 58 may extend a portion of the way or all of the way over to where the detector is . the opacity of layer 58 is chosen in conjunction with its thickness to allow transmission of substantially all of the light from emitter 52 through the layer , while substantially reducing the amount of light shunted in a path transverse through the layer from the emitter to the detector . layer 58 preferably attenuates the shunted light so that it is less than 10 %, and more preferably less than 1 % of the total light received by the detector . additionally , of the light detected by the detector and converted into electrical signal , the portion of the electrical signal due to shunted light is preferably less than 10 % and more preferably less than 1 % of the signal value . the layer may be made substantially opaque through coloring . one such color would be a gray created by suspension of carbon black particles in the base material of the layer . this would be substantially opaque to both red and infrared . fig6 shows another embodiment of the invention in which a layer 60 over an emitter 62 and detector 64 has a series of perforations 66 . these perforations block the light path and scatter the light attempting to shunt between the emitter 62 and detector 64 through layer 60 . although light tends to jump air gaps , by providing multiple air gaps in different orientations , the light can be somewhat effectively scattered . alternately , the perforations could be filled with a colored filling material or putty to block the light that might otherwise jump the air gaps , or could have the inside walls of the perforations colored . alternately , embossing ( or other variations in thickness ) could be used rather than perforations . fig7 illustrates a layer 70 having an emitter 72 and detector 74 , covered by another layer 76 . layer 76 may be partially transparent for light to exit from emitter 72 and re - enter to detector 74 . layer 76 has a thinned portion 78 , and layer 70 has a corresponding thinned portion 79 . these portions make the layers thin in that area , thus limiting the amount of light that may be shunted . the layer could be made thin by a number of techniques , such as embossing , welding or heat sealing . the width of the thinned area could be varied , and the shape could be varied as desired . for instance , the thinned area could extend around the sides of the emitter and detector , to prevent shunting of light from the edges of the layers when they are wrapped around a finger . the thinness of the layer contributes to absorption of the light because light which is traveling in a thin layer will more often bounce off the layer boundaries than it would in a thick layer . this provides more chances to escape the layer and be lost or absorbed in an adjoining layer with absorption characteristics . the thickness is preferably less than 0 . 25 mm and more preferably no more than 0 . 025 mm . the length of the thin section is preferably greater than 1 mm and more preferably greater than 3 mm . the thin layer approach could be applied to a re - manufacture or other modification of a sensor which involves adding a layer over the emitter and detector . the entire layer could be made thin , preferably less than 0 . 25 mm , more preferably no more than 0 . 025 mm , in order to limit its shunting effect . fig8 shows a sensor having a layer 80 for an emitter 81 and a detector 82 , having transparent windows 83 and 84 , respectively . a substrate layer 85 supports the emitter and detector , with light being transmitted through transparent window 83 and received through window 84 . in one embodiment , the entire layer 80 is opaque , leaving transparent portions 83 and 84 . alternately , the entire layer 80 may be transparent , or of one color with the windows of another or transparent . in addition , a portion 86 of layer 80 between the emitter and detector may be colored a substantially opaque color to prevent the shunting of light of the wavelengths of interest . in alternate embodiments , portion 86 may be of different shapes , and may partially or totally enclose the windows for the emitter and detector . fig9 shows another embodiment of a sensor according to the present invention mounted on a finger 90 . two portions of a first layer , 91 , 91 ′ have the emitter 92 and detector 93 , respectively , attached to them . a break between layers 91 and 91 ′ is provided in between the emitter and detector , which will be at the tip of finger 90 . normally , this gap would provide an air gap through which light can be shunted between the emitter and detector across the top of the finger . however , by using a backing layer 94 , with an adhesive in the portion between layers 91 and 91 ′, this layer can stick to the tip of finger 90 , removing the air gap and thus substantially preventing shunting between the layers . an alternate embodiment is shown in fig1 , with the finger 100 having a sensor with layers 91 and 91 ′ and emitter 92 and detector 93 as in fig9 . here , however , a separate layer 94 is provided with a foam or other resilient or compressible pad 96 mounted on layer 94 between layers 91 and 91 ′. this material will compress against the tip of the finger , thus also blocking the air gap and preventing the shunting of light if the material is made of a substantially opaque material , such as a color that is substantially opaque to the wavelengths of interest ( e . g ., red and infrared ), or is made of woven material or other material opaque to the light . fig1 is another embodiment of the present invention showing a layer 110 having an emitter 112 and a detector 114 mounted thereon . a covering , transparent layer 116 provides a covering and a window for the transmission and detection of light . shunting of light is prevented by crimping the layers with a metal or other crimp 118 , 120 . the metal or other material is substantially opaque to the shunted light of the wavelengths of interest , and completely penetrates the layer , or substantially penetrates the layer . fig1 shows an alternate embodiment in which a layer 121 has an emitter 122 and a detector 124 ( both shown in phantom ) mounted thereon . over the emitter area is a first transparent layer 126 , with a second transparent layer 128 over the detector 124 . as can be seen , the two layers are overlapping , with the end 129 of layer 128 being on top of layer 126 . thus , instead of an air gap , any shunted light from layer 128 is deflected to be above layer 126 , and vice versa . alternately , since the light will originate from the emitter , it may be more preferable to have the layer overlaying the emitter be on top of the layer overlaying the detector . in the overlapping portion , a radiation blocking layer may be included , such as a colored adhesive . fig1 shows an alternate embodiment of the present invention in which a flexible circuit is printed onto a layer 130 . as shown , emitter 132 and detector 134 are mounted on the flexible layer 130 . a covering layer 133 is provided . layers 130 and 133 may be partially or substantially opaque to prevent the shunting of light . in between the layers , metal traces 136 and 138 can be used to block the shunting of light . instead of making these traces run lengthwise , leaving a clear path between the emitter and detector , they instead follow a tortuous path . this tortuous path not only goes lengthwise , but also goes across the width of the layer 130 , thus providing a barrier to block shunting the light between the emitter and detector . fig1 shows another embodiment of the present invention for modifying a sheath such as sheath 32 of fig2 . fig1 shows a sheath 140 having a first , adhesive layer 142 , and a second layer 144 being transparent and forming a pocket for the insertion of a sensor . layer 144 has opaque colored rings 146 and 148 surrounding windows 147 and 149 , respectively . these windows allow the transmission of light to and from the emitter and detector , while the opaque rings prevent the shunting of light through transparent layer 144 . alternately , more or less of the transparent layer 144 could be colored with an opaque color to prevent the shunting of light . alternately , in the embodiment of fig1 , windows 147 and 149 could be one color , while areas 146 and 148 , which may extend over the rest of the layer 144 , could be of a second color . the second color would be chosen to prevent shunting , while the first color would be chosen to allow the transmission of light while also being of a color which is compatible with the calibration data for an oximeter sensor . if the color over the emitter and detector is not chosen properly , it may interfere with the choice of a proper calibration curve in the oximeter sensor for the particular wavelength of the emitter being used . typically , leds of slightly varying wavelengths are used , with a coding resistor indicating the exact wavelength . the coding resistor is used to choose a particular calibration curve of coefficients in the oximeter sensor . thus , by using a differentially - colored sheath or reinforcing laminate or other layer , with the layer near the emitter and detector chosen to be white , clear or other color which does not interfere with the calibration , shunting can be prevented while allowing the sensor to be used without affecting its standard calibration . preferably , the regions over the emitter and detector have a radius extending at least 2 mm . beyond the borders of the emitter and detector , and preferably at least 5 mm beyond the borders of the emitter and detector . any of the shunt barriers described above could be incorporated into layer 144 of sheath 140 of fig1 . alternately , or in addition , the shunt barriers could be incorporated into a lamination or other layer placed over a sensor in a modifying process . such a modifying process may , for instance , place a non - adhesive layer over an adhesive layer to convert a disposable sensor into a reusable sensor . the shunt barriers described above may also be in an original layer in a sensor , or in a replacement layer added in a remanufacturing process for recycling disposable sensors . as will be understood by those of skill in the art , the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof . accordingly , the foregoing description is intended to be illustrative , but not limiting , of the scope of the invention which is set forth in the following claims . | 0 |
the aliphatic group represented by r includes a linear , branched or cyclic alkyl group , alkenyl group or alkynyl group , which preferably has from 1 to 30 carbon atoms . the branched alkyl group may be cyclized to form a saturated hetero ring containing one or more hetero atoms therein . for example , the group r may be a methyl group , a t - butyl group , an n - octyl group , a t - octyl group , a cyclohexyl group , a hexenyl group , a pyrrolidyl group , a tetrahydrofuryl group , or an n - dodecyl group . the aromatic group represented by r may be a monocyclic or a bicyclic aryl group , for example , a phenyl group , or a naphthyl group . the heterocyclic group represented by r can be a 3 - membered to 10 - membered unsaturated or saturated heterocyclic group having at least one hetero atom of nitrogen , oxygen , or sulfur , it may be monocyclic or may form a condensed ring with other aromatic ring ( s ) and / or hetero ring ( s ). the hetero ring is preferably a 5 - or 6 - membered aromatic hetero ring , for example , a pyridine ring , an imidazolyl ring , a quinolinyl group , a benzimidazolyl group , a pyrimidinyl group , a pyrazolyl group , an isoquinolinyl group , a benzothiazolyl group , or a thiazolyl gorup . the group represented by r may optionally be substituted by one or more substituents . in addition , these substituent groups may be further substituted . for example , the substituents may be an alkyl group , an aralkyl group , an alkenyl group , an alkynyl group , an alkoxy group , an aryl group , a substituted amino group , a ureido group , a urethane group , an aryloxy group , a sulfamoyl group , a carbamoyl gorup , an alkylthio group , an arylthio group , an alkyl - or arylsulfonyl group , an alkyl - or arylsulfinyl group , a hydroxyl group , a halogen atom , a cyano gorup , a sulfo group , an alkyloxycarbonyl group , an aryloxycarbonyl group , an acyl group , an acyloxy group , a carbonamido group , a sulfonamido group , or a carboxyl group . if possible , these groups may also be bound to each other to form a ring . the divalent organic group represented by l may be an aliphatic gorup , an aromatic group , or a group of the following structural formula : ## str7 ## wherein l &# 39 ; represents an aromatic group or a heterocyclic group ; r 0 1 to r 0 4 each independently represents a hydrogen atom , a halogen atom , or an alkyl group ; and r and s each represents 0 or 1 . the aliphatic group which may be represented by l is a linear , branched , or cyclic alkylene group , alkenylene group , or alkynylene group . the aromatic group which may be represented by l is a monocyclic or bicyclic arylene group , for example , a phenylene group , or a naphthylene group . especially preferred is a phenylene group . the group represented by l may optionally have one or more substituents . these substituents include a group of r -- y -- nh -- and those as referred to , above , as substituents on r . time represents a divalent organic group which may have a timing adjustment function . t means 0 or 1 ; and when t is 0 , pug is directly bound to the carbonyl group in the formula . a divalent organic group for time is a group capable of releasing pug from the moiety time - pug which is released from the oxidation product of the redox nucleus . this release can be via a one step reaction or a reaction having plural steps . examples of the divalent organic group for time include those which release pug by an intramolecular ring closure reaction of p - nitrophenoxy derivatives as described in u . s . pat . no . 4 , 248 , 962 ( jp - a - 54 - 145135 ); groups that release pug by a ring cleavage reaction followed by an intramolecular ring closure reaction as described in u . s . pat . no . 4 , 310 , 612 ( jp - a - 55 - 53330 ) and u . s . pat . no . 4 , 358 , 525 ; groups that release pug by an intramolecular ring closure reaction of the carboxyl group of succinic acid monoesters or their analogs with formation of an acid anhydride as described in u . s . pat . nos . 4 , 330 , 617 , 4 , 446 , 216 and 4 , 483 , 919 and jp - a - 59 - 121328 ; groups that release pug by an electron transfer of the aryloxy or heterocyclic oxy group via the conjugated double bond to form a quinomonomethane or its analog as described in u . s . pat . nos . 4 , 409 , 323 , 4 , 421 , 845 , research disclosure , item no . 21228 ( december , 1981 ), u . s . pat . no . 4 , 416 , 977 ( jp - a - 57 - 135944 ) and jp - a - 58 - 209736 and jp - a - 58 - 209738 ; groups that release pug by electron transfer of the enamine structure moiety of the nitrogen - containing ring from the gamma position of the enamine as described in u . s . pat . no . 4 , 420 , 554 ( jp - a - 57 - 136640 ), jp - a - 57 - 135945 , jp - a - 57 - 188035 , jp - a - 58 - 98728 and jp - a - 58 - 209737 ; groups that release pug by an intramolecular ring closure reaction of the hydroxyl group formed by electron transfer of the carbonyl group conjugated with the nitrogen atom of the nitrogen - containing hetero ring as described in jp - a - 57 - 56837 ; groups that release pug with formation of aldehydes as described in u . s . pat . no . 4 , 146 , 396 ( jp - a - 52 - 90932 ), jp - a - 59 - 93442 , jp - a - 59 - 75475 , jp - a - 60 - 249148 and jp - a - 60 - 249149 ; groups that release pug with the decarbonylation of the carboxyl group as described in jp - a - 51 - 146828 , jp - a - 57 - 179842 and jp - a - 59 - 104641 ; groups having -- o -- coocr 2 r 6 -- pug that release pug by decarbonylation followed by formation of aldehydes ; groups that release pug by formation of isocyanates as described in jp - a - 60 - 7429 ; and groups that release pug by a coupling reaction with the oxidation product of a color developing agent as described in u . s . pat . no . 4 , 438 , 193 . preferably , the divalent group represented by time in formula ( 1 ) may be selected from those of the following formulae ( t - 1 ) to ( t - 6 ), where (*) indicates the position where time is bonded to ## str8 ## and (**) indicates the position where time is bonded to pug . ## str9 ## wherein w represents an oxygen atom , a sulfur atom or ## str10 ## r 11 and r 12 each independently represents a hydrogen atom or a substituent ; r 13 represents a substituent ; t represents 1 or 2 , and when t is 2 , two ## str11 ## may be the same or different . where r 11 and r 12 are substituents , specific examples of the substituents are r 14 , r 14 co --, r 14 so 2 --, ## str12 ## r 14 represents an aliphatic group , an aromatic group or a heterocyclic group ; and r 15 represents an aliphatic group , an aromatic group , a heterocyclic group , or a hydrogen atom . examples of the substituents as r 13 include the same substituents as r 11 and r 12 as described above . r 11 , r 12 and r 13 each may be a divalent group to form a cyclic structure . specific examples of the groups represented by formula ( t - 1 ) are mentioned below . ## str13 ## wherein nu represents a nucleophilic group , and an oxygen atom or a sulfur atom are examples of nucleophilic nuclides ; e represents an electrophilic group and it is nucleophilically attacked by nu to be able to cleave the bond to the position of (**); link represents a linking group which participates in the steric configuration of nu and e so that nu and e may be subjected to intramolecular nucleophilic substitution reaction therebetween . specific examples of the groups represented by formula ( t - 2 ) are mentioned below . ## str14 ## wherein w , r 11 , r 12 and t have the same meaning as those in formula ( t - 1 ). specific examples of the groups of formula ( t - 3 ) are mentioned below . ## str15 ## in these formulae , w and r 11 have the same meanings as those in formula ( t - 1 ). specific examples of the groups of formula ( t - 6 ) are mentioned below . ## str16 ## specific examples of the divalent organic groups for time are also described in detail in jp - a - 61 - 236549 and jp - a - 64 - 88451 and japanese patent application no . 63 - 98803 . preferred examples of these groups are mentioned below . ## str17 ## the group pug represents a photographically useful compound that can be present as either ( time ) t - pug or pug . examples of photographically useful groups are development inhibitors , development accelerators , nucleating agents , foggants , couplers , diffusible or nondiffusible dyes , desilvering accelerators , desilvering inhibitors , silver halide solvents , competing compounds , developing agents , auxiliary developing agents , fixation accelerators , fixation inhibitors , image stabilizers , color toning agents , processing dependence improving agents , dot improving agents , color image stabilizers , photographic dyes , surfactants , hardening agents , desensitizing agents , contrast enhancing agents , chelating agents , brightening agents , acids , bases , and precursors of acids or bases . examples of these photographically useful compounds are described in , for example , t . h . james , the theory of the photographic process , 4th ed . ( published by macmillan , 1977 ). more precisely , development inhibitors , dyes , couplers and developing agents are described in detail in u . s . pat . no . 4 , 248 , 962 ; foggants in jp - a - 59 - 170840 ; and desilvering accelerators ( bleach accelerators ) in jp - a - 62 - 168159 . photographically useful groups often overlap with each other with respect to their usefulness . as a typical exampl of the group , a development inhibitor is discussed in detail below . the development inhibitor represented by pug or ( time ) t - pug may be a known development inhibitor containing hetero atoms . such an inhibitor is bound to ## str18 ## in formula ( 1 ) via the hetero atom . examples of such development inhibitors are described , for example , in c . e . k . mees and t . h . james , the theory of photographic processes , 3rd ed . ( published by macmillan 1966 ), pages 344 to 346 . they include , for example , mercaptotetrazoles , mercaptotriazoles , mercaptoimidazoles , mercaptopyrimidines , mercaptobenzimidazoles , mercaptobenzothiazoles , mercaptobenzoxazoles , mercaptothiadiazoles , benzotriazoles , benzimidazoles , indazoles , adenines , guanines , tetrazoles , tetraazaindenes , triazaindenes and mercaptoaryls . the development inhibitors represented by pug may optionally be substituted . in addition , these substituents may be further substituted . an example of a group that may be a substituent is an alkyl group , an aralkyl group , an alkenyl group , an alkynyl group , an alkoxy group , an aryl group , a substituted amino group , a ureido group , a urethane group , an aryloxy group , a carbamoyl group , an alkylthio group , an arylthio gorup , an alkyl - or arylsulfonyl group , an alkyl - or arylsulfinyl group , a hydroxyl group , a halogen atom , a cyano group , an aryloxycarbonyl group , an acyl group , an alkoxycarbonyl group , an acyloxy group , a carbonamido group , a sulfoxy group , or a phosphoric acid amido group . when the development inhibitors represented by pug have a nitro group , it is preferred that t in ( time ) t is 1 . in formula ( 1 ), the group r or -( time ) t - pug may contain a ballast group which is generally contained in a nondiffusible photographic additive such as a coupler or a gorup that accelerates adsorption of the compound of formula ( 1 ) to silver halide grains . the ballast group usable for this purpose is an organic group which may give sufficient molecular weight to the compound of formula ( 1 ) so that the compound would not substantially diffuse into other layers or into the processing solution . the ballast group is composed of one or more of the following groups : an alkyl gorup , an aryl group , a heterocyclic group , an ether group , a thioether group , an amido group , a ureido group , a urethane group , or a sulfonamido group . preferably , the ballast group contains a substituted benzene ring ; especially preferred is ballast gorup having a benzene ring substituted with a branched alkyl group . examples of groups that accelerate the adsorption of the compound of formula ( 1 ) to silver halides are the following : cyclic thioamido groups ( such as 4 - thiazoline - 2 - thione , 4 - imidazoline - 2 - thione , 2 - thiohydantoin , rhodanine , thiobarbituric acid , tetrazoline - 5 - thione , 1 , 2 , 4 - triazoline - 3 - thione , 1 , 2 , 4 - oxazoline - 2 - thione , benzimidazoline - 2 - thione , benzoxazoline - 2 - thione , benzothiazoline - 2 - thione , thiotriazine and 1 , 3 - imidazoline - 2 - thione ); chain thioamido groups ; aliphatic mercapto groups ; aromatic mercapto groups ; heterocyclic mercapto groups ( when a nitrogen atom is adjacent to the carbon atom bonded to -- sh , the groups have the same meaning as the cyclic thioamido groups which are tautomers of the groups , and specific examples of the groups are the same as those mentioned above ); groups containing disulfido bond ; 5 - membered or 6 - membered nitrogen - containing heterocyclic groups composed of a combination of nitrogen , oxygen , sulfur and carbon atoms ( such as benzotriazoles , triazoles , tetrazoles , indazoles , benzimidazoles , imidazoles , benzothiazoles , thiazoles , thiazolines , benzoxazoles , oxazoles , oxazolines , thiadiazoles , oxathiazoles , triazines , azaindenes ); and heterocyclic quaternary salts such as benzimidazoliniums . these groups may further be substituted , if desired . examples of these substituents are those discussed as representative of r , above . specific examples of compounds of formula ( 1 ) employable in the present invention are given below . these are not , however , intended to limit the present invention . ## str19 ## the compounds of formula ( 1 ) used in the present invention are produced in accordance with the methods described in jp - a - 61 - 213847 and jp - a - 62 - 260153 , u . s . pat . no . 4 , 684 , 604 , and japanese patent application no . 63 - 98803 . the compounds of formula ( 1 ) can be incorporated into the photographic emulsion layer or hydrophilic colloid layer of the silver halide photographic materials of the present invention . the compound of formula ( 1 ) may be first dissolved in water or in a water - miscible organic solvent ( if desired , in the presence of an alkali hydroxide or a tertiary amine for salt formation ), the resulting solution may then be added to the hydrophilic colloid liquid ( such as silver halide emulsion or aqueous gelatin solution ), and the ph of the resulting colloid liquid may be adjusted by addition of an acid or alkali , if desired . the compounds of formula ( 1 ) can be employed singly or in combinations of two or more when incorporated into the photographic material . the amount of the compound of formula ( 1 ) to be added to the photographic material is preferably from 1 × 10 - 6 to 5 × 10 - 2 mol , more preferably from 1 × 10 - 5 to 1 × 10 - 2 mol , per mol of the silver halide in the material . a pertinent amount may be added , as known in the art , in accordance with the properties of the silver halide emulsion combined with the compound . the compound of formula ( 1 ) is preferably employed in combination with a hydrazine derivative of general formula ( 2 ). ## str20 ## wherein r 31 represents an aliphatic group or an aromatic group ; r 32 represents a hydrogen atom , an alkyl group , an aryl group , an alkoxy group , an aryloxy group , an amino group , a carbamoyl group , or an oxycarbonyl group ; g 1 represents a ## str21 ## a thiocarbonyl group , or an iminomethylene group ; and both a 1 and a 2 are hydrogen atoms , or one of them is a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group , a substituted or unsubstituted arylsulfonyl group , or a substituted or unsubstituted acyl group . in formula ( 2 ), the aliphatic group represented by r 31 is preferably a linear , branched or cyclic alkyl group having from 1 to 30 carbon atoms , more preferably from 1 to 20 carbon atoms . the branched alkyl groups may be cyclized to form a saturated hetero ring containing one or more hetero atoms . the alkyl groups may optionally be substituted by the following substituent ( s ): an aryl group , an alkoxy group , a sulfoxy group , a sulfonamido group , or a carbonamido group . in formula ( 2 ), the aromatic group represented by r 31 is a monocyclic or bicyclic aryl group or unsaturated heterocyclic group . the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a hetero aryl group . examples of these groups are a benzene ring , a naphthalene ring , a pyridine ring , a pyrimidine ring , an imidazole ring , a pyrazole ring , a quinoline ring , an isoquinoline ring , a benzimidazole ring , a thiazole ring , and a benzothiazole ring . especially preferred is a benzene ring . the aryl group or unsaturated heterocyclic group represented by r 31 may optionally be substituted . typical substituents are an alkyl group , an aralkyl group , an alkenyl group , an alkynyl group , an alkoxy group , an aryl group , a substituted amino group , a ureido group , a urethane group , an aryloxy group , a sulfamoyl group , a carbamoyl group , an alkylthio group , an arylthio group , an alkyl - or arylsulfonyl group , an alkyl or arylsulfinyl group , a hydroxyl group , a halogen atom , a cyano group , a sulfo group , an aryloxycarbonyl group , an acyl group , an alkoxycarbonyl group , an acyloxy group , a carbonamido group , a sulfonamido group , a carboxyl group , a phosphoric acid amido group , a diacylamino group , an imido group , and an ## str22 ## preferably , the substituents are a linear , branched , or cyclic alkyl group ( preferably having from 1 to 20 carbon atoms ), an aralkyl group ( preferably a monocyclic or bicyclic group where the alkyl moiety has from 1 to 3 carbon atoms ), an alkoxy group ( preferably having from 1 to 20 carbon atoms ), a substituted amino group ( preferably an amino group substituted by one or more alkyl groups each having from 1 to 20 carbon atoms ), an acylamino group ( preferably having from 2 to 30 carbon atoms ), a sulfonamido group ( preferably having from 1 to 30 carbon atoms ), a ureido group ( preferably having from 1 to 30 carbon atoms ), or a phosphoric acid amido group ( preferably having from 1 to 30 carbon atoms ). in formula ( 2 ), the alkyl group represented by r 32 is preferably an alkyl group having from 1 to 4 carbon atoms , which may be optionally substituted by the following substituent ( s ): a halogen atom , a hydroxyl group , a cyano group , a carboxyl group , a sulfo group , an alkoxy group , a phenyl group , an alkyl - or arylsulfonyl group , an acyl group , an alkoxycarbonyl group , an aryloxycarbonyl group , a carbamoyl group , a sulfamoyl group , a nitro group , a heterocyclic aromatic group , or an ## str23 ## these groups may further be substituted . the aryl group represented b r 32 is preferably a monocyclic or bicyclic aryl group , for example , containing a benzene ring . the aryl group may be optionally substituted by substituent ( s ), such as , for example , a halogen atom , an alkyl group , a cyano group , a carboxyl group , a sulfo group , or a sulfonyl group . the alkoxy group represented by r 32 is preferably an alkoxy group having from 1 to 8 carbon atoms , which may be optionally substituted by one or more substituents that are either a halogen atom or an aryl group . the aryloxy group represented by r 32 is preferably monocyclic , and may be optionally substituted by a halogen atom or the like . the amino group represented by r 32 is preferably an unsubstituted amino group , an alkylamino group having from 1 to 10 carbon atoms , or an arylamino group . it may be optionally substituted by one or more of the following substituents : an alkyl group , a halogen atom , a cyano group , a nitro group , and / or a carboxyl group . the carbamoyl group represented b r 32 is preferably an unsubstituted carbamoyl group , or an alkylcarbamoyl group having from 1 to 10 carbon atoms or an arylcarbamoyl group . it may be optionally substituted by one or more of the following substituents : an alkyl group , a halogen atom , a cyano group , and / or a carboxyl group . the oxycarbonyl group represented by r 32 is preferably an alkoxycarbonyl group having from 1 to 10 carbon atoms or an aryloxycarbonyl group , and it may be optionally substituted by one or more of the following substituents : an alkyl group , a halogen atom , a cyano group , and / or a nitro group . where g 1 is ## str24 ## r 32 is preferably a hydrogen atom , an alkyl group ( e . g ., methyl , trifluoromethyl , 3 - hydroxypropyl , 3 - methanesulfonamidopropyl , phenylsulfonylmethyl ), an aralkyl group ( e . g ., o - hydroxybenzyl ), or an aryl group ( e . g ., phenyl , 3 , 5 - dichlorophenyl , o - methanesulfonamidophenyl , 4 - methanesulfonylphenyl , 2 - hydroxymethylphenyl ); and it is most preferably a hydrogen atom . where g 1 is -- so 2 --, r 32 is preferably an alkyl group ( e . g ., methyl ), an aralkyl group ( e . g ., o - hydroxybenzyl ), an aryl group ( e . g ., phenyl ), or a substituted amino group ( e . g ., dimethylamino ). where g 1 is -- so --, r 32 is preferably a cyanobenzyl group or a methylthiobenzyl group . where g 1 is ## str25 ## group , r 32 is preferably a methoxy group , an ethoxy group , a butoxy group , a phenoxy group , or a phenyl group ; most preferably a phenoxy group . where g 1 is an n - substituted or unsubstituted iminomethylene group , r 32 is preferably a methyl group , an ethyl group , or a substituted or unsubstituted phenyl group . substituents on r 32 , if any , are the same as those mentioned for r 31 , above . in formula ( 2 ), g 1 is most preferably a ## str26 ## group . r 32 may also be such a group that causes release of the -- g 1 -- r 32 moiety from the remaining molecule followed by a cyclization reaction to form a cyclic structure containing the atoms of the thus released -- g 1 -- r 32 moiety . such an r 32 group is represented by the following formula ( a ): wherein z 31 represents a group which nucleophilically attacks the group g 1 to cleave the -- g 1 -- r 33 -- z 31 moiety from the remaining molecule ; where r 33 represents a group derived from r 32 by the removal of one hydrogen atom . in the group represented by formula ( a ), z 31 nucleophilically attacks g 1 and , as a result , g 1 , r 33 and z 31 form a cyclic structure . more precisely , z 31 is a group that easily reacts nucleophilically with g 1 , when the hydrazine compound of formula ( 2 ) forms a reaction intermediate of : by oxidation , thereby cleaving the r 31 -- n ═ n -- moiety from group g 1 . specifically , z 31 may be a functional goup which directly reacts with group g 1 , such as oh , sh or nhr 34 ( where r 34 represents a hydrogen atom , an alkyl group , an aryl group , -- cor 35 , or -- so 2 r 35 ; and r 35 represents a hydrogen atom , an alkyl group , an aryl group or a heterocyclic group ), or cooh , these groups oh , sh , nhr 34 , and cooh , may be temporarily protected so that the free group is formed by hydrolysis with an alkali or the like . alternatively , z 31 may also be a functional group which may react with the g 1 group after reacting with a nucleophilic agent such as a hydroxyl ion or a sulfite ion . examples of such functional groups are ## str27 ## ( where r 36 and r 37 each represents a hydrogen atom , an alkyl group , an alkenyl group , an aryl group , or a heterocyclic group ). the ring formed by g 1 , r 33 and z 31 is preferably a 5 - membered or 6 - membered one . of the formula ( a ) groups , those represented by the following formulae ( b ) and ( c ) are preferred . ## str28 ## wherein r b 1 to r b 4 each represents a hydrogen atom , an alkyl group ( preferably having from 1 to 12 carbon atoms ), an alkenyl group ( preferably having from 2 to 12 carbon atoms ), or an aryl group ( preferably having from 6 to 12 carbon atoms ), and these may be the same or different ; b represents an atomic group necessary for completing an optionally substituted 5 - membered or 6 - membered ring ; and m and n each represents 0 or 1 where ( n + m ) is 1 or 2 . examples of 5 - membered or 6 - membered rings formed by b are a cyclohexene ring , a cyclopentene ring , a benzene ring , a naphthalene ring , a pyridine ring , and a quinoline ring . z 31 in formula ( b ) represents the same groups as it does in formula ( a ), above . ## str29 ## wherein r c 1 and r c 2 each represents a hydrogen atom , an alkyl group , an alkenyl group , an aryl group , or a halogen atom , and these may be the same or different ; r c 3 represents a hydrogen atom , an alkyl group , an alkenyl group , or an aryl group ; and p represents 0 or 1 , and q represents 1 , 2 , 3 , or 4 . r c 1 , r c 2 and r c 3 may be bonded to each other to form a ring , provided that z 31 has a structure capable of attacking group g 1 by an intramolecular nucleophilic reaction . r c 1 and r c 2 each are preferably a hydrogen atom , a halogen atom , or an alkyl group ; and r c 3 is preferably an alkyl group or an aryl group . q is preferably 1 , 2 , or 3 . when q is 1 , p is 1 ; when q is 2 , p is 0 or 1 ; when q is 3 , p is 0 or 1 ; and when q is 2 or 3 , the plural (-- cr c 1 r c 2 )&# 39 ; s may be the same or different . z 31 in formula ( c ) represents the same groups as it does in formula ( a ), above . a 1 and a 2 each represents a hydrogen atom ; an alkylsulfonyl or arylsulfonyl group having 20 or less carbon atoms ( preferably an unsubstituted phenylsulfonyl group or a phenylsulfonyl group so substituted that the total of the hammett &# 39 ; s substituent constants is - 0 . 5 or more ); an acyl group having 20 or less carbon atoms ( preferably an unsubstituted benzoyl group or a benzoyl group so substituted that the total of the hammett &# 39 ; s substituent constants is - 0 . 5 or more ); or a linear , branched or cyclic substituted or unsubstituted aliphatic acyl group ( where the substituents of the group are , for example , a halogen atom , an ether group , a sulfonamido group , a carbonamido group , a hydroxyl group , a carboxyl group , or a sulfonic acid group ). r 31 or r 32 in formula ( 2 ) may have a ballast group which is generally present in a nondiffusible photographic additive such as a coupler . the ballast group is a group which is relatively inactive in terms of photographic properties and has 8 or more carbon atoms . examples of ballast groups are an alkyl group , an alkoxy group , a phenyl group , an alkylphenyl group , a phenoxy group , or an alkylphenoxy group . r 31 or r 32 in formula ( 2 ) may have a group which functions to enhance the adsorption of the compound of formula ( 2 ) to the surface of silver halide grains . examples of such adsorbing groups are thiourea groups , heterocyclic thioamido groups , mercaptoheterocyclic groups , triazole groups as well as the groups mentioned in u . s . pat . nos . 4 , 385 , 108 and 4 , 459 , 347 , jp - a - 59 - 195233 , jp - a - 59 - 200231 , jp - a - 59 - 201045 , jp - a - 59 - 201046 , jp - a - 59 - 201047 , jp - a - 59 - 201048 , jp - a - 59 - 201049 , jp - a - 61 - 170733 , jp - a - 61 - 270744 , jp - a - 62 - 948 , jp - a - 63 - 234244 , jp - a - 63 - 234246 , and japanese patent application no . 62 - 67501 . specific nonlimiting examples of compounds of formula ( 2 ) are given below . ## str30 ## hydrazine derivatives usable in the present invention , in addition to the above - mentioned compounds , are described in research disclosure , item no . 23516 ( november , 1983 , page 346 ) and the literature as referred to therein ; as well as in u . s . pat . nos . 4 , 080 , 207 , 4 , 269 , 929 , 4 , 276 , 364 , 4 , 278 , 748 , 4 , 385 , 108 , 4 , 459 , 347 , 4 , 560 , 638 , 4 , 478 , 928 , british patent 2 , 011 , 391b , european patent 217 , 310 or u . s . pat . no . 4 , 686 , 167 , jp - a - 60 - 179734 , jp - a - 62 - 270948 , jp - a - 63 - 29751 , jp - a - 61 - 170733 , jp - a - 61 - 270744 , jp - a - 62 - 948 , jp - a - 62 - 178246 , jp - a - 63 - 32538 , jp - a - 63 - 104047 , jp - a - 63 - 121838 , jp - a - 63 - 129337 , jp - a - 63 - 223744 , jp - a - 63 - 234244 , jp - a - 63 - 234245 , jp - a - 63 - 234246 , jp - a - 63 - 294552 , jp - a - 63 - 306438 , jp - a - 1 - 100530 , jp - a - 1 - 105941 , jp - a - 1 - 105943 , jp - a - 64 - 10233 , jp - a - 1 - 90439 , and japanese patent application nos . 63 - 105682 , 63 - 114118 , 63 - 110051 , 63 - 114119 , 63 - 116239 , 63 - 147339 , 63 - 179760 , 63 - 229163 , hei - 1 - 18377 , 1 - 18378 , 1 - 18379 , 1 - 15755 , 1 - 16814 , 1 - 40792 , 1 - 42615 , 1 - 42616 , 1 - 123693 , 1 - 126284 . in accordance with the present invention , the amount of the hydrazine derivative to be added to the photographic material is preferably from 1 × 10 - 6 mol to 5 × 10 - 2 mol , most preferably from 1 × 10 - 5 mol to 2 × 10 - 2 mol , per mol of the silver halide in the material . the hydrazine derivatives can be incorporated into the photographic emulsion layer or hydrophilic colloid layer of the photographic material of the present invention . by combining a compound of formula ( 1 ) and a hydrazine derivative of formula ( 2 ) with a negative emulsion , a negative image having high contrast can be formed . in addition , a compound of formula ( 1 ) and a derivative of formula ( 2 ) may also be combined with an internal latent image - type silver halide emulsion . it is preferred that a compound of formula ( 1 ) be combined with a hydrazine derivative of formula ( 2 ) and a negative emulsion for forming a negative image having high contrast . where a compound of formula ( 1 ) is utilized to form a negative image having high contrast , the silver halide grains employed are preferably fine grains having a mean grain size of 0 . 7 μm or less , more preferably 0 . 5 μm or less . although the molecular size distribution of the silver halide grains is not specifically limited , the emulsion is preferably a monodispersed emulsion . the &# 34 ; monodispersed emulsion &# 34 ; as used herein means that at least 95 % by number or by weight of the silver halide grains in the emulsion have a grain size falling within the range of the mean grain size , or plus or minus 40 %. the silver halide grains in the photographic emulsion may be regular crystals such as cubic , octahedral , rhombic dodecahedral or tetradecahedral crystals ; they may be irregular crystals such as spherical or tabular crystals ; or they may be composite crystals composed of a variety of regular and irregular crystal forms . the silver halide grains may be composed of a uniform phase throughout the whole grain or a different phase inside the grain and at the surface layer of the grain . the silver halide grains of the emulsion of the present invention may be formed or physically ripened in the presence of a cadmium salt , a sulfite , a lead salt , a thallium salt , a rhodium salt , a complex rhodium salt , an iridium salt , or a complex iridium salt . specifically , the silver halide grains for use in the present invention are prepared in the presence of an iridium salt or a complex iridium salt present in an amount of from 10 - 8 to 10 - 5 mol per mol of silver . these silver halide grains are silver haloiodides where the silver iodide content of the surface of the grain is larger than the mean silver iodide content of the whole grain . by using an emulsion containing such silver haloiodide grains , a photographic material having a much higher sensitivity and a much higher gamma value can be obtained . the silver halide emulsion employed in the present invention may or may not be chemically sensitized . chemical sensitization of silver halide grains is known using a sulfur sensitization , a reduction sensitization , or a noble metal sensitization . any of these sensitizations can be employed singly or in a combination of two or more for chemical sensitization of the emulsion of the invention . gold sensitization is a typical noble metal sensitization method , which uses gold compounds that are essentially gold complexes . needless to say , other noble metals , such as platinum , palladium , or rhodium , may also be used for a noble metal sensitization . examples of the compounds usable in such sensitization methods are described in u . s . pat . no . 2 , 448 , 060 and british patent 618 , 016 . examples of sulfur sensitizing agents are sulfur compounds that are contained in gelatin as well as other sulfur compounds , such as thiosulfates , thioureas , thiazoles and rhodanines . any of these can be employed in the present invention . in the above - mentioned chemical sensitization , it is preferred to use an iridium salt or a rhodium salt before the physical ripening of the silver halide emulsion is completed . more preferred is to use the sensitizer during formation of the silver halide grains . in the present invention , it is preferred that the silver halide emulsion layer contains two mono - dispersed emulsions each having a different mean grain size as illustrated in jp - a - 61 - 223734 and jp - a - 62 - 90646 , whereby the maximum density ( dmax ) is elevated . of the two emulsions , the small sized monodispersed grains are preferably chemically sensitized , most preferably by sulfur sensitization . the other large sized mono - dispersed grains may or may not be chemically sensitized . since sensitized large sized monodispersed grains often cause generation of black peppers , they are not generally chemically sensitized . however , if they are chemically sensitized , it is especially desired that the chemical sensitization is lightly effected so that it does not cause generation of black peppers . the phrase &# 34 ; chemical sensitization is lightly effected &# 34 ; means that the time of chemical sensitization of the large sized grains is shorter than that of the small sized grains , or the temperature is lowered , or the amount of the chemical sensitizing agent to be added is reduced . although not specifically limited , the difference in the sensitivity between the large sized monodispersed emulsion and the small sized monodispersed emulsion is preferably from 0 . 1 to 1 . 0 , more preferably from 0 . 2 to 0 . 7 , as δlog e . that is , it is preferred that the sensitivity of the large sized monodispersed emulsion is higher . the sensitivity of the emulsion is one as measured by coating an emulsion containing a hydrazine derivative on a support and processing the coated layer with a developer containing a sulfite ion in an amount of 0 . 15 mol / liter or more having a ph value of from 10 . 5 to 12 . 3 . the mean grain size of the small sized monodispersed grains is 90 % or less of that of the large sized monodispersed grains and is preferably 80 % or less thereof . the mean grain size of the silver halide grains for use in the present invention is preferably within the range of from 0 . 02 μm to 1 . 0 μm , more preferably from 0 . 1 μm to 0 . 5 μm . it is more preferred that the mean grain sizes of both the large sized grains and the small sized grains are within the given ranges . where two or more emulsions each having a different mean grain size are employed in the present invention , the amount of the silver ion the small sized monodispersed emulsion coated is preferably from 40 to 90 % by weight , more preferably from 50 to 80 % by weight , of the total amount of silver coated . where two or more emulsions each having a different mean grain size are employed in the present invention , they may be incorporated into the same emulsion layer or may be separately incorporated into different emulsion layers . in the latter case of introducing the emulsions into different emulsion layers , it is preferred that the large sized emulsion layer is an upper layer and the small sized emulsion layer is a lower layer . the total amount of silver coated is preferably from 1 g / m 2 to 8 g / m 2 . the photographic materials of the present invention can contain various sensitizing dyes , for example , those described in jp - a - 55 - 52050 , pages 45 to 53 ( such as cyanine dyes or merocyanine dyes ), for the purpose of elevating the sensitivity of the material . these sensitizing dyes may be added to the photographic material singly or in combinations of two or more . the combination of sensitizing dyes is often employed for the purpose of super color sensitization . additionally , dyes which do not have a color sensitizing effect by themselves or substances which do not substantially absorb visible rays but have a super color sensitizing capacity may also be incorporated into the emulsion of the photographic material of the invention , along with the sensitizing dyes . usable sensitizing dyes , combinations of dyes for super color sensitization and super color sensitizing substances are described in detail in research disclosure , vol . 176 , item no . 17643 ( december , 1978 ), page 23 , jv - j . the photographic materials of the present invention can contain various compounds for the purpose of preventing the materials from fogging during manufacture , storage , or photographic processing , or for the purpose of stabilizing the photographic properties of the materials . for instance , various compounds which are known as an antifoggant or stabilizer can be employed . these include azoles such as benzothiazolium salts , nitroindazoles , chlorobenzimidazoles , bromobenzimidazoles , mercaptothiazoles , mercaptobenzothiazoles , mercaptothiadiazoles , aminotriazoles , benzothiazoles , nitrobenzotriazoles ; mercaptopyrimidines ; mercaptotriazines ; thioketo compounds such as oxazolinethione ; azaindenes such as triazaindenes , tetraazaindenes ( especially 4 - hydroxy - substituted ( 1 , 3 , 3a , 7 ) tetraazaindenes ), pentaazaindenes ; as well as benzenethiosulfonic acids , benzenesulfinic acids ; and benzenesulfonic acid amides . above all , benzotriazoles ( for example , 5 - methylbenzotriazole ) and nitroindazoles ( for example , 5 - nitroindazole ) are preferred . these compounds may be added to the processing solutions . examples of development accelerators or an accelerator for nucleating infectious development suitably employed in the present invention are the compounds illustrated in jp - a - 53 - 77616 , jp - a - 54 - 37732 , jp - a - 53 - 137133 , jp - a - 60 - 140340 and jp - a - 60 - 14959 , as well as other compounds containing nitrogen and / or sulfur atom ( s ). the optimum amount of accelerator applied to the photographic materials of the present invention , although varying in accordance with the kind of the compound of the agent , is desirably from 1 . 0 × 10 - 3 to 0 . 5 g / m 2 and preferably from 5 . 0 × 10 - 3 to 0 . 1 g / m 2 . the photographic materials of the present invention can contain a desensitizing agent in the photographic emulsion layer or in any other hydrophilic colloid layers . a desensitizing agent for use in the present invention may be an organic desensitizing agent , as defined by the polarographic half - wave potential or by the oxidation reduction potential as determined by polarography . that is , the agent is defined so that the sum of the polarographic anode potential and the polarographic cathode potential is positive . the method of measuring the polarographic oxidation reduction potential is described , for example , in u . s . pat . no . 3 , 501 , 307 . an organic desensitizing agent for use in the present invention is preferably one having at least one water - soluble group . for instance , the water - soluble group may be a sulfonic acid group , a carboxylic acid group , or a phosphonic acid group , and it may be in the form of a salt with an organic base ( for example , ammonia , pyridine , triethylamine , piperidine or morpholine ) or an alkali metal ( for example , sodium or potassium ). as preferred organic desensitizing agents for use in the present invention , the compounds of formulae ( iii ) to ( v ) described in jp - a - 63 - 133145 , pages 55 to 72 are mentioned . in accordance with the present invention , the organic desensitizing agent is preferably incorporated into the silver halide emulsion layer in an amount of from 1 . 0 × 10 - 8 to 1 . 0 × 10 - 4 mol / m 2 , preferably from 1 . 0 × 10 - 7 to 1 . 0 × 10 - 5 mol / m 2 . the photographic materials of the present invention can contain water - soluble dyes in the emulsion layer or in any other hydrophilic colloid layers , as a filter dye , for the purpose of antiirradiation , or for any other purpose known in the art . the filter dyes are those having a function of further lowering the photographic sensitivity of the photographic materials . they are preferably ultraviolet absorbents having a spectral absorption maximum in the intrinsic sensitivity range of the silver halides of the materials or dyes , and they exhibit substantial light absorption from about 380 nm to 600 nm for the purpose of elevating safety to a safelight when the materials are handled under daylight conditions . these dyes are added to the emulsion layer , the upper layer of the silver halide emulsion layer , or the non - light - sensitive hydrophilic colloid layer depending on which is more remote from the support than the silver halide emulsion layer . the chosen dye ( s ) are preferably fixed to the layer along with a mordant agent . ultraviolet absorbents are added to the photographic materials in an amount of from 10 - 2 g / m 2 to 1 g / m 2 , preferably from 50 mg / m 2 to 500 mg / m 2 , in accordance with the molar extinction coefficient thereof . the ultraviolet absorbents may be dissolved in a pertinent solvent ( for example , water ; alcohols , such as methanol , ethanol or propanol ; acetone ; methyl cellosolve ; or mixed solvents ) and the resulting solution added to the coating composition . the ultraviolet absorbents usable in the present invention , for example , are aryl group - substituted benzotriazole compounds , 4 - thiazolidone compounds , benzophenone compounds , cinnamic acid ester compounds , butadiene compounds , benzoxazole compounds , and ultraviolet absorbing polymers . specific examples of the usable ultraviolet absorbents are described , for example , in u . s . pat . nos . 3 , 533 , 794 , 3 , 314 , 794 , 3 , 352 , 681 , 3 , 705 , 805 , 3 , 707 , 375 , 4 , 045 , 229 , 3 , 700 , 455 and 3 , 499 , 762 , west german patent ( ols ) no . 1 , 547 , 863 , and jp - a - 46 - 2784 . the filter dyes usable in the present invention include oxonol dyes , hemioxonol dyes , styryl dyes , merocyanine dyes , cyanine dyes , and azo dyes . for the purpose of decreasing the residual color in the photographic materials as developed , water - soluble dyes or dyes which may be decolored by alkali substances or sulfite ion are preferred as the filter dyes . specific examples of such filter dyes are the pyrazoloneoxonol dyes described in u . s . pat . no . 2 , 274 , 782 ; the diarylazo dyes described in u . s . pat . no . 2 , 956 , 879 ; the styryl dyes or butadienyl dyes described in u . s . pat . nos . 3 , 423 , 207 and 3 , 384 , 487 ; the merocyanine dyes described in u . s . pat . no . 2 , 527 , 583 ; the merocyanine dyes or oxonol dyes described in u . s . pat . nos . 3 , 486 , 897 , 3 , 652 , 284 and 3 , 718 , 472 ; the enaminohemioxonol dyes described in u . s . pat . no . 3 , 976 , 661 . in addition , the dyes described in british patents 584 , 609 and 1 , 177 , 429 , jp - a - 48 - 85130 , jp - a - 49 - 99620 , jp - a - 49 - 114420 , and u . s . pat . nos . 2 , 533 , 472 , 3 , 148 , 187 , 3 , 177 , 078 , 3 , 247 , 127 , 3 , 540 , 887 , 3 , 575 , 704 and 3 , 653 , 905 may also be used . the dyes are dissolved in an appropriate solvent ( for example , water ; alcohols , such as methanol , ethanol , or propanol ; acetone ; methyl cellosolve ; or mixed solvents thereof ). the resulting solution may be added to the coating composition to form the non - light - sensitive hydrophilic colloid layer in photographic materials of the present invention . the preferred amount of the dyes to be incorporated into the layer may be from 10 - 3 g / m 2 to 1 g / m 2 , more preferred is from 10 - 3 g / m 2 to 0 . 5 g / m 2 . the photographic materials of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or in any other hydrophilic colloid layers . for instance , chromium salts , aldehydes ( e . g ., formaldehyde , glutaraldehyde ), n - methylol compounds ( e . g ., dimethylolurea ), active vinyl compounds ( e . g ., 1 , 3 , 5 - triacryloylhexahydro - s - triazine , 1 , 3 - vinylsulfonyl - 2 - propanol ), active halogen compounds ( e . g ., 2 , 4 - dichloro - 6 - hydroxy - s - triazine ) and mucohalogenic acids can be employed singly or in combination of two or more of them as the hardening agent . the photographic materials of the present invention can further contain various surfactants in the photographic emulsion layer or in any other hydrophilic colloid layers for various purposes such as coating assistance , prevention of static charge , improvement of slide properties , emulsification and dispersion , prevention of surface blocking , and improvement of photographic characteristics ( for example , acceleration of developability , elevation of cotnrast and enhancement of sensitivity ). surfactants especially preferably employed in the present invention are polyalkylene oxides having a molecular weight of 600 or more , such as those described in u . s . pat . no . 4 , 221 , 857 and jp - b - 58 - 9412 ( the term &# 34 ; jp - b &# 34 ; as used herein refers to an &# 34 ; examined japanese patent publication &# 34 ;). where the surfactants employed act as an antistatic agent , fluorine - containing surfactants ( described in detail in u . s . pat . no . 4 , 201 , 586 and jp - a - 60 - 80849 and jp - a - 59 - 74554 ) are particularly preferred . the photographic materials of the present invention may contain a matting agent such as silica , magnesium oxide , or polymethyl methacrylate in the photographic emulsion layer or in any other hydrophilic colloid layer to prevent surface blocking . additionally , the photographic materials of the present invention may also contain a dispersion of a water - insoluble or hardly water - soluble synthetic polymer in the photographic emulsion for the purpose of improving dimensional stability . for instance , polymers or copolymers composed of monomers of alkyl ( meth ) acrylates , alkoxyalkyl ( meth ) acrylates and / or glycidyl ( meth ) acrylates singly or in combinations . optionally , these monomers may be employed along with other comonomers of acrylic acids and / or methacrylic acids . the photographic materials of the present invention preferably contain an acid group - containing compound in the silver halide emulsion layer or in any other layers . as the acid group - containing compound can be , for example , organic acids ( such as salicylic acid , acetic acid , or ascorbic acid ) as well as polymers or copolymers composed of acid monomers ( such as acrylic acid , maleic acid , or phthalic acid as the repeating unit ). the description of these compounds is further detailed in jp - a - 61 - 223834 , jp - a - 61 - 228437 , jp - a - 62 - 25745 and jp - a - 62 - 55642 . among the compounds , ascorbic acid is especially preferred as an example of a low molecular compound , and a water - dispersed latex of a copolymer composed of an acid monomer such as acrylic acid and a crosslinking monomer having two or more unsaturated groups such as divinylbenzene is preferred as the example of a high molecular compound . photographic images having ultrahigh contrast and high sensitivity can be obtained by processing silver halide photographic materials of the present invention in infectious developers or high - alkali developers having a ph value of nearly 13 as described in u . s . pat . no . 2 , 419 , 975 , as well as in any stable developer . specifically , silver halide photographic materials of the present invention are processed with a developer containing sulfite ion as a preservative in an amount of 0 . 15 mol / liter or more and having a ph of from 10 . 5 to 12 . 3 , preferably from 11 . 0 to 12 . 0 , to obtain ultrahard negative images . the developing agent of the developer used for processing the photographic materials of the present invention is not specifically limited . but it is preferred that the developer contain dihydroxybenzenes in order to yield good dot image quality . a combination of dihydroxybenzenes and 1 - phenyl - 3 - pyrazolidones or a combination of dihydroxybenzenes and p - aminophenols may also be employed . in general , the developer preferably contains developing agent in an amount of from about 0 . 05 mol / liter to 0 . 8 mol / liter . where the combination of dihydroxybenzenes and 1 - phenyl - 3 - pyrazolidones or p - aminophenols is employed , the content of the former is preferably from about 0 . 05 mol / liter to 0 . 5 mol / liter and that of the latter is from 0 . 06 mol / liter or less . sulfite preservatives for use in the present invention are , for example , sodium sulfite , potassium sulfite , lithium sulfite , ammonium sulfite , sodium bisulfite , potassium metabisulfite , and formaldehyde - sodium metabisulfite . the concentration of the sulfite is preferably 0 . 4 mol / liter or more , preferably 0 . 5 mol / liter or more . the developer to be employed in the present invention can contain the compounds described in jp - a - 56 - 24347 as a silver stain inhibitor . the developer may further contain a solubilizer aid , which may be selected from the compounds described in u . s . pat . no . 4 , 740 , 452 ( corresponding to jp - a - 61 - 267759 ). the developer may also contain a ph buffer , which may be selected from the compounds described in u . s . pat . no . 4 , 569 , 904 ( corresponding to jp - a - 60 - 93433 ) or the compounds described in jp - a - 62 - 186259 . the compound of formula ( 1 ) can be combined with a negative emulsion and incorporated into a high contrast photographic material as mentioned above . additionally , it may be combined with an internal latent image type silver halide emulsion as described below . if combined with an internal latent image type silver halide emulsion , the compound of formula ( 1 ) is preferably incorporated into the internal latent image type silver halide emulsion layer . it may also be incorporated into the hydrophilic colloid layer adjacent to the internal latent image type silver halide emulsion layer . such an adjacent layer may be a colorant - containing layer , an interlayer , a filter layer , a protective layer , or an antihalation layer , provided that it does not interfere with the diffusion of the nucleating agent into the silver halide grains of the adjacent emulsion layer . the quantity of the compound of formula ( 1 ) in the emulsion layer may vary broadly depending on the characteristics of the silver halide emulsion used , the chemical structure of the nucleating agent , as well as the development conditions , but the practically useful range is from about 0 . 005 mg to about 500 mg per mol of silver in the internal latent image type silver halide emulsion . more preferably , the range of the quantity of the compound of formula ( 1 ) in the emulsion layer is from about 0 . 01 mg to about 100 mg per mol of silver . where it is incorporated into the hydrophilic colloid layer adjacent to the emulsion layer , the amount of the compound may fall within the above - mentioned range based on the amount of silver contained in the same area of the adjacent internal latent image type emulsion layer . the details of the definition of the internal latent image type silver halide emulsion as referred to herein are described in jp - a - 61 - 170733 , page 10 , upper column and british patent 2 , 089 , 057 , pages 18 to 20 . specific examples of internal latent image type emulsions which are preferably employed in the present invention are described in jp - a - 63 - 108336 , from page 28 , line 14 to page 31 , line 2 ; and those of the silver halides which are preferably employed in the present invention are described in the same patent specification , from page 31 , line 3 to page 32 , line 11 . in the photographic materials of the present invention , the internal latent image type emulsions may optionally be color sensitized to blue light , green light , red light , or infrared light having a relatively long wavelength by the use of sensitizing dyes . sensitizing dyes usable for the purpose are cyanine dyes , merocyanine dyes , complex cyanine dyes , complex merocyanine dyes , holopolar cyanine dyes , styryl dyes , hemicyanine dyes , oxonol dyes , and hemioxonol dyes . such sensitizing dyes include the cyanine dyes and merocyanine dyes described in jp - a - 59 - 40638 , jp - a - 59 - 40636 , and jp - a - 59 - 38739 . the photographic materials of the present invention can contain developing agents such as hydroxybenzenes ( for example , hydroquinones ), aminophenols , or 3 - pyrazolidones . these can be included , for example , in the emulsion layer of the material . the photographic emulsion of the present invention can be combined with a color diffusion transfer dye - forming compound ( colorant ) capable of releasing a diffusion dye with the development of the silver halide , in order to obtain a transfer image on an image - receiving layer after proper development . various color diffusion transfer colorants of this type are known . colorants that are originally nondiffusible , but are cleaved to release a diffusion dye by an oxidation reduction with the oxidation product of a developing agent ( or an electron transfer agent ) ( hereinafter referred to as &# 34 ; drr compounds &# 34 ;) are preferably employed in the present invention . in particular , the drr compounds containing an o - hydroxyarylsulfamoyl group described in u . s . pat . nos . 4 , 005 , 428 , 4 , 053 , 312 and 4 , 336 , 322 and the drr compounds containing a redox nucleus described in jp - a - 53 - 149328 are especially preferred when they are combined with the nucleating agent of the present invention . by combining such drr compounds and a nucleating agent of the present invention , the temperature dependence of the resulting photographic materials is noticeably lowered . examples of drr compounds , in addition to those described above , are 1 - hydroxy - 2 - tetramethylenesulfamoyl - 4 -[ 3 &# 39 ;- methyl - 4 &# 39 ;-( 2 &# 34 ;- hydroxy - 4 &# 34 ;- methyl - 5 &# 34 ;- hexadecyloxyphenylsulfamoyl ) phenylazo ] naphthalene as a magenta dye image - forming substance and 1 - phenyl - 3 - cyano - 4 -[( 2 &# 34 ;&# 39 ;, 4 &# 34 ;&# 39 ;- di - tert - pentylphenoxyacetamino ) phenylsulfamoyl ] phenylazo )- 5 - pyrazolone as a yellow dye image - forming substance . it is preferred that the photographic materials of the present invention are imagewise exposed and then color developed with a surface developer containing an aromatic primary amine color developing agent and a ph value of 11 . 5 or less , during or after fogging treatment of the exposed material under light or with a nucleating agent . the thus developed material is bleached and fixed to form a direct positive color image . the developer to be used in the process preferably has a ph value of from 11 . 0 to 10 . 0 . the fogging treatment applied to the photographic material of the present invention in the above - mentioned process may be either a &# 34 ; light fogging method &# 34 ; where the complete surface of the light - sensitive layer is subjected to the second light exposure or a &# 34 ; chemical fogging method &# 34 ; where the material is developed in the presence of a nucleating agent . in addition to these methods , the material may also be developed in the presence of a nucleating light and under exposure to light . alternatively , a nucleating agent may have been previously be incorporated into a photographic material , which is then subjected to fogging exposure . the light fogging method is described in detail in jp - a - 63 - 108336 ( corresponding to european patent 267 , 482a ), from page 47 , line 4 to page 49 , line 5 ; and nucleating agents employable in the present invention are described in detail in the same patent application , from page 49 , line 6 to page 67 , line 2 . in particular , the compounds of formulae ( n - 1 ) and ( n - 2 ) as mentioned therein are prefrred . specific examples of the compounds are mentioned in the same patent application , and the compounds ( n - i - 1 ) to ( n - i - 10 ) described in pages 56 to 58 and the compounds ( n - ii - 1 ) to ( n - ii - 12 ) described in pages 63 to 66 are particularly preferred . a nucleation accelerating agent can be employed in the present invention , and examples of the agent are described in the above - mentioned jp - a - 63 - 108336 , from page 68 , line 11 to page 71 , line 3 . in particular , the compoiunds ( a - 1 ) to ( a - 13 ) mentioned in pages 69 to 70 of jp - a - 63 - 108336 are especially preferably employed in the present invention . the details of the color developer employable for development of the present invention are described in jp - a - 63 - 108336 , from page 71 , line 4 to page 72 , line 9 . in particular , p - phenylenediamine compounds are especially preferred as the aromatic primary amine color developing agent to be used for developing the materials of the present invention . specific examples of these compounds are 3 - methyl - 4 - amino -- n - ethyl -- n -( β - methanesulfonamidoethyl ) aniline ; 3 - methyl - 4 - amino -- n - ethyl - n -( β - hydroxyethyl ) aniline ; 3 - methyl - 4 - amino -- n - ethyl -- n - methoxyethylaniline ; and salts of these compounds ( such as sulfates or hydrochlorides ). where a direct positve color image is formed from the photographic material of the present invention by a clor diffusion transfer process , black - and - white developing agents such as phenidone derivatives can be used in addition to the above - mentioned color developing agent . the color developed photographic emulsion layer is generally bleached . bleaching may be effected simultaneously with fixation by a monobath bleach - fixation system or separately . in order to accelerate the processing procedure , bleach - fixation may be effected before or after bleaching . the bleaching solution or bleach - fixing solution to be employed in the present invention generally contains an aminopolycarboxylate - iron complex as a bleaching agent . as additives to the bleaching solution or bleach - fixing solution various compounds can be employed . these are described in detail in jp - a - 62 - 215272 , at pages 22 to 30 . after the desilvering step ( bleach - fixation or fixation ), the photographic materials are rinsed in water and / or stabilized . it is prefrred that softened water be used as the rinsing water or in the stabilizing solution . as the means for softening water the methods of using an ion exchange resin or a reverse osmosis apparatus , as described in detail in jp - a - 62 - 288838 , can be employed . additives usable in the rinsing or stabilization step are described in detail in jp - a - 62 - 215272 , pages 30 to 36 . the amount of the replenisher necessary in the respective processing steps is preferably small . the amount is preferably from 0 . 1 to 50 times , more preferably from 3 to 30 times , of the carry over of the previous bath per unit area of photographic material being processed . the compounds of the present invention can be applied to heat developing photographic materials . heat developing photographic materials are illustrated in , for example , u . s . pat . nos . 4 , 463 , 079 , 4 , 474 , 867 , 4 , 478 , 927 , 4 , 507 , 380 , 4 , 500 , 626 , 4 , 483 , 914 , jp - a - 58 - 149046 , jp - a - 58 - 149047 , jp - a - 59 - 152440 , jp - a - 59 - 154445 , jp - a - 59 - 165054 , jp - a - 59 - 180548 , jp - a - 59 - 168439 , jp - a - 59 - 174832 , jp - a - 59 - 174833 , jp - a - 59 - 174834 , jp - a - 59 - 174835 , jp - a - 61 - 232451 , jp - a - 62 - 65038 , jp - a - 62 - 253159 , jp - a - 63 - 316848 , jp - a - 64 - 13546 , and european patent laid - open nos . 210 , 660a2 , 220 , 746a2 . the above - mentioned heat developing photographic materials essentially have light - sensitive silver halides , binders , dye - forming compounds and reducing agents ( as the case may be , dye - forming compounds may also act as a reducing agent ), on a support . if desired , the materials may further contain organic silver salts and other additives . the above - mentioned heat developing materials may be either those capable of forming negative images by exposure or those capable of forming positive images by exposure . the system of forming positive images may be either a system of using a direct positive emulsion as a silver halide emulsion or a system of using a dye - forming compound capable of positively releasing a diffusion dye image . the former system includes two types , one is to use a nucleating agent and the other is to be fogged with light . there are a variety of diffusion dye transfer systems , which are , for example , a system of transferring a diffusion dye to a dye - fixing layer by the action of an image - forming solvent such as water , a system of transferring a diffusion dye to a dye - fixing layer by the action of a high boiling point organic solvent , a system of transferring a diffusion dye to a dye - fixing layer by the action of a hydrophilic heat solvent , and a system of transferring a diffusion dye to a dye - receiving polymer - having dye - fixing layer by means of the heat diffusibility or sublimability of the diffusion dye . any one of the said systems can be employed in the present invention . as an example of the above - mentioned image - forming solvent , there is known water , and the water is not limited to only a pure water but it may be a so - called ordinary water with a broad meaning . the following examples are intended to illustrate the present invention in more detail but not to limit it in any way . unless otherwise indicated , all parts and percents are by weight . an aqueous solution of silver nitrate , and an aqueous solution of potassium iodide and potassium bromide were simultaneously added to an aqueous gelatin solution kept at 50 ° c . in the presence of 4 × 10 - 7 mol per mol of silver of potassium iridium ( iii ) hexachloride and ammonia , over a period of 60 minutes . the pag of the reaction system was maintained at 7 . 8 . this resulted in a cubic monodispersed emulsion having a mean grain size of 0 . 28 μm and a mean silver iodide content of 0 . 3 mol %. the emulsion was desalted by flocculation , and inert gelatin was added in an amount of 40 g per mol of silver . this was added to a 10 - 3 mol per mol of silver of ki solution of 50 ° c . containing a sensitizing dye of 5 , 5 &# 39 ;- dichloro - 9 - ethyl - 3 , 3 &# 39 ;- bis ( 3 - sulfopropyl ) oxacarbocyanine . the mixture was allowed to stand for 15 minutes and the temperature of the reaction system was lowered to 8 ° c . the emulsion prepared above was redissolved and the following hydrazine derivatives were added thereto at 40 ° c . ## str31 ## next , a compound of formula ( 1 ) of the invention or a comparative compound , as indicated in table 1 , below , were added . additionally , 5 - methylbenzotriazole , 4 - hydroxy - 1 , 3 , 3a , 7 - tetraazaindene , compounds ( a ) and ( b ), polyethyl acrylate 30 wt % to gelatin , and compound ( c ) ( a gelatin hardening agent ) were added . the resulting composition was coated on a polyethylene terephthalate film ( thickness : 150 μm ) having a vinylidene copolymer subbing layer ( thickness : 0 . 5 μm ), in an amount of 3 . 8 g / m 2 of silver . ## str32 ## a protective layer comprising 1 . 5 g / m 2 of gelatin and 0 . 3 g / m 2 of polymethyl methacrylate grains ( mean grain size : 2 . 5 μm ) were coated over the emulsion layer using the following surfactants . ## str33 ## the samples thus prepared were exposed to a tungsten light of 3 , 200 ° k . through an optical wedge and a contact screen ( 150 chain dot type , manufactured by fuji photo film co ., ltd .) and developed with the following developer at 34 ° c . for 30 seconds , fixed , rinsed in water , and dried . ______________________________________composition of developer : ______________________________________hydroquinone 50 . 0 gn - methyl - p - aminophenol 0 . 3 gsodium hydroxide 18 . 0 g5 - sulfosalicylic acid 55 . 0 gpotassium sulfite 110 . 0 gdisodium ethylenediaminetetraacetate 1 . 0 gpotassium bromide 10 . 0 g5 - methylbenzotriazole 0 . 4 g2 - mercaptobenzimidazole - 5 - sulfonic acid 0 . 3 gsodium 3 -( 5 - mercaptotetrazole )- 0 . 2 gbenzenesulfonic acidn - n - butyldiethanolamine 15 . 0 gsodium toluenesulfonate 8 . 0 gwater to make 1 literpotassium hydroxide to make ph of 11 . 0______________________________________ the dot image quality and the dot gradation of these processed samples were measured . the results obtained are shown in table 1 , below . the dot gradation was represented by the following formula : the dot quality was visually evaluated by five ranks . in this five rank evaluation , &# 34 ; 5 &# 34 ; is the best and &# 34 ; 1 &# 34 ; is the worst . the ranks &# 34 ; 5 &# 34 ; and &# 34 ; 4 &# 34 ; are practical for use as a dot image plate in photomechanical printing ; the rank &# 34 ; 3 &# 34 ; is the critical level for the practical use ; and the ranks &# 34 ; 2 &# 34 ; and &# 34 ; 1 &# 34 ; indicate emulsions that are practically useless . as shown in table 1 , the compounds of the present invention were extremely effective for improving or broadening the dot gradation of the processed samples . thus , samples containing compounds of the invention exhibited an unexpected improvement in dot image quality , compared to the samples containing the comparative compounds according to the prior art . table 1__________________________________________________________________________ kind of amount added dot gradationsample compound added ( mol / m . sup . 2 ) ( δloge ) dot image quality__________________________________________________________________________comparative example comparative compound1 -- -- 1 . 19 32 a 2 . 0 × 10 . sup .- 5 1 . 32 43 b &# 34 ; 1 . 23 34 c &# 34 ; 1 . 20 35 d &# 34 ; 1 . 19 3 compound ( according toexample the invention ) 1 2 2 . 0 × 10 . sup .- 5 1 . 45 42 3 &# 34 ; 1 . 43 43 8 3 . 0 × 10 . sup .- 6 1 . 42 44 19 2 . 0 × 10 . sup .- 5 1 . 46 55 21 &# 34 ; 1 . 47 56 24 &# 34 ; 1 . 35 47 26 &# 34 ; 1 . 40 48 30 &# 34 ; 1 . 35 49 23 &# 34 ; 1 . 38 4__________________________________________________________________________comparative compound - a ( according to jp - a - 61 - 213847 ) ## str34 ## comparative compound - b ( according to jp - a - 61 - 213847 ) ## str35 ## comparative compound - c ( according to u . s . pat . no . 4 , 684 , 604 ) ## str36 ## comparative compound - d ( according to u . s . pat no . 4 , 684 , 604 ) ## str37 ## the same samples as those of example 1 were exposed in the same manner as described in example 1 . these sampels were processed using a photomechanical process automatic developing machine ( type fg660f , manufactured by fuji photo film co ., ltd . ), using the same developer as described in example 1 in the machine . the samples were developed for 30 seconds at 34 ° c . under the following conditions , fixed , rinsed in water , and dried . ( a ) ( development with fresh solution ) immediately after the temperature of the developer in the developing machine reached 34 ° c ., development was started . ( b ) ( development with air fatigued solution ) the developer in the developing machine was allowed to stand for 4 days before the development was started . ( c ) ( development with forcedly fatigued solution by developing a lot of sheets ) the developing machine was filled with developer , and 200 sheets / day of a partially exposed film so that 50 % of the area of the film was developed after processing ( fuji film grandex ga - 100 ) having a size of 50 . 8 cm × 61 . 0 cm were developed with the machine for 5 days , whereupon 100 cc / sheet of a fresh developer was replenished . the photographic properties of the thus processed samples are shown in table 2 , below . in view of the running processing stability , it is desired that the difference between the photographic properties obtained by process ( b ) or ( c ) and those obtained by process ( a ) be negligible . as shown in table 2 , the running processing stability of the samples containing the compounds of the present invention was unexpectedly improved over those containing the comparative compounds of the prior art . table 2______________________________________ running processing stability air fatigued forcedly fatiguedsample no . ( δs . sub . b - a )* ( δs . sub . c - a )* ______________________________________1 comparative + 0 . 07 - 0 . 14 example 12 comparative + 0 . 04 - 0 . 08 example 23 comparative + 0 . 07 - 0 . 14 example 34 comparative + 0 . 08 - 0 . 15 example 45 comparative + 0 . 07 - 0 . 15 example 56 example 1 of + 0 . 03 - 0 . 06 the invention7 example 2 of + 0 . 03 - 0 . 06 the invention8 example 3 of + 0 . 03 - 0 . 07 the invention9 example 4 of + 0 . 02 - 0 . 07 the invention10 example 5 of + 0 . 02 - 0 . 06 the invention11 example 6 of + 0 . 03 - 0 . 07 the invention12 example 7 of + 0 . 03 - 0 . 07 the invention13 example 8 of + 0 . 03 - 0 . 07 the invention14 example 9 of + 0 . 03 - 0 . 06 the invention______________________________________ *( δs . sub . b - a ): difference between the sensitivity ( s . sub . b ) as developed with air fatigued solution and the sensitivity ( s . sub . a ) as developed with fresh solution . *( δs . sub . c - a ): difference between the sensitivity ( s . sub . c ) as developed with forcedly fatigued solution and the sensitivity ( s . sub . a ) a developed with fresh solution . an aqueous silver nitrate solution and an aqueous sodium chloride solution were simultaneously added to and blended with an aqueous gelatin solution of 50 ° c . in the presence of 5 . 0 × 10 - 6 mol of ( nh 4 ) 3 rh cl 6 per mol of silver , and the soluble salts removed . gelatin was added . the mixture was not chemically ripened , rather a stabilizer of 2 - methyl - 4 - hydroxy - 1 , 3 , 3a , 7 - tetraazaindene ( 1 . 3 mg / m 2 ) was added to it . the result was a monodispersed emulsion containing cubic grains having a mean grain size of 0 . 15 μm . the following hydrazine compound ( 49 mg / m 2 ) was added to the emulsion . ## str38 ## next , a compound of the invention or a comparative compound , as indicated in table 3 below , was then added . additionally , a polyethyl acrylate latex ( 30 wt % to gelatin ) and a hardening agent of 1 , 3 - vinylsulfonyl - 2 - propanol were added . the resulting composition was coated on a polyester support in an amount of 3 . 8 g / m 2 of ag . the gelatin content in the coated layer was 1 . 8 g / m 2 . next , a protective layer comprising gelatin ( 1 . 5 g / m 2 ); a mat agent of polymethyl methacrylate grains ( mean grain size : 2 . 5 μm ) at 0 . 3 g / m 2 ; the following surfactants as coating aids ; the following stabilizers ; and the following ultraviolet absorbing dye were coated over the formed emulsion layer and dried . ______________________________________ surfactants : ## str39 ## 37 mg / m . sup . 2 ## str40 ## 37 mg / m . sup . 2 ## str41 ## 2 . 5 mg / m . sup . 2stabilizerthioctic acid 2 . 1 mg / m . sup . 2ultraviolet absorbing dye : ## str42 ## 100 mg / m . sup . 2______________________________________ these samples were imagewise exposed through an embodiment of the invention as illustrated in fig1 using a daylight printer ( p - 607 , manufactured by dai - nippon screen co .) and developed at 38 ° c . for 20 seconds , fixed , rinsed in water , and dried . the thus processed samples were evaluated with respect to the quality of the superimposed letter image formed by way of a 5 - rank evaluation . for the 5 - rank superimposed letter image evaluation , the photographic material sample was perperly exposed through an embodiment of the invention as illustrated in fig1 so that 50 % of the dot area of the original would be 50 % of the dot area of the reproduced image on the sample by contact dot - to - dot work . the rank &# 34 ; 5 &# 34 ; in the evaluation indicates that 30 μm width letters were well reproduced and the superimposed letter image quality was excellent . the rank &# 34 ; 1 &# 34 ; indicates that only letters of 150 μm width or more were reproduced and the superimposed letter image quality was bad . the other rankings of from &# 34 ; 4 &# 34 ; to &# 34 ; 2 &# 34 ; were conducted by functional evaluation . ranks of &# 34 ; 3 &# 34 ; or more indicate the practical working level . the results are shown in table 3 below . these results illustrate that the samples of the present invention have excellent superimposed letter image quality . table 3______________________________________ kind of superimposed compound amount added letter imagesample no . added ( mol / m . sup . 2 ) quality______________________________________1 -- -- 3 . 0 ( comparison ) 2 comparative 5 . 0 × 10 . sup .- 5 3 . 5 ( comparison ) compound - a3 comparative &# 34 ; 3 . 0 ( comparison ) compound - b4 comparative &# 34 ; 3 . 0 ( comparison ) compound - c5 comparative &# 34 ; 3 . 0 ( comparison ) compound - d6 compound 3 5 . 0 × 10 . sup .- 5 4 . 0 ( invention ) 7 compound 19 &# 34 ; 4 . 0 ( invention ) 8 compound 21 &# 34 ; 4 . 5 ( invention ) 9 compound 14 &# 34 ; 4 . 5 ( invention ) 10 compound 16 &# 34 ; 5 . 0 ( invention ) 11 compound 4 7 . 0 × 10 . sup .- 6 4 . 5 ( invention ) 12 compound 22 &# 34 ; 4 . 5 ( invention ) 13 compound 26 5 . 0 × 10 . sup .- 5 4 . 0 ( invention ) 14 compound 23 &# 34 ; 4 . 0 ( invention ) ______________________________________ emulsions for photographic layers , a dispersion of zinc hydroxide , a dispersion of active charcoal , a dispersion of an electron transmitting agent , dispersions of yellow , magenta , and cyan couplers and a dispersion for an interlayer were prepared as mentioned below . using them , a photographic material ( sample no . 801 ) was prepared , as mentioned below . additionally , an image - receiving material was prepared , also as mentioned below . the following solution ( 1 ) and solution ( 2 ) were simultaneously added to a well stirred aqueous gelatin solution ( which was prepared by adding 20 g of gelatin , 3 g of potassium bromide , 0 . 03 g of the following compound ( 1 ) and 0 . 25 g of ho ( ch 2 ) 2 s ( ch 2 ) 2 s ( ch 2 ) 2 oh to 800 cc of water and heated at 50 ° c . ), over a period of 30 minutes . afterwards , the following solution ( 3 ) and solution ( 4 ) were further added thereto at the same time over a period of 20 minutes . 5 minutes after the initiation of adding solution ( 3 ), a dye solution mentioned below was added over a period of 18 minutes . after washed with water and desalted , 20 g of lime - processed ossein gelatin was added , the ph was adjusted to 6 . 2 , and the pag to 8 . 5 . next , sodium thiosulfate , 4 - hydroxy - 6 - methyl - 1 , 3 , 3a , 7 - tetraazaindene and chloroauric acid were added for optimum chemical sensitization . thus , 600 g of a monodispersed cubic silver chlorobromide emulsion having a mean grain size of 0 . 40 μm was obtained . ______________________________________ solution solution solution solution ( 1 ) ( 2 ) ( 3 ) ( 4 ) ______________________________________agno . sub . 3 30 g -- 70 g -- kbr -- 17 . 8 g -- 49 gnacl -- 1 . 6 g -- -- water to make 180 cc 180 cc 350 cc 350 cc______________________________________ the following solutions ( i ) and ( ii ) were added to an aqueous gelatin solution ( see below ) well stirred and heated at 50 ° c ., over a period of 30 minutes . next , solutions ( iii ) and ( iv ) were added over a period of 30 minutes , whereupon a dye solution mentioned below was added 1 minute after the completion of the addition of solutions ( iii ) and ( iv ). ______________________________________gelatin 20 gnacl 6 gkbr 0 . 3 g ## str46 ## 0 . 015 gh . sub . 2 o 730 ml______________________________________ solution solution solution solution ( i ) ( ii ) ( iii ) ( iv ) ______________________________________agno . sub . 3 50 g -- 50 g -- kbr -- 21 g -- 28 gnacl -- 6 . 9 g -- 3 . 5 gwater to make 200 cc 200 cc 200 cc 200 cc______________________________________ thus , a monodispersed cubic emulsion having a grain size of 0 . 40 μm was obtained . the yield was 63 g . __________________________________________________________________________ composition of dye solution : __________________________________________________________________________ ## str47 ## 0 . 23 gmethanol 154 cc__________________________________________________________________________ after being washed with water and desalted , 20 g of gelatin was added , the ph and pag were adjusted , and triethylthiourea , chloroauric acid and 4 - hydroxy - 6 - methyl - 1 , 3 , 3a , 7 - tetraazaindene were added for optimum chemical sensitization . the following solutions ( v ) and ( vi ) were added to a well stirred aqueous gelatin solution ( which was prepared by adding 20 g of gelatin , 0 . 3 g of potassium bromide , 6 g of sodium chloride and 30 mg of the following compound ( 1 ) to 800 ml of water and heated at 50 ° c .) at the same time and at the same flow rate over a period of 30 minutes . afterwards , the following solutions ( vii ) and ( viii ) were also added at the same time over a period of 30 minutes . 3 minutes after the initiation of adding solutions ( vii ) and ( viii ), a dye solution mentioned below was added over a period of 20 minutes . after being washed with water and desalted , 22 g of lime - processed ossein gelatin was added , the ph was adjusted to 6 . 2 , and the pag to 7 . 7 . next , sodium thiosulfate , 4 - hydroxy - 6 - methyl - 1 , 3 , 3a , 7 - tetraazaindene and chloroauric acid were added for optimum chemical sensitization at 60 ° c . thus , a monodispersed cubic silver chlorobromide emulsion having a mean grain size of 0 . 38 μm was obtained . the yield was 635 g . ______________________________________ solution ( v ) solution ( vi ) ______________________________________agno . sub . 3 50 . 0 g -- kbr -- 28 . 4 gnacl -- 3 . 4 gwater to make 200 ml 200 ml______________________________________ solution ( vii ) solution ( viii ) ______________________________________agno . sub . 3 50 . 0 g -- kbr -- 35 . 0 gwater to make 200 ml 200 ml______________________________________ ## str48 ## 67 mg of the following dye ( a ) and 133 mg of the following dye ( b ) were dissolved in 100 ml of methanol . ## str49 ## next , a dispersion of zinc hydroxide was prepared as mentioned below . 12 . 5 g of zinc hydroxide having a mean grain size of 0 . 2 μm , 1 g of carboxymethyl cellulose as a dispersing agent , and 0 . 1 g of sodium polyacrylate were added to 100 cc of a 4 % aqueous gelatin solution and milled for 30 minutes with glass beads having a mean grain size of 0 . 75 mm . the glass beads were removed , and a dispersio of zinc hydroxide was obtained . 2 . 5 g of active charcoal powder ( special grade chemical , product by wako pure chemical ), 1 g of demole n ( product by kao soap co .) as a dispersing agent , and 0 . 25 g of polyethylene glycol nonylphenylether were added to 100 cc of a 5 % aqueous gelatin solution , and milled for 120 minutes with glass beads having a mean grain size of 0 . 75 mm . after the glass beads were removed , a dispersion of active charcoal having a mean grain size of 0 . 5 μm was obtained . a dispersion of an electron transmitting agent was prepared as follows : 10 g of an electron transmitting agent mentioned below , 0 . 5 g of polyethylene glycol as a dispersing agent , and 0 . 5 g of an anionic surfactant mentioned below were added to a 5 % aqueous gelatin solution , and milled for 60 minutes with glass beads having a mean grain size of 0 . 75 mm . after the glass beads were removed , a dispersio of an electron transmitting agent having a mean grain size of 0 . 3 μm was obtained . ## str50 ## gelatin dispersions each containing a dye - forming compound were prepared as mentioned below . a yellow , magenta or cyan dye - forming composition as indicated below was added to 50 cc of ethyl acetate and dissolved under heat at about 60 ° c . to form a uniform solution . this was blended with 100 g of 10 % lime - processed gelatin - containing aqueous solution , 0 . 6 g of sodium dodecylbenzenesulfonate and 50 cc of water by stirring and then dispersed for 10 minutes with a homogenizer at 10 , 000 rpm . the dispersion thus prepared is called a gelatin dispersion of a dye - forming compound . __________________________________________________________________________ yellow magenta cyan__________________________________________________________________________dye forming compound ( 1 ) 13 g ( 2 ) 15 . 5 g ( 3 ) 16 . 6 gmentioned belowelectron donating compound ( 1 ) 10 . 2 g 8 . 6 g 8 . 1 gmentioned belowhigh boiling point solvent ( 2 ) 6 . 5 g 7 . 8 g 8 . 3 gmentioned belowelectron transmitting agent 0 . 4 g 0 . 7 g 0 . 7 gprecursor ( 3 ) mentioned belowcompound ( a ) 3 . 9 g -- -- mentioned below__________________________________________________________________________dye forming compound ( 1 ): ## str51 ## dye forming compound ( 2 ): ## str52 ## dye forming compound ( 3 ): ## str53 ## electron donating compound ( 1 ): ## str54 ## high boiling point solvent ( 2 ): ## str55 ## electron transmitting agent precursor ( 3 ): ## str56 ## compound ( a ): ## str57 ## a gelatin dispersion of electron donating compound ( 4 ) for an 23 . 6 g of the following electron donating compound ( 4 ) and 8 . 5 g of the above - mentioned high boiling point solvent ( 2 ) were added to 30 cc of ethyl acetate to form a uniform solution . the solution was blended with 100 g of a 10 % aqueous solution of lime - processed gelatin , 0 . 25 g of sodium hydrogensulfite , 0 . 3 g of sodium dodecylbenzenesulfonate , and 30 cc of water with stirring , and then dispersed for 10 minutes with a homogenizer at 10 , 000 rpm . the resulting dispersion is called a gelatin dispersion of electron donating compound ( 4 ). ## str58 ## ______________________________________sixth layer : protective layergelatin 900 mg / m . sup . 2silica ( size : 4 μm ) 40 mg / m . sup . 2zinc hydroxide 900 mg / m . sup . 2surfactant ( 5 ) (* 1 ) 130 mg / m . sup . 2surfactant ( 6 ) (* 2 ) 26 mg / m . sup . 2polyvinyl alcohol 63 mg / m . sup . 2lactose 155 mg / m . sup . 2water - soluble polymer (* 3 ) 8 mg / m . sup . 2fifth layer : blue - sensitive emulsion layerlight - sensitive silver halide 380 mg / m . sup . 2 as agemulsionantifoggant ( 7 ) (* 4 ) 0 . 9 mg / m . sup . 2gelatin 560 mg / m . sup . 2yellow dye forming compound ( 1 ) 400 mg / m . sup . 2electron donating compound ( 1 ) 320 mg / m . sup . 2electron transmitting agent 25 mg / m . sup . 2precursor ( 3 ) compound ( a ) 120 mg / m . sup . 2high boiling point solvent ( 2 ) 200 mg / m . sup . 2surfactant ( 8 ) (* 5 ) 45 mg / m . sup . 2water - soluble polymer (* 3 ) 13 mg / m . sup . 2fourth layer : interlayergelatin 555 mg / m . sup . 2electron donating compound ( 4 ) 130 mg / m . sup . 2high boiling point solvent ( 2 ) 48 mg / m . sup . 2electron transmitting agent ( 10 ) (* 7 ) 85 mg / m . sup . 2surfactant ( 6 ) (* 2 ) 15 mg / m . sup . 2surfactant ( 8 ) (* 5 ) 4 mg / m . sup . 2surfactant ( 9 ) (* 6 ) 30 mg / m . sup . 2polyvinyl alcohol 30 mg / m . sup . 2lactose 155 mg / m . sup . 2water - soluble polymer (* 3 ) 19 mg / m . sup . 2hardening agent ( 11 ) (* 8 ) 37 mg / m . sup . 2third layer : green - sensitiveemulsion layerlight - sensitive silver halide 220 mg / m . sup . 2 as agemulsionantifoggant ( 12 ) (* 9 ) 0 . 7 mg / m . sup . 2gelatin 370 mg / m . sup . 2magenta dye forming compound ( 2 ) 350 mg / m . sup . 2electron donating compound ( 1 ) 195 mg / m . sup . 2electron transmitting agent 33 mg / m . sup . 2precursor ( 3 ) high boiling point solvent ( 2 ) 175 mg / m . sup . 2surfactant ( 8 ) (* 5 ) 47 mg / m . sup . 2water - soluble polymer (* 3 ) 11 mg / m . sup . 2second layer : interlayergelatin 650 mg / m . sup . 2zinc hydroxide 300 mg / m . sup . 2electron donating compound ( 4 ) 130 mg / m . sup . 2high boiling point solvent ( 2 ) 50 mg / m . sup . 2surfactant ( 6 ) (* 2 ) 11 mg / m . sup . 2surfactant ( 8 ) (* 5 ) 4 mg / m . sup . 2surfactant ( 9 ) (* 6 ) 50 mg / m . sup . 2polyvinyl alcohol 50 mg / m . sup . 2lactose 155 mg / m . sup . 2water - soluble polymer (* 3 ) 12 mg / m . sup . 2active charcoal 25 mg / m . sup . 2first layer : red - sensitive emulsion layerlight - sensitive silver halide 230 mg / m . sup . 2 as agemulsionantifoggant ( 12 ) (* 9 ) 0 . 7 mg / m . sup . 2gelatin 330 mg / m . sup . 2cyan dye forming compound ( 3 ) 340 mg / m . sup . 2electron donating compound ( 1 ) 133 mg / m . sup . 2electron transmitting agent 30 mg / m . sup . 2precursor ( 3 ) high boiling point solvent ( 2 ) 170 mg / m . sup . 2surfactant ( 8 ) (* 5 ) 40 mg / m . sup . 2water - soluble polymer (* 3 ) 5 mg / m . sup . 2support : polyethylene terephthalate ( 96 μm thick )( carbon black was added to the backinglayer ) ______________________________________ compounds used above are as follows : (* 1 ) surfactant ( 5 ): ## str59 ## (* 2 ) surfactant ( 6 ): ## str60 ## - (* 3 ) watersoluble polymer : ## str61 ## - (* 4 ) antifoggant ( 7 ): ## str62 ## - (* 5 ) surfactant ( 8 ): ## str63 ## - (* 6 ) surfactant ( 9 ): ## str64 ## - (* 7 ) electron transmitting agent ( 10 ): ## str65 ## - (* 8 ) hardening agent ( 11 ): 1 , 2 - bis ( vinylsulfonylacetamide ) ethane (* 9 ) antifoggant ( 12 ): ## str66 ## ______________________________________third layer : gelatin 0 . 05 g / m . sup . 2silicone oil ( 1 ) 0 . 04 g / m . sup . 2surfactant ( 1 ) 0 . 001 g / m . sup . 2 . sup . surfactant ( 2 ) 0 . 02 g / m . sup . 2surfactant ( 3 ) 0 . 10 g / m . sup . 2matting agent ( 1 ) 0 . 02 g / m . sup . 2guanidine picolinate 0 . 45 g / m . sup . 2water - soluble polymer ( 1 ) 0 . 24 g / m . sup . 2second layer : mordant agent ( 1 ) 2 . 35 g / m . sup . 2water - soluble polymer ( 1 ) 0 . 20 g / m . sup . 2gelatin 1 . 40 g / m . sup . 2water - soluble polymer ( 2 ) 0 . 60 g / m . sup . 2high boiling point solvent ( 1 ) 1 . 40 g / m . sup . 2guanidine picolinate 2 . 25 g / m . sup . 2brightening agent ( 1 ) 0 . 05 g / m . sup . 2surfactant ( 5 ) 0 . 15 g / m . sup . 2first layer : gelatin 0 . 45 g / m . sup . 2surfactant ( 3 ) 0 . 01 g / m . sup . 2water - soluble polymer ( 1 ) 0 . 04 g / m . sup . 2hardening agent ( 1 ) 0 . 30 g / m . sup . 2support ( 1 ): see below . first backing layer : gelatin 3 . 25 g / m . sup . 2hardening agent ( 1 ) 0 . 25 g / m . sup . 2second backing layer : gelatin 0 . 44 g / m . sup . 2silicone oil ( 1 ) 0 . 08 g / m . sup . 2surfactant ( 4 ) 0 . 04 g / m . sup . 2surfactant ( 5 ) 0 . 01 g / m . sup . 2matting agent ( 2 ) 0 . 03 g / m . sup . 2______________________________________ ______________________________________surface subbing layer : 0 . 1 μm ( thickness ) gelatinsurface pe layer ( glossy ): 45 . 0 μm ( thickness ) low density polyethylene 89 . 2 parts ( density : 0 . 923 ) surface - treated titanium oxide 10 . 0 partsultramarine 0 . 8 partspulp layer : 92 . 6 μm ( thickness ) high quality paper ( lbkp / nbkp = 1 / 1 , density : 1 . 080 ) back surface pe layer ( matting ): 36 . 0 μm ( thickness ) high density polyethylene ( density : 0 . 960 ) back surface subbing layer : gelatin 0 . 05 μm ( thickness ) colloidal silica 0 . 05 μm ( thickness ) total 173 . 8 μm ( thickness ) ______________________________________ in the same manner as the preparation of sample no . 801 , other sample nos . 802 to 805 were prepared , as indicated in table 4 below . sample nos . 802 to 805 each contained a compound of the present invention , which had been dispersed in gelatin by an oil dispersion method , in the second and fourth layers each in an amount of 3 × 10 - 5 mol / m 2 . sample nos . 801 to 805 thus prepared were exposed with a spectrophotometric camera through an optical wedge where the optical density continuously varied in the direction vertical to the wavelength . the exposed samples were then wetted with water by applying a hot water ( 35 ° c .) to the emulsion surface of each sample in an amount of 15 ml / m 2 for 3 seconds . the thus wetted sample was attached to the previously prepared image receiving material so that the coated surfaces of the two faced to each other . the combined sample was then heated with a heat roller for 15 seconds whereupon the temperature of the wetted layer was adjusted to 78 ° c . next , the image receiving material was peeled off from the photographic material and , as a result , a blue - green - red spectrogram was formed on the image receiving layer in accordance with the wavelength of the light as exposed . the density of each of the yellow , magenta and cyan colors was measured with 310 type densitometer ( manufactured by x - rite co .). the results obtained are shown in table 4 below . table 4______________________________________ comparison invention 801 802 803 804 805______________________________________compound added to -- ( 1 ) ( 8 ) ( 29 ) ( 34 ) second and fourthlayersblue - exposed regionyellow 0 . 75 0 . 60 0 . 65 0 . 65 0 . 60magenta 2 . 00 2 . 15 2 . 05 2 . 10 2 . 10cyan 2 . 05 2 . 15 2 . 10 2 . 10 2 . 15green - exposed regionyellow 1 . 90 2 . 05 2 . 00 2 . 05 2 . 05magenta 0 . 70 0 . 55 0 . 60 0 . 60 0 . 55cyan 2 . 00 2 . 15 2 . 10 2 . 10 2 . 15red - exposed regionyellow 1 . 90 2 . 00 1 . 95 2 . 00 2 . 00magenta 1 . 90 2 . 05 2 . 00 1 . 95 2 . 10cyan 0 . 40 0 . 30 0 . 35 0 . 35 0 . 30______________________________________ from the results above , it is noted that the density of all the blue , green and red colors increased by addition of the compound of the present invention . additionally , the color purity also increased by such addition , since the complementary color component decreased . accordingly , it was proved that the compounds of the present invention had an excellent capacity of improving the color reproducibility . next , the above - mentioned photographic material samples were stored for 1 month under the condition of 30 ° c . and 70 % rh and then subjected to the same treatment as described above . after the treatment , the same results as those in the above - mentioned table 4 were obtained . accordingly , it was confirmed that the compounds of the present invention have no harmful influence on the stabilities with the laps of time of the photographic materials containing the same . each of 0 . 825 mmol / m 2 of compound ( 1 ), ( 6 ), ( 30 ), and ( 27 ) of the present invention was added to the timing layer of the cover sheet of example 1 of jp - a - 63 - 289551 to prepare cover sheets ( 9 - 1 ), ( 9 - 2 ), ( 9 - 3 ), and ( 9 - 4 ). each of these cover sheets was attached to light - sensitive sheet ( 102 ) of the same example and then processed in the same manner as in the same example . the liquid spreading temperature was 10 ° c ., 25 ° c . and 35 ° c . as a result , it was found that all the samples had little processing temperature dependence and had excellent photographic properties with a high dmax value and a low dmin value . a light - sensitive sheet was prepared in the same manner as in example 5 , except that the same molar amount of compound ( 36 ) of the present invention was used in place of the yellow dye releasing redox compound in the tenth layer . the light - sensitive sheet was combined with the cover sheet and the processing solution of example 1 of jp - a - 63 - 289551 and processed at 25 ° c . in the same manner as in the same example . it was found that the light - sensitive sheet of the present invention had a rapid speed of increasing b density and a short period of time of completing the color image . accordingly , the sheet of the present invention could form a color image in a short period of time . 3 mg / m 2 of compound ( 1 ), ( 29 ) or ( 34 ) of the present invention was added to each of the third , fourth , sixth , seventh , ninth and tenth layers of sample no . 102 of example 1 of jp - a - 1 - 112241 , respectively , to prepare samples ( 11 - 1 ), ( 11 - 2 ) and ( 11 - 3 ). these samples were processed in the manner as described in the same example , and it was confirmed that all these samples had an excellent color reproducibility . 15 mg of compound ( 1 ) of the present invention was added to the third , fourth , fifth , seventh , eighth , ninth , eleventh , twelfth , and thirteenth layers of sample no . 101 of example 1 of jp - a - 1 - 267638 to prepare sample no . ( 8 - 1 ). this was processed and evaluated in accordance with the manner described in the same example . as a result , the sample was proved to have excellent sharpness and color reproducibility . 20 mg of compound ( 28 ) of the present invention was added to the fourth , fifth , sixth , ninth , tenth , eleventh , fourteenth , fifteenth and sixteenth layers of sample ( 208 ) of example 2 of jp - a - 1 - 291250 to prepare sample no . ( 9 - 1 ). this was processed in accordance with the manner described in the same example . as a result , the sample was found to have excellent sharpness , graininess and color reproducibility . 3 mg / m 2 of compound ( 1 ) of the present invention was added to each of the third , fourth , sixth , seventh , eleventh and twelfth layers of sample ( 502 ) of example 4 of european patent 327066a to prepare sample no . ( 10 - 1 ). this was processed in accordance with the manner described in the same example . as a result , the sample was found to have an excellent color reproducibility . compound ( 1 ) of the present invention was added to the emulsion layer of sample ( 1 ) of example 1 of jp - a - 1 - 234840 in an amount of 560 mg per mol of the silver halide in the layer to prepare sample no . ( 11 - 1 ). this was processed in accordance with the manner described in the same example . as a result , the sample formed a high quality image having a high black density . while the invention has been described in detail and with reference to specific embodiments thereof , it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof . | 8 |
the present invention concerns an improvement in the method of removing sulfur dioxide from an exhaust gas containing sulfur dioxide in which method , after an exhaust gas containing sulfur dioxide is brought into contact with an aqueous solution containing alkali sulfite to absorb sulfur dioxide in the aqueous soultion as an acidic alkali sulfite , calcium carbonate is added to the aqueous solution containing the acidic alkali sulfite to form calcium sulfite by double decomposition , which is in turn separated by filtration and discharged to outside of the system , the filtrate being circulated for absorbing sulfur dioxide , characterized in that the accumulation of alkali sulfate formed in the step of absorbing sulfur dioxide and in the step of separation of calcium sulfite by the oxidation of a part of alkali sulfite is effectively prevented . the above - mentioned prevention of accumulation of alkali sulfate in the system is carried out by the following steps . the above - mentioned double decomposition of acidic alkali sulfite by calcium carbonate is performed in two stages such that in the first stage , relatively coarse particles of calcium carbonate with a diameter of 60 to 300 micron are added in an amount corresponding to 20 to 60 % by weight of acidic alkali sulfite in the effluent from the absorbing tower to react at a ph of lower than 6 . 8 , preferably lower than 6 . 7 to form and separate out calcium sulfite along with calcium sulfate ( gypsum ), and in the second stage , finer particles of calcium carbonate are added to the above - mentioned reaction mixture in an amount to correspond to the remaining amount of acidic alkali sulfite in the reaction mixture to complete the double decomposition to form and separate out calcium sulfite along with calcium sulfate and then the separated calcium sulfite and calcium sulfate are removed by filtration , the filtrate being circulated to the step of absorption of sulfur dioxide . in the method of the present invention , the solid material formed by the above - mentioned double decomposition is filtered , preferably , in an atmosphere of carbon dioxide generated in the step of double decomposition for the purpose of excluding oxygen which oxidizes a part of alkali sulfite to form alkali sulfate . that is , in the case where the oxygen content of the exhaust gas is small , the above - mentioned method of two stage reaction of the double decomposition alone is satisfactorily able to prevent the accumulation of alkali sulfate in the absorbing solution . however , in the case where the oxygen content of the exhaust gas is more than 4 % by volume , especially in the case of an exhaust gas from a coal boiler containing more than 5 % by volume of oxygen , the amount of formation of alkali sulfate is so great than even the above - mentioned method of double decomposition is not able to remove the alkali sulfate satisfactly . for that purpose , by carrying out the filtration , in which step the amount of formation of alkali sulfate is next to that in the step of absorption , in an atmosphere of carbon dioxide the formation of alkali sulfate in this step is effectively prevented resulting in the suppression of the amount of alkali sulfate formation in the total system . the present invention had made it possible to prevent the accumulation of alkali sulfate in the absorbing solution even when the exhaust gas contains much oxygen by combining the thus devised double decomposition and the thus devised process of filtration without providing any special step for removing the alkali sulfate as in the conventional process . generally , it has been considered that in cases where gypsum co - exists in a system containing a water - soluble alkali sulfite , according to the following reaction ( 3 ), calcium sulfite which is less soluble than gypsum separates out and gypsum cannot exist stably and so the alkali sulfate in the above - mentioned system of double decomposition cannot be removed from the system as gypsum : however , the solid formd by the double decomposition according to the present invention contains a considerable amount of gypsum together with calcium sulfite , unreacted calcium carbonate and impurities within calcium carbonate , etc . the gypsum is considered to be in a specific state in which gypsum is covered not to be brought into the reaction ( 3 ) with alkali sulfite , for instance , in the state of covered with crystals of being calcium sulfite . also , it is considered that a reason why such a large amount of gypsum separates out is the formation of an unstable and soluble calcium salt , presumably an acidic calcium carbonate , on the surface of calcium carbonate , and the reaction of this unstable and soluble salt not only with alkali sulfite but also with alkali sulfate . in order to have a larger amount of gypsum which separates together with calcium sulfite in the above - mentioned reaction of double decomposition , it is necessary to use coarser particles of calcium carbonate having an average diameter of 60 to 300 micron , preferably 70 to 150 micron , at a ph of lower than 6 . 8 , preferably lower than 6 . 7 . although the ph of the system of the above - mentioned double decomposition becomes higher as the reaction proceeds , the amount of separation of gypsum is larger when the ph is lower and smaller when the ph is higher . accordingly , in the present invention , at first calcium carbonate is added in an amount to make 20 to 60 % by weight of the acidic alkali sulfite react at a ph lower than 6 . 8 and then calcium carbonate is further added in an amount which is sufficient to doubly decompose the remaining amount of acidic alkali sulfite , the size of calcium carbonate particles used in the second step being preferably smaller than that of calcium carbonate used in the first step . in the above - mentioned first step of double decomposition , the amount of separated gypsum is made larger by the use of relatively coarse particles of calcium carbonate with an average diameter of 60 to 300 micron . this fact is presumably attributed to the phenomenon that because of the high concentration of acidic alkali sulfite in the aqueous solution which has absorbed sulfur dioxide in the first step , the reaction between the coarse particles of calcium carbonate and the acidic alkali sulfite becomes slower and the concentration of the above - mentioned unstable and soluble acidic calcium carbonate is raised , and as the result , the amount of separation of gypsum is raised . however , when coarser particles of calcium carbonate of an average diameter of larger than 300 micron are used , its reactivity with the acidic alkali sulfite becomes too low , and on the other hand , when finer particles of calcium carbonate of an average diameter of smaller than 60 micron are used the amount of formation of gypsum is greatly reduced , that is , the particles larger or smaller than those mentioned above are not preferable . hitherto , in the double decomposition of the acidic alkali sulfite , according to the consideration of the reactivity to the acidic alkali sulfite and the utilizability of calcium carbonate , finer particles of calcium carbonate having an average diameter smaller than 40 micron have been utilized , and in these cases the amount of gypsum separating together with calcium sulfite has been only slight , and so the method was not effective in preventing the accumulation of alkali sulfate which is formed as a by - product . in addition , from the consideration of its reactivity and utilizability , particles of finer size of calcium carbonate less than 30 micron in diameter are used in the second stage of the double decomposition to complete the reaction . by carrying out the double decomposition in two stages , that is relatively coarse particles of calcium carbonate being used in the first stage at a lower ph to react such particles of calcium carbonate with acidic alkali sulfite and then in the second stage , finer particles of calcium carbonate being used to cause the reaction of double decomposition to be completed , we have succeeded in making the amount of unreacted calcium carbonate smaller while making the separated amount of calcium sulfate ( gypsum ) larger . by doing so , it is possible to remove at least all the amount of alkali sulfate in the step of absorbing sulfur dioxide from the exhaust gas containing the same . on the contrary , in the case where the double decomposition is carried out in one stage , the use of coarser particles of calcium carbonate , as is seen in the comparative example described later , results in a greater amount of unreacted calcium carbonate left in the separated solid with poor utilizability , and the use of finer particles of calcium carbonate results in a smaller amount of calcium sulfate ( gypsum ) which separates out , and further , the use of a mixture of coarser and finer particles of calcium carbonate makes the finer particles to react faster to raise the ph of the reactant , rapidly resulting in insufficient separation of gypsum . the filtration of the solid matter which separated in the double decomposition and is composed mainly of calcium sulfite may be carried out in a usual manner , however , in order to suppress the formation of alkali sulfate and to prevent its accumulation throughout the system , the filtration is preferably carried out in an atmosphere of carbon dioxide . for the better understanding of the step of filtration of calcium sulfite , mentioned above , according to the present invention , an explanation of the total system of removing sulfur dioxide from an exhaust gas is now given while referrring to the figure as follows : the exhaust gas containing sulfur dioxide is introduced into an absorbing tower 1 via a pipe 2 , and after having been brought into contact with an aqueous solution containing alkali sulfite charged into the tower 1 via a pipe 3 , the gas is discharged from the top part of the tower 1 via a pipe 4 . on the other hand , the effluent containing acidic alkali sulfite from the bottom part of the tower 1 is sent to the first double decomposition vessel 5 and therein the acidic alkali sulfite in the effluent is brought into reaction with coarse particles of calcium carbonate to give rise to calcium sulfite and at the same time calcium sulfate and carbon dioxide . the slurry containing the thus formed calcium sulfite and calcium sulfate is further sent to the second double decomposition vessel 6 to be further reacted with thereby added finer particles of calcium carbonate to finish the reaction . the slurry containing the reaction mixture is sent to the vacuum filter 7 and filtered , preferably in an atmosphere of carbon dioxide which is generated in the vessels 5 and 6 and delivered by a pipe 8 into the covering 9 covering the vacuum filter 7 gas - tight from outside when the vacuum pump 10 is in operation . as the carbon dioxide which generates in the vessels 5 and 6 only contains water vapour without containing oxygen , oxidation of alkali sulfite in the reaction mixture , that is , the formation of alkali sulfate in the steps of delivery and filtration is effectively preventable even if there is a vigorous contact between the carbon dioxide and the liquid of the slurry in the step of filtration . there is a circulation of carbon dioxide from the gas - liquid separator 11 to the covering 9 via the vacuum pump 10 via a pipe 12 , the excess carbon dioxide being discharged from a pipe 13 . solid matter comprising calcium sulfite and calcium sulfate from the filter 7 is discharged from a port 14 and taken out by a shoot 15 , and the filtrate is circulated to the absorbing tower 1 via the gas - liquid separator 11 and a receiver 16 . as has been described , in the case where sulfur dioxide in an exhaust gas is absorbed in an aqueous alkali sulfite solution and calcium carbonate is brought into reaction with the acidic alkali sulfite formed in the aqueous solution which has absorbed sulfur dioxide , according to the present invention , the accumulation of alkali sulfate in the system for removal of sulfur dioxide from the exhaust gas is extremely effectively preventable by carrying out the above - mentioned reaction in two steps using particles of calcium carbonate of specified sizes and by carrying out the filtration of calcium sulfite formed by the above - mentioned reaction in an atmosphere of carbon dioxide which generates by the above - mentioned reaction . the following is a concrete explanation of the present invention referring to the annexed drawings by showing examples , wherein % means % by weight unless specified : in a system illustrated in figure , an exhaust gas of combustion containing 3 , 000 ppm of sulfur dioxide ( so 2 ) and 3 . 6 % by volume of oxygen ( o 2 ) was introduced into an absorbing tower 1 ( 5 m in height ) via a pipe 2 at a rate of 5 , 000 nm 3 / hour . an aqueous solution containing 0 . 3 % of sodium hydrogen sulfite ( nahso 3 ), 9 . 3 % of sodium sulfite ( na 2 so 3 ) and 9 . 3 % of sodium sulfate ( na 2 so 4 ) was supplied to the absorbing tower 1 via a pipe 3 at a rate of 2 , 300 kg / hour to absorb the so 2 in the exhaust gas . as a result of absorption of so 2 , the content of so 2 in the treated exhaust gas discharged from the absorbing tower 1 through a pipe 4 was 150 ppm . also , an aqueous solution containing 6 % of nahso 3 , 6 % of na 2 so 3 and 10 % of na 2 so 4 at a ph of about 6 . 0 was removed from the absorbing tower to a first double decomposition vessel 5 at a rate of 2 , 180 kg / hour . in the absorbing tower 1 , a part of the sulfites was oxidized and about 4 kg / hour of na 2 so 4 were formed . pulverized lime stone with an average diameter of 150 micron was thrown into the first double decomposition vessel 5 warmed to a temperature of 80 ° to 90 ° c . at a rate of 29 kg / hour corresponding to about 46 % of nahso 3 to be brought into reaction at a ph lower than 6 . 55 . the reaction mixture in a state of slurry was removed to a second double decomposition vessel 6 . in this case , the composition of solid matter collected in a pipe connecting the two vessels was 74 . 7 % of caso 3 . 1 / 2 h 2 o , 21 . 9 % of caso 4 . 2h 2 o and 1 . 5 % of caco 3 , showing the information of 8 . 6 kg / hour of gypsum . into the second double decomposition vessel 6 also warmed to a temperature of 80 ° to 90 ° c ., pulverized lime stone with an average diameter of 40 micron was introduced at a rate of about 35 kg / hour corresponding to remaining 54 % of nasho 3 . the resultant slurry was filtered by a vacuum filter 7 to remove the solid matter which was discharged by a shoot 15 after water - washing . the composition of the thus separated solid matter was 83 . 7 % of caso 3 . 1 / 2 h 2 o , 11 . 6 % of caso 4 . 2h 2 o and 3 . 1 % of caco 3 . the amount of the solid matter was about 84 kg / hour . that is to say , the total formation of gypsum in the first and the second double decomposition vessels was about 9 . 7 kg / hour corresponding to about 8 kg / hour of the decrease of naso 4 . into a similar absorbing tower as in example 1 , an exhaust gas of combustion containing 900 ppm of sulfur dioxide ( so 2 ) and 3 . 6 % of oxygen was introduced at a rate of 5 , 000 nm 3 / hour . an aqueous solution containing 0 . 1 % of nahso 3 , 9 . 3 % of na 2 so 3 and 8 . 9 % of na 2 so 4 was supplied into the absorbing tower from a pipe 3 at a rate of 680 kg / hour to absorb so 2 in the gas . the concentration of so 2 in the treated exhaust gas at the outlet 4 was about 20 ppm . from the bottom part of the absorbing tower , an aqueous solution containing each 6 % of nahso 3 and na 2 so 3 and 10 % of na 2 so 4 at a ph of about 6 was discharged at a rate of 632 kg / hour and it was removed to the first double decomposition vessel 5 . a part of the sulfites was oxidized to form about 2 kg / hour of na 2 so 4 . pulverized lime stone having an average diameter of 70 micron was thrown into the first double decomposition vessel 5 at a rate of 11 kg / hour corresponding to 60 % of the nahso 3 in the aqueous solution supplied to the vessel 5 to bring into reaction at a ph lower than 6 . 66 . the reaction mixture in a state of slurry was removed from the vessel 5 to the second double decomposition vessel 6 . the composition of the solid matter in the slurry was 71 . 0 % of caso 3 . 1 / 2h 2 o , 21 % of caso 4 . 2h 2 o and 6 . 8 % of caco 3 corresponding to the formation of about 3 . 1 kg / hour of gypsum . into the second double decomposition vessel 6 , pulverized lime stone having an average diameter of 40 micron was supplied at a rate of about 8 . 3 kg / hour corresponding to the remaining amount ( 40 %) of nahso 3 in the slurry . the slurry discharged from the vessel 6 was separated into 25 . 6 kg / hour of a solid matter containing 80 . 9 % of caso 3 . 1 / 2h 2 o , 13 . 3 % of caso 4 . 2h 2 o and 4 . 7 % of caco 3 and about 680 kg / hour of a filtrate by the separator 7 and the filtrate was circulated into the absorbing tower . in total , 3 . 4 kg / hour of gypsum were separated in the system , corresponding to about 2 . 8 kg / hour of na 2 so 4 . an exhaust gas containing 3 , 000 ppm of sulfur dioxide and 5 % by volume of oxygen was introduced into the absorbing tower in example 1 at a rate of 5 , 000 nm 3 / hour . an aqueous solution containing 0 . 3 % by weight of nahso 3 , 9 . 3 % by weight of na 2 so 3 and 9 . 3 % by weight of na 2 so 4 was supplied into the absorbing tower at a rate of 2 , 300 kg / hour to absorb sulfur dioxide in the exhaust gas . the content of sulfur dioxide in the thus treated exhaust gas at the outlet 4 of the absorbing tower was about 150 ppm . from the absorbing tower , an aqueous soulution containing 6 . 4 % by weight of nahso 3 , 5 . 9 % by weight of na 2 so 3 and 10 . 1 % by weight of na 2 so 4 at a ph of about 5 . 9 was drawn out at a rate of 2 , 180 kg / hour and transferred to the first double decomposition vessel 5 . meanwhile , a part of sulfite in the solution was oxidized in the absorbing tower to form na 2 so 4 at a rate of about 6 kg / hour . at the first double decomposition vessel 5 which was warmed in advance to a temperature of 50 ° to 70 ° c ., particles of calcium carbonate with a diameter of 150 micron were thrown into the above mentioned solution at a rate of 27 kg / hour corresponding to about 40 % by weight of acidic sodium sulfite at a ph of lower than 6 . 5 . the composition of the solid matter of the thus formed slurry was 69 . 2 % by weight of caso 3 . 1 / 2h 2 o , 24 . 2 % by weight of caso 4 . 2h 2 o and 5 . 2 % by weight of caco 3 which corresponded to the formation of about 8 . 8 kg / hour of calcium sulfate ( gypsum ). at the second double decomposition vessel 6 , which received the slurry from the first double decomposition vessel 5 and warmed to a temperature of 80 ° to 90 ° c ., particles of calcium carbonate with a diameter of 30 micron were thrown into the slurry at a rate of 41 kg / hour corresponding to a slight excess of remaining acidic sodium sulfite ( 60 % by weight of the total amount ). after the reaction was over , the slurry was filtered by the vacuum filter 7 to separate solid matter which was washed with water to be discharged from the port 14 and the filtrate which was returned to the absorbing tower via a pipe 3 . the composition of the solid matter was 83 . 9 % by weight of caso 3 . 1 / 2 h 2 o , 11 . 1 % by weight of caso 4 . 2h 2 o and 3 . 5 % by weight of caco 3 , and the amount of the solid matter was about 89 kg / hour . the result shows that formation of calcium sulfate ( gypsum ) in the first and the second reaction vessels was about 9 . 9 kg / hour corresponding to the reduction of about 8 . 2 kg / hour of sodium sulfate , na 2 so 4 , from the absorbing solution . there was another formation of sodium sulfate , na 2 so 4 , in the system except the absorbing tower , and especially a formation of about 2 . 6 kg / hour of na 2 so 4 was observed in the vacuum filter 10 . when this amount is added to the amount of formation of 6 kg / hour of na 2 so 4 in the absorption tower , the sum attains 8 . 6 kg / hour which is larger than the amount removed by the above - mentioned double decomposition of 8 . 2 kg / hour . then , in the second run of removal of sulfur dioxide from the same exhaust gas carried out under the conditions as identical as possible to those of the first run except the step of filtration , about 11 kg / hour of carbon dioxide which generated in the first reaction vessel and about 17 kg / hour of the same which generated in the second reaction vessel were assembled and introduced into the vacuum filter to intercept the contact of air to sulfite . as a result , the formation of sodium sulfate in the step of filtration was substantially prevented . accordingly , the concentration of sodium sulfate in the absorbing solution could be maintained at a constant value without providing any step of conversion of sodium sulfate or without drawing a part of sodium salt out of the system . a similar run was carried out as in example 1 except that the supply of lime stone was carried out in one step and carbon dioxide was not supplied to the step of filtration of the slurry containing calcium sulfite . on supplying about 64 kg / hour of pulverized lime stone having an average particle size of 150 micron only into the first double decomposition vessel 5 ( at a time ), the composition of the solid matter separated by the vacuum filter 7 was 64 . 4 % of caso 3 . 1 / 2h 2 o , 13 . 1 % of caso 4 . 2h 2 o and 20 . 1 % of caco 3 rich in remaining caco 3 , and the filtrate contained 1 . 4 % of nahso 3 , 8 . 6 % of na 2 so 3 and 9 . 1 % of na 2 so 4 and so it was inproper to be used for the absorption of so 2 . in another run similarly carried out as above , on supplying pulverized lime stone having an average diameter of 40 micron in an amount of about 64 kg / hour corresponding to the formation of nahso 3 at a time only into the first double decomposition vessel 5 , the composition of the solid matter separated by the vacuum filter 7 was 92 . 3 % of caso 3 . 1 / 2h 2 o , 2 . 5 % of caso 4 . 2h 2 o and 2 . 8 % of caco 3 and the filtrate contained 0 . 1 % of nahso 3 , 9 . 1 % of na 2 so 3 and 9 . 4 % of na 2 so 4 . these figures were all desirable , however , the separated amount of gypsum was 2 . 1 kg / hour corresponding to only about 1 . 7 kg / hour of na 2 so 4 . this actual capacity was far short for treating the total amount of 6 to 7 kg / hour of na 2 so 4 formed in the total system and it was impossible to maintain the concentration of na 2 so 4 in the solution unless providing a step of conversion of na 2 so 4 . | 1 |
fig1 shows a heat exchanger 1 of a gas hot air heating apparatus according to one embodiment of the present invention which uses a combustion exhaust gas as an internal fluid and indoor air as an external fluid . the heat exchanger 1 is constituted by connecting six cylindrical members 2 between an inflow pipe 11 and an outflow pipe 12 of the internal fluid . each of the cylindrical members 2 includes an intermediate portion 21 having an increased diameter and both end portions 22 , 23 having a hollow cylindrical shape having a reduced diameter . a baffle plate 3 for regulating the internal fluid is fitted inside the intermediate portion 21 of each cylindrical member 2 . the number of cylindrical members 2 constituting one heat exchanger 1 is determined appropriately in accordance with the heat exchange capacity , the limitation of a physical size , etc , but is preferably from four to eight from the aspect of heat exchange efficiency . the intermediate cylindrical members 2 among a line 20 of the six cylindrical members described above other than the cylindrical member 2a on the inflow side connected to the inflow pipe 11 having an increased diameter and the cylindrical member 2b on the outflow side connected to the outflow pipe 12 having a reduced diameter all have the following same construction . a first shell member 4 having a small connection port 41 having a reduced diameter atone of the ends thereof and a large connection port 42 having an increased diameter at the other end and a second shell member 5 having a small connection port 51 having a reduced diameter and a large connection port 52 having an increased diameter at the other end are butted against each other at their large connection ports 42 and 52 . the baffle plate 3 described above is clamped between the butt surfaces and the outer peripheries of these butt surfaces are clamped and is hermetically connected . in this embodiment , the first shell member 4 is shaped by pressing a heat - resistant metal plate as shown in fig2 and an inner cylindrical portion 43 as a caulking margin is so formed as to protrude in a downstream direction ( the fight - hand direction in the drawing ) at the small connection port 41 which is set on the upstream side ( the left - hand direction in the drawing ). a ring - like butt flat surface 44 is disposed around the outer periphery of the inner cylindrical portion 43 , and an inner conical surface 45 is so formed around the outer periphery of this butt flat surface 44 as to extend therefrom . a ring - like flat surface 46 is so formed around the outer periphery of the inner conical surface 45 as to extend therefrom . an outer conical surface 47 is further formed around the outer periphery of the ring - like flat surface 46 , and a cylindrical portion 48 is so formed as to extend from the outer periphery of the outer conical surface 47 toward the downstream side . a flange portion 49 as a butt surface is annularly formed from the rear end portion of this cylindrical portion 48 . an outer cylindrical portion 40 as a caulking margin is formed around the outer periphery of the flange portion 49 in such a manner as to extend in the downstream direction . the first shell member 4 and the second shell member 5 have the same shape with the exception of the difference between the inner cylindrical portion 43 and the inner cylindrical portion 53 as the caulking margin and the difference between the outer cylindrical portion 40 and the flange portion 59 . the second shell member 5 is formed by press molding , and an inner cylindrical portion 53 which fits to the inner cylindrical portion 43 is formed at the connection port 51 having a reduced diameter , which is set on the downstream side , in such a manner as to protrude in the downstream direction . a ring - like butt surface 54 is formed around the outer periphery of the inner cylindrical portion 53 , and an inner conical surface 55 is formed in such a manner as to extend from the outer periphery of the butt surface 54 . further , a ring - like flat surface 56 is formed around the outer periphery of the inner conical surface 55 . an outer conical surface 57 is formed around the outer periphery of the ring - like flat surface 56 , and a cylindrical portion 58 is extended from the outer periphery of the outer conical surface 57 toward the downstream side . a flange portion 59 as a butt surface is annularly formed in such a manner as to extend from the rear end of the cylindrical portion 58 . three recesses 50 comprising a flat surface swelling inside the shell member and inclined in a radial direction are equidistantly formed in the ring - like flat surface 46 and the outer conical surface 47 , and in the ring - like flat surface 56 and the outer conical surface 57 , and improve the mechanical strength of each shell member as a rib . the first shell member 4 and the second shell member 5 are hermetically connected to each other by butting the flange portion 49 of the large connection port 42 and the flange portion 59 of the large connection port 52 while clamping the baffle plate 3 between them , caulking the outer cylindrical portion 40 inward and wrap - clamping it around the outer peripheral portion of the flange portion 59 . the second cylindrical member 2 connected to the cylindrical member 2 described above is hermetically connected by butting the small connection port 41 of the third shell member 4 , which is the same as the first shell member 4 , against the small connection port 51 of the second shell member 5 in the first cylindrical member 2 and caulking the inner cylindrical portion 43 and the inner cylindrical portion 53 in an expanding direction . next , the large connection portion 42 of the third shell member 4 and the large connection port 52 of the fourth shell member 5 , which is the same as the second shell member 5 , are butted against each other , the baffle plate 3 is then clamped between both butt surfaces , and the outer peripheries of the butt surfaces is caulked and is hermetically connected . the heat exchanger 1 is produced by connecting a predetermined number of cylindrical members 2 by sequentially repeating the steps described above . as shown in fig2 the cylindrical member 2a on the inflow side is equipped on the inner periphery of the ring - like flat surface 46 with an inner cylindrical portion 4b as a caulking margin which protrudes toward the downstream side for the purpose of connection with the inflow pipe 11 of the shell member 4a on the upstream side . the distal end portion of the inflow pipe 11 is inserted into this inner cylindrical portion 4b , and is wound and fastened ( co - winding ) in the expanding direction as shown in fig3 . the other construction is the same as that of the intermediate cylindrical member 2 . the cylindrical member 2b on the outflow side is equipped on the shell member 5a on the downstream side with the inner cylindrical portion 5b as the caulking margin on the inner periphery of the ring - like flat surface 56 which protrudes on the upstream side . the distal end portion of the outflow pipe 12 is inserted into this inner cylindrical portion and is wound and fastened ( co - winding ) in the expanding direction in the same way as described above . the other construction is the same as that of the intermediate cylindrical member 2 . the outer diameter of the baffle plate 3 is set to be the same size as the outer diameter of the flange portions 49 , 59 , and its central portion has a shape of a circular truncated cone which swells toward the upstream side . the baffle plate 3 undergoes swelling due to the heat of the combustion exhaust gas as the internal fluid during use , and this circular truncated cone unifies the expanding direction between the baffle plates . in this way , it becomes possible to prevent variations of the expanding directions of the baffle plates 3 when they undergo swelling due to variance in the production and assembly . as a result , the disadvantages such as variance of heat exchange performance , the generation of noise when the baffle plate 3 returns from the swollen state to the flat plate , etc , can be avoided . a slit hole group comprising eight outer peripheral flow holes 31 which have a fan shape and are disposed equidistantly is formed at the outer peripheral portion of each baffle plate 3 . the formation positions of these outer peripheral flow holes 31 in the radial direction correspond to the outer conical surfaces 47 , 57 . a round hole group comprising four central flow holes 32 formed equidistantly on the same circumference is disposed at the conical surface portion at the center . by the way , the outer flow hole 31 may be a notch and the central flow hole 32 may be a slit , and the shape of the holes and their number can be selected appropriately . though this embodiment uses the shape of the circular truncated cone , the same effect can be obtained when the shape is spherical , too . in order to reduce the flow resistance and to accomplish uniform heat exchange efficiency throughout the entire length , the ratio of the flow rate of the slit hole group of the outer peripheral flow holes 31 to that of the round hole group of the central flow holes 32 is preferably at least 1 : 2 and at most 2 : 1 . when directionality in fitting is provided to the baffle plate 3 and the open area of the outer peripheral flow hole 31 on the upstream side of the flow of the external fluid , that is , on the upstream side of the heat exchanger , is made greater than that on the downstream side , the heat exchange proportion to the external fluid having a lower temperature on the upstream side can be made greater and heat exchange efficiency can be improved . when the open area of the outer peripheral flow hole 31 of the baffle plate 3 positioned on the upstream side of the heat exchanger is made greater then that on the downstream side , the heat exchange proportion to the external fluid having a lower temperature can be made uniform . the internal fluid flowing through the heat exchanger 1 is deflected by the baffle plate 3 as indicated by arrows in fig1 and at least 1 / 3 but less than 2 / 3 of the fluid passes through the outer peripheral flow holes 31 while less than 2 / 3 but at least 1 / 3 of the fluid passes through the central flow holes 32 . the internal fluid m passing through the outer peripheral flow holes 31 flows along the inner walls of the ring - like flat surfaces 46 , 56 , the outer conical surfaces 47 , 57 and the cylindrical portions 48 , 58 , changes to a turbulent flow , and efficiently exchanges heat with the external fluid , though the flow resistance is great . the internal fluid n passing through the central flow holes 32 is hardly subjected to heat exchange but flows downstream of the baffle plates 3 with a small flow resistance . the internal fluid m and the internal fluid n mix with each other downstream of the baffle plate 3 and the mixture is supplied to the cylindrical member 2 on the downstream side . accordingly , because heat exchange is gradually effected in the heat exchanger 1 throughout its full length , heat exchange efficiency becomes uniform from the cylindrical member 2a on the inflow side to the cylindrical member 2b on the outflow side . as a result , the temperature distribution of the external fluid subjected to the heat exchange can be made uniform . further , because the flow resistance of the central flow holes 32 is small , the overall pressure loss can be reduced . fig4 shows a gas hot air heater 100 equipped with the heat exchanger 1 according to the present invention . in this hot air heater 100 , an centrifugal type combustion blower b is mounted to the right side portion of a flat casing 200 formed by thin plate working and elongated in the transverse direction , and a transverse cylindrical combustion cylinder 13 is disposed at a lower portion of the casing 200 . a gas burner 14 is fitted to the right end portion of the combustion cylinder 13 and combustion air is supplied to it from the blower b , is mixed with a gas supplied from a control mechanism 15 of a fuel gas and is burnt . the heat exchanger 1 is transversely disposed above the combustion cylinder 13 inside the casing 200 . the left - hand end of the combustion cylinder 13 and the left - hand end of the inflow pipe 11 are connected by a connecting cylinder 16 having a square section . an exhaust cylinder 17 is interposed between the heat exchanger 1 and the combustion cylinder 13 in parallel with them . the right - hand end of the outflow pipe 12 connected to the right - hand end of the heat exchanger 1 is connected to the right - hand end of the exhaust cylinder 17 by a connecting cylinder 18 having a square section . the distal end ( left - hand end ) of the exhaust cylinder 17 penetrates through the back plate of the casing 200 and protrudes rearward . it is further connected to an exhaust outer pipe d disposed in a feed / exhaust hole h which is so defined on the chamber wall as to communicate the inside of the chamber with the outside . a fan f for blowing heating air having a thinly elongated cylindrical fan is disposed transversely at the upper part of the casing 200 . this fan f for blowing heating air blows forward indoor air , sucked from an indoor air suction port 19a defined at the upper part of the back plate of the casing 200 , via a hot air blow port 19b defined at the lower part of the front plate of the casino 200 . air for heating flows around the heat exchanger 1 , the exhaust pipe 17 and the combustion cylinder 13 as represented by a blank arrow , is so subjected to heat exchange , reaches a high temperature and is blown forward via the hot air blow port 19b . a water pan 1a for humidification is placed on the bottom plate of the casing below the combustion cylinder 13 inside the casing 200 in such a manner that it can be pulled out forward . since heating air is uniformly heated and blown out into the room in this gas hot air heater , the heater has a high heating effect . | 5 |
to test the receptor binding properties of mouse vegf - d , a plasmid was constructed for expression of the vegf homology domain ( vhd ) of mouse vegf - d . a dna fragment encoding amino acid residues 92 to 201 ( seq id no : 6 ) of full - length mouse vegf - d2 ( seq id no : 4 ) was amplified by polymerase chain reaction ( pcr ) with pfu dna polymerase , using as template a plasmid comprising full - length mouse vegf - d cdna ( seq id nos : 1 or 3 ). the amplified dna fragment , the correctness of which was confirmed by nucleotide sequencing , was then inserted into the expression vector pefbossflag ( a gift from dr . clare mcfarlane at the walter and eliza hall institute for medical research ( wehi ), melbourne , australia ). the pefbossflag vector contains dna encoding the signal sequence for protein secretion from the murine interleukin - 3 ( il - 3 ) gene and the flag ® octapeptide ( ibi / kodak ). the flag ® octapeptide can be recognized by commercially available antibodies such as the m2 monoclonal antibody ( ibi / kodak ). the vegf - d pcr fragment was inserted into the vector such that the il - 3 signal sequence was immediately upstream from the flag ® octapeptide , which was in turn immediately upstream from the truncated vegf - d sequence . all three sequences were in the same reading frame , so that translation of mrna resulting from transfection of pefbossflag - mousevegf - dδnδc into mammalian cells would give rise to a protein which would have the il - 3 signal sequence at its n - terminus , followed by the flag ® octapeptide and the truncated vegf - d sequence . cleavage of the signal sequence and subsequent secretion of the protein from the cell would give rise to a vegf - d polypeptide which is tagged with the flag ® octapeptide adjacent to the n - terminus . this protein was designated mouse vegf - dδnδc . the expression cassette encoding the flag - tagged truncated vegf - d construct was subcloned into the papex - 3 expression vector and then transiently expressed in 293ebna - 1 cells using fugene ( boehringer mannheim ) mediated transfection . after seven days of incubation , the conditioned medium was collected ( approximately 150 ml ) and subjected to affinity chromatography using the m2 ( anti - flag ) beads ( ibi / kodak ) according to the manufacturer . mouse vegf - dδnδc arising from affinity chromatography and purified human vegf - dδnδc ( for comparison purposes ) were analyzed by western blotting . about 50 ng of each protein was separately combined with sds - page sample buffer under reducing ( 2 % β - mercaptoethanol ) conditions , boiled and resolved by sds - page . the proteins were transferred to nitrocellulose and blotted with m2 antibody . as seen in fig2 both human and mouse vegf - dδnδc subunits have the expected molecular weight of 22 kda . the capacity of mouse vegf - dδnδc to bind and cross - link vegfr - 2 and vegfr - 3 was tested in bioassays . fig3 and 4 shows the results of analysis of mouse vegf - dδnδc protein using a vegfr - 2 /- 3 bioassay , respectively . the bioassay was performed using ba / f3 cells which express a chimeric receptor consisting of the extracellular domain of mouse vegfr - 2 or human vegfr - 3 and the transmembrane and cytoplasmic domains of the mouse erythropoietin receptor ( epor ). these cell lines die in the absence of il - 3 , unless they are supplied with ligands that cross - link the chimeric receptors . cross - linking of the vegfr / epor chimeric receptors induces signaling from the epor cytoplasmic domains that stimulates cell survival and proliferation . the cells were maintained in dulbecco &# 39 ; s modified eagle medium ( dmem ) containing 10 % fetal bovine serum ( fbs ), 50 mm l - glutamine , 50 μg / ml gentamicin and 10 % of the walter and eliza hall institute of medical research ( wehi )- 3d - conditioned medium as a source of interleukin - 3 ( il - 3 ) cells expressing the vegfr - 2 - epor or vegfr - 3 - epor chimeric receptor were washed three times in phosphate buffered saline ( pbs ), and once in complete medium lacking il - 3 . cells ( 10 4 ) were aliquoted into 96 - well microtiter plates containing dilutions of the test reagent or medium alone . cells were incubated for 48 hours at 37 ° c . in a humidified atmosphere of 5 % co 2 . cell proliferation was quantified by the addition of 1 μci of 3 h - thymidine for four hours prior to harvesting . incorporation of 3 h - thymidine was determined using a cell harvester and β - counting . as mentioned above , activation of the chimeric receptor rescues the cells from their dependence on il - 3 and causes the cells to proliferate in the absence of il - 3 . human vegf - dδnδc which is a ligand for both vegfr - 2 and vegfr - 3 , stimulates growth of these cell lines in a specific and dose - dependent fashion ( see fig3 and 4 , respectively ). mouse vegf - dδnδc was able to simulate growth of vegfr - 3 / epor cell line in a specific and dose - dependent fashion , but had no significant effect on the vegfr - 2 / epor cell line even at a concentration as high as 4 μg / ml ( see fig4 and 3 , respectively ). assays were carried out in duplicate and error bars denote a standard deviation of +/− 1 . 0 . this unexpected finding demonstrates that mouse vegf - dδnδc is not an activating ligand for vegfr - 2 . note that the vegfr - 2 extracellular domain in the chimeric vegfr - 2 / epor receptor expressed in the ba / f3 - vegfr - 2 - epor cell line was derived from mouse vegfr - 2 . therefore the inability of mouse vegf - dδnδc to induce survival and proliferation of these cells was not due to a species difference between this ligand and the extracellular domain of the chimeric receptor . the foregoing description and examples have been set forth merely to illustrate the invention and are not intended to be limiting . since modifications of the disclosed embodiments incorporating the spirit and substance of the invention may occur to persons skilled in the art , the invention should be construed broadly to include all variations falling within the scope of the appended claims and equivalents thereof . | 2 |
the present invention will now be described in detail with reference to the drawings , in which like reference numerals are used to refer to like elements throughout . fig1 illustrates a typical small area liquid crystal display that is well known in the art . the display includes a liquid crystal display panel 1 and a backlight unit 2 . the backlight unit 2 includes a number of components that are relevant to discuss here . a white light source 3 , that can be a fluorescent tube , a led with phosphor , rgb led group , a laser or other light source , is positioned to inject light into the edge of a thin lightguide 4 . the lightguide 4 is designed to transfer by total internal reflection ( tir ) 14 the light across the area of the display . at least one large or major face , which can be the top , bottom ( illustrated ) or both major faces , has features 6 that disrupt tir 15 in the lightguide 4 so that the light 13 leaves the lightguide 4 . the light 13 that leaves the lightguide 4 generally has the wrong angular brightness characteristics for the display , so four additional layers , a strong diffuser 7 , two crossed prism sheets 8 and 9 in orthogonal directions , and a weak diffuser 10 are used to produce the correct angular distribution . in many cases the weak diffuser 10 is incorporated into the top prism layer 9 . a further layer 11 can be a polarization conversion film , which is typically an interference film that reflects one polarization and transmits the other . the reflected light is recycled through the diffusers to become unpolarized and is then reflected by a back reflector 5 to the film again . the result is that the light is polarized so that it is better transmitted by the rear polarizer 12 of the liquid crystal slm 1 . the efficiency of this interference film is limited , however . an overview of a first embodiment of the present invention is shown in fig2 . the first embodiment of the present invention includes a backlight 20 that will be described in reference to the conventional backlight 2 of fig1 and the relevant changes only will be described here . as is shown in fig2 , the device in accordance with the invention includes a liquid crystal spatial light modulator ( slm ) 1 and a backlight 20 . the backlight includes a light source 3 , a lightguide 4 , and a reflector 5 . two sheets , a weak diffuser 21 and a polarization conversion film 11 , are individually possible but not required in this arrangement . the lightguide 4 has sub - wavelength extraction features 23 that can be positioned on one or both major faces of the lightguide 4 . in this example , the extraction features 23 are on the top surface . light 22 in the lightguide 4 is transmitted to the extraction features by tir 14 and extracted at the surface 24 by the extraction features 23 . the form of these extraction features 23 is shown in fig3 a . specifically , the extraction features 23 are formed by two or more interleaved gratings . in the present embodiment , two respective gratings are lenticular and the cross section is shown in fig3 a . the gratings are arranged on the surface of the lightguide 4 so that the intensity of light emitted from the lightguide 4 is substantially the same over the display . this can be achieved by arranging the diffractive features into areas whose density or sizes alter with position on the lightguide . the extraction feature cross section includes the symmetrical interleaving of two parallel square gratings 30 and 31 , one grating having a spatial frequency preferably exactly twice that of the other . the height 34 , 35 and the peak width 32 , 33 for the gratings 30 and 31 , respectively , are different . the peak width 33 of the high spatial frequency grating 31 is less than the peak width 32 of the low spatial frequency grating 30 . this composite grating represented in fig3 a , when incident with light from a range of angles and polarizations that are typical in a light illuminated lightguide , emits light in the main diffractive order that is strongly polarized . the strength of polarization ( te / tm ratio ) and width of the peaks depends on the conditions of the light illumination , but typically this will be light within the tir cone of the lightguide 4 . with a single lightguide 4 and a single wavelength light source 3 such as an led , te / tm ratios greater than 10 are readily possible . the grating 23 has no opaque areas on the surface , and is simply a refractive grating . the inventive concept of this invention primarily concerns the structure of the extraction features as shown in fig3 a . more specifically the design takes advantage of the intrinsic phase difference that occurs between te and tm polarizations as they reflect on the upper and bottom interfaces in a lightguide , 4 . the lenticular grating structure 23 is made from two different gratings , the second of which alters the height of the first grating . the effect of this is that the emitted field from one grating layer is in anti - phase from the field emitted from the second grating layer for one polarization . therefore , light of the first polarization emanating from the two grating layers interferes destructively and since it cannot transmit through the grating it all reflects back to the lightguide , 25 . however , due to the intrinsic phase difference between the two polarizations , interference cannot be destructive for the second polarization which is allowed to transmit through the grating leading to a well polarized beam out - coupled from the lightguide . fig3 b shows the variation of te , 36 , and tm , 37 , extracted from the lightguide as a function of the second grating height 35 , for a particular value of pitch 31 , and first grating height 34 , and for a particular incident angle light in the lightguide . fig3 c shows the te / tm ratio as a function of the height 35 . at certain values of height , maxima are seen , 38 a and 38 b corresponding to the destructive interference . the peaks are dependent on the refractive index of the lightguide material , the wavelength of the light in the lightguide and the range of angles in the lightguide . which peak is used will depend on a balance on these values . an example of this arrangement with a high te / tm ratio with a 405 nm led is as follows . the value of the spatial pitch of the grating 31 is 155 . 14 nm , the pitch of the grating 30 is 310 . 28 nm . the peak width 33 is 77 . 1 nm , the peak width 32 is 155 . 14 nm . the height 35 is 130 . 6 nm and the height 34 is 163 . 3 nm . it should be noted that these are only examples in a particular case , and that the invention describes the general shape of multiple gratings interacting that can be applied to a range of wavelengths , lightguide shapes and layers . this invention should not be limited to simply two gratings . multiple gratings that have a pitch that is an integer multiple of the smallest pitch can be combined to improve the performance of this system . in the extreme , multiple gratings can be combined to approximate a continuous curve cross section similar to a discrete fourier cosine distribution . a second embodiment of the present invention is shown in fig4 . for sake of brevity , only the relevant differences between this embodiment and the embodiment of fig2 are described herein . in this aspect the lightguide 4 of the backlight 40 has a second layer 41 , in which the refractive index of this layer 41 is less than that of the lightguide 4 . the diffractive features 23 are placed on the second layer 41 . in this arrangement the range of angles in the second layer 41 is much reduced . this means the quality of the out - coupled light is significantly improved over the single - lightguide approach . extraction of light at 42 from the main lightguide 4 into the secondary lightguide formed by the second layer 41 can be controlled by appropriate non - diffractive features on the opposite face of the lightguide 4 , for example shallow wedge shaped features 48 that redirect at 47 a small proportion of the lightguide light 45 into the second layer 41 . the number of such additional layers is not fixed , and they can be on the lower or both surfaces of the lightguide 4 and any of the faces or interfaces can have one or more extraction arrangements . in a further embodiment shown in fig5 , a modified lightguide arrangement is suggested . only relevant differences over the embodiment of fig2 are described herein for sake of brevity . in the embodiment of fig2 , if the extraction is a significant amount of the light in the lightguide , extraction of one polarization will reduce the amount of that polarization relative to the other in the lightguide 4 . thus the assumption of non - polarized light becomes less true as te light is extracted , the te / tm light ratio in the lightguide 4 reduces , thus extraction te / tm further away from the light source 3 will reduce . to prevent this , a second layer 50 is added to the face of the lightguide 4 opposite the extraction features 23 . the layer 50 is such that its does not deflect the light ( so does not disrupt tir ), but affects the phase of the incident light at angles to the normal that are typical to tir light , such that the plane of polarization after reflection has rotated by 90 degrees ( a quarter wave plate layer ). unpolarized light 52 is incident on the layer of polarized extraction features 23 that emits te light 51 from the surface . the reflected light 53 has a relatively enhanced tm component . the light is then incident on the quarter wave plate layer 50 and totally internally reflected 54 . the reflected light is rotated to the te direction 55 so that extraction for the polarization layer will then be more efficient and maintain the polarization out - coupled . the next pass will rotate the plane of polarization back so that the light in the lightguide 4 is on average unpolarized , and the light incident on the extraction features 23 is slightly biased towards the preferential te mode , enhancing further the extraction efficiency and te / tm ratio . in a further embodiment as shown in fig6 based on the embodiment of fig5 , the nature of the diffractive features is such that there may be a component of light 61 , in the preferential te mode directed back into the lightguide 4 . typically this light will be in a direction that will not be totally internally reflected by the lightguide 4 and will be extracted by reflection from the reflector 5 . in the case where the quarter wave plate layer 50 is at the bottom of the lightguide 4 , the light 61 would pass through as 62 in a circular polarization state , reflected as 64 in a circular polarization state and will pass through the quarter wave plate layer 50 to produce light 65 in a tm mode . this will then be extracted . this light will reduce the final te / tm ratio of the backlight . this can be removed , as is shown in fig6 , by another quarter wave plate layer 60 positioned on the reflector 5 . this layer 60 is not in optical contact with the other layer 50 . the light passing through the first quarter wave plate layer 50 will be circularly polarized as 62 but corrected at 63 by the second quarter wave plate layer 60 to give a circularly rotated beam 64 that will become a te beam 65 upon passing through the first quarter wave plate 50 again . this will then contribute to an improved te / tm ratio for the system . a further embodiment is shown in fig7 . a detail on this embodiment is shown in fig8 . this is described with reference to the embodiment of fig2 , but improvements of the subsequent embodiments can be applied to this embodiment . referring only to the relevant differences , the backlight 70 in this embodiment makes use of a birefringent diffractive layer 71 on the lightguide 4 in place of the layer of extraction features 23 . the birefringent diffractive layer 71 creates diffraction peaks at two angles for two different polarizations 86 and 87 from unpolarized light 84 incident on the area 85 . the beams are then passed through a lens layer 72 and then a patterned retarder layer 73 which converts one of the beams into the opposite polarization state to make a polarized emission , both beams 74 a and 74 b are in the same polarization state . this embodiment does not have an issue with the changing polarization state in the lightguide 4 . the birefringent layer 71 may include , for example , a lenticular square grating , patterned as described above , made up of a square array of birefringent , reactive mesogen or liquid crystal material 83 . in this case “ lenticular ” refers to line strips perpendicular to the plane of the page and have the same cross section along the length . the lens array 72 may include lenticular lenses 80 , and the retarder film 73 may include lenticular strips 81 of birefringent half wave layers that rotate the plane of polarization by 90 degrees . the retarder area can be made of the same material as that of the birefringent diffractive area . unpolarized light 84 in the lightguide 4 meets the diffractive structure 83 . the diffractive structure may be the same structure shape as in fig3 a or may be a square grating where the height 35 is zero . in the case of this embodiment , the features may or may not be made of the same material as the lightguide , but would be created of a birefringent material . this means that the light 84 reaching the grating is diffracted at different angles 86 and 87 according to polarization , because the diffractive nature of the grating is dependent on the refractive index . the diffraction split will be in one plane as shown in the diagram , but in a lenticular form . a lenticular lens 72 collimates the two beams , where the separation of the lens 72 and the rating plane 71 is approximately equal to the focal length in the material separating the layers ( e . g . glue or air ). the collimation will be spatially split in terms of polarization , so a second layer 73 above the lens consisting of lenticular stripes of birefringent material 81 , in a half - wave thickness , is aligned with the lens layer . the pitch of the stripes is the same as the lens and the width of the stripes is approximately half the pitch . one polarization is then rotated producing light emerging from the stripes , 74 a and 74 b with the same polarization state . all aspects of this invention will work with a white light source , but a broad wavelength spectrum of the source would not be optimum for a single design of the extraction films . one aspect whereby the polarization state can be improved by having a coloured source is by mixing different designs that are optimized for high te / tm at different wavelengths with the source spectrum . for example , extraction features optimized for red , green and blue emission ( for example , different values of 30 , 31 , 32 , 33 , 34 , and 35 ) can be mixed together rather than using a single mean design . another aspect is shown in fig9 and is whereby three lightguides with three red , green , blue light sources 91 , 92 and 93 , and three designs of extraction features 94 , 95 and 96 will produce a higher te / tm ratio than the preferred embodiment with a single lightguide and source . another variation that can be applied to the embodiments described above is shown in fig1 . the display 100 has multiple colour phosphor layers 101 under internal polarizer structures 102 with the liquid crystal region in the slm . in this case only one wavelength , that will excite the phosphors , is necessary for the backlight to illuminate the panel . the colour emission is made from the amount of the emitted light 22 passing through the slm pixels to the particular phosphor . the extraction features can then be designed for this wavelength . another variation is shown in fig1 . a modified display 111 and backlight component 110 is described with reference to the embodiment of fig2 . this involves a choice of design of extraction features 112 in place of the extraction features 23 so that the extracted polarized light 113 is extracted normal to the lightguide surface . in this case a lens array 114 can be used to focus light through pixels 115 onto phosphor areas 116 printed on the outside of the liquid crystal cell 111 . the extraction features 112 would be of the same general design as that described in the preferred embodiment and subsequent embodiments , but may have a different set of dimensions for the same materials . the phosphors then produced the colour required 103 . the liquid crystal cell need not then have any colour filters and thus would improve the brightness of the system . in addition the polarizers 12 and 117 are standard polarizers , so that this design would be easier to manufacture . the extraction features described here can be manufactured using nano - imprint techniques that are well known in the prior art . although the invention has been shown and described with respect to certain preferred embodiments , it is obvious that equivalents and modifications will occur to others skilled in the art upon the reading and understanding of the specification . the present invention includes all such equivalents and modifications , and is limited only by the scope of the following claims . | 6 |
fig1 illustrates a block diagram of an example embodiment of secure software and hardware association ( ssha ) circuitry 100 . as will be discussed below , ssha includes two modes : ( 1 ) original equipment manufacturer ( oem ) hardware will only run oem software ; and ( 2 ) oem software will only run on oem hardware . as illustrated , the ssha circuitry 100 includes a code authentication unit ( cau ) 110 , code decryption logic ( cdl ) 120 and first - time boot logic ( ftbl ) 130 . the ssha circuitry 100 is configured to be coupled between a processor ( e . g ., semiconductor 610 of fig6 a and 6b ) and program code memory ( e . g ., program code flash memory 630 of fig6 a and 6b ) to control the loading of the program code by the processor . the program code may be boot code or application software the cal 110 , cdl 120 and ftbl 130 may be programmable logic or in a processor . further , in certain embodiments , a configurable ( e . g ., time based ) bypass may exist for debugging , development or evaluation purposes . the ssha circuitry 100 further includes memory 140 configured to store a public asymmetric encryption key 145 associated with the oem . the cau 110 authenticates initial program code . the cal 110 is configured to retrieve the public key 145 associated with the oem from the memory 140 . the cau 110 further is configured to load initial program code for the processor from the program code memory . the cal 110 then authenticates the initial program code for the processor retrieved from the program code memory by using the public key 145 retrieved from the memory 140 . in particular embodiments in which the initial program code identifies a secure location associated with the oem ( e . g ., secure location 650 of fig6 a and 6b ) storing encrypted program code ( e . g ., encrypted program code 655 of fig6 a and 6b ), the ftbl 130 establishes a secure connection to the secure location storing the encrypted program code . the ftbl then receives a command from the secure location signed by a private asymmetric encryption key associated with the oem requesting a chip identifier token ( chipid token ) and , in response , generates the chipid token by encrypting a chip identifier ( chipid ) stored in memory by using the public key 145 . the ftbl 130 then transmits the chipid token to the secure location to be verified by the oem by matching the chipid against chipids stored in a database ( not shown ). the database may be maintained by the oem . if the chipid is a match , the ftbl 130 receives encrypted program code encrypted by a symmetric code encryption key ( cek ) from the database and signed using the oem private key . the cau 110 then authenticates the signed encrypted program code by using the public key 145 . the cdl then decrypts the authenticated encrypted program code by using a corresponding symmetric cek 155 stored in memory 150 . in a preferred embodiment , the cek is not transmitted during the secure connection , but rather is known as previously provided via an out - of - band communication fig2 is a flow diagram 200 illustrating an example embodiment method of ssha installation . during the production of semiconductor products , chips , processors or other embodiments of ssha circuitry , such as a system - on - a - chip ( soc ), a semiconductor provider marks each embodiment of the ssha circuitry as installed or disabled ( 210 ) in a process referred to herein as ssha installation . semiconductor products with ssha installed are referred to herein as ssha - enabled products . in a preferred embodiment , the semiconductor provider will not ship any semiconductor products without some form of ssha circuitry installed , either installed or disabled . ssha may be installed by burning a fuse or setting a flag inside one - time programmable ( otp ) memory . during ssha installation , a public asymmetric encryption key associated with an oem ( 220 ) is retrieved from a certificate authority . in some embodiments , the oem itself can be the certificate authority . the oem public key may use any asymmetric cryptographic standard such as elliptic curve cryptography ( ecc ) and rivest shamir / adleman ( rsa ). further , a cdl ( e . g ., cdl 120 of fig1 ) generates a number referred to herein as a chipid ( e . g ., chipid 160 of fig1 ) ( 230 ) and an associated symmetric chipid encryption key ( cek ) ( e . g ., cek 155 of fig1 ) ( 240 ). the chipid is a value used as a unique identifier for the semiconductor product and may be any number , a random number , or associated with the asymmetric public and private key pair . similarly , the cek may be any symmetric encryption key or may be associated with the asymmetric public and private key pair . the oem public key , chipid and cek are stored in otp memory or secure non - volatile memory ( 250 ). the chipid and cek preferably are not exposed or read - able in plain format . further , the cek may be changed over a secure connection by receiving a request signed by an associated asymmetric oem private key that provides a new symmetric cek as described further herein . the chipid is encrypted by the associated oem public key to generate a chipid token ( 260 ). similarly , the cek is encrypted by the associated oem public key to generate a cek token ( 270 ). during the ssha installation process , the chipid token and cek token are provided one time to the semiconductor provider to be stored in a vendor token database ( vtd ) 280 . providing tokens generated by encrypting the chipid and cek using the oem public key is to enforce viewing of the actual chipid and cek values by only the oem who has access to an asymmetric oem private key . the oem private key preferably is not revealed to other parties , including the semiconductor manufacturer . although ssha installation is managed by the semiconductor provider , in a preferred embodiment , the semiconductor provider does not know the value of the chipid and cek and only temporarily knows the values of the chipid token and cek token so they may be stored in the vtd . the semiconductor provider then signs the vtd using its private key ( 285 ) and transfers the entire vtd to the oem over a secure connection ( 290 ), such as ssl . in a further preferred embodiment , the semiconductor provider then destroys its copy of the vtd ( 295 ). thus , any record of production of the ssha - enabled products is only available to the oem as stored in the vtd . fig3 a is a flow diagram 300 a illustrating a process flow of a first ssha mode in which oem - approved hardware only runs oem - approved software . following ssha installation by the semiconductor provider ( e . g ., as illustrated in fig2 ), ssha - enabled products allow enforcement of an authenticated program code process mode called “ oem - approved hardware only runs oem - approved software ” using the associated oem public key stored in memory during ssha installation . as will be discussed below , a further mode may be enabled called “ oem - approved software only runs on oem - approved hardware .” after ssha installation by the semiconductor provider , at first power - on of the semiconductor following receipt by a contract manufacturer ( cm ) or original design manufacturer ( odm ) ( 305 ), embodiments the ssha circuitry are configured to determine whether ssha was installed or disabled during ssha installation ( 310 ) by detecting the state of the internal otp memory or fuse . if ssha has been disabled permanently , the ssha circuitry effectively functions as a wire to allow the processor of the semiconductor product to load program code normally . however , if ssha has been installed , the ssha process continues to authenticate initial program code . the initial program code is sent from the oem ( 312 ) and may be in two forms : ( 1 ) signed by the oem private key and unencrypted ; or ( 2 ) signed by the oem private key and encrypted using a symmetric cek . the cau reads the oem public key ( 315 ) and loads the initial program code from program code memory ( 320 ). in this example embodiment , the cau uses public key infrastructure ( pki ) techniques to authenticate the initial program code to ensure it was issued by the oem ( 325 ). in other words , the initial program code must have been signed using the oem private key to be retrieved successfully by the oem public key stored in memory during ssha installation . the pki scheme may use any asymmetric cryptographic standard such as ecc and rsa . if the initial program code was signed by the oem private key but not encrypted , the initial program code is accessible to the processor in a transparent manner and the processor begins the normal program code loading process ( 330 ) in the mode “ oem - approved hardware only runs oem - approved software .” however , the initial program code may be a restricted or initialization program code to enforce the mode “ oem - approved software will only run on oem - approved hardware .” fig3 b is a flow diagram 300 b illustrating a process flow of a second ssha mode in which oem - approved software only runs on oem - approved hardware . in this mode , the authenticated initial program code , such as the initialization program code authenticated as described above with reference to fig3 a , is a restricted program code that is used to establish a secure connection with a secure location to get encrypted program code . such a secure connection is typically a network connection . to access the encrypted program code , the cdl establishes a secure connection ( 335 ), such as a secure sockets layer ( ssl ) session , with a secure location operated by the oem that will authenticate the request for encrypted program code and then send the encrypted program code . after the secure connection is established , the secure location requests a chipid token by sending a command signed using the oem private key ( 340 ). in response , the cdl authenticates the request and encrypts the chipid using the oem public key stored in memory to generate a chipid token ( 345 ) and transmits the chipid token to the secure location ( 350 ). the chipid token is then decrypted using the oem private key to retrieve the chipid at the secure location ( 355 ). the retrieved chipid is then matched against chipids stored in the vtd ( 360 ). if the chipid is a match , the symmetric cek associated with the chipid is retrieved from the vtd ( 365 ). the cek is used to encrypt the program code which is the signed by the oem private key ( 370 ). the signed and encrypted program code is then sent to the cdl ( 375 ). if the chipid is not a match , encrypted program code is not provided . upon receipt of signed and encrypted program code , the cau authenticates the signed and encrypted program code using the oem public key stored in memory . then the cdl decrypts the authenticated encrypted program code using the symmetric cek stored in memory ( 385 ). in a preferred embodiment , the cek is not exchanged during the secure connection . the cdl can use any symmetric cryptographic algorithms , such as advanced encryption standard ( aes ) and data encryption standard ( des ). after successful cdl decryption , the program code is accessible to the semiconductor in a transparent manner and the semiconductor begins the normal program code loading process ( 390 ). fig4 is a flow diagram 400 illustrating a method by which program code may be updated or replaced . to update or replace program code , the updated program code is encrypted using the symmetric cek ( 410 ) and signed using the oem private key ( 420 ). the signed and encrypted program code is then released to the oem &# 39 ; s customer base ( 430 ). this may be by distribution of a physical disk , a link to a secure location or via a command sent to the semiconductor . an update command sent by the oem may be encrypted using the symmetric cek unique to the semiconductor to ensure that boot code or associated application software upgrade is not possible if the oem &# 39 ; s asymmetric private key is compromised . after receipt of the updated program code , the cau authenticates it as from the oem using the oem public key ( 440 ). the authenticated encrypted updated program code is then decrypted using the symmetric cek stored in memory ( 450 ). the updated program code then may be loaded ( 460 ). similar to the scenario described above during the first boot , for the mode “ oem - approved software will only run on oem - approved hardware ,” the updated program code may not contain actual program code but rather may establish a secure connection from the semiconductor to a secure location operated by the oem that will deliver new program code encrypted using the associated cek . fig5 is a flow diagram 500 illustrating a method by which an oem public asymmetric encryption key and a symmetric cek may be changed if an oem private asymmetric key has been compromised . if the oem private key is compromised , systems deployed in the field cannot be upgraded remotely because the source of the code cannot be trusted , rather , the system may be upgraded by a secure physical connection , such as a universal serial bus ( usb ) memory key . to protect the cek from physical attacks , such as chip - cover - popping or bit - reads from silicon , the cek may be masked via a hardware algorithm that uses a random number as a seed , covered in epoxy , or protected with key zeroization hardware . the algorithm to mask the secret key can be any masking or encryption scheme . key zeroization mechanisms built into the hardware may be used in conjunction with attack prevention techniques described by the federal information processing standard ( fips ) publication 140 - 2 . however , although the oem private key has been compromised , if the cek has not been compromised and if the oem public key and cek are stored in non - volatile memory , the oem public key and the cek may be changed by providing commands encrypted by the symmetric cek ( 510 ) via a secure physical connection . in one embodiment this secure physical connection may connect directly into the ssha circuitry . even though the oem private key is compromised , the encrypted program code will not be compromised because , in a preferred embodiment , the semiconductor product does not provide the symmetric cek , but rather only accepts new keys and program code after a secure connection . the commands then may be decrypted using the symmetric cek stored in memory ( 520 ), the new oem public asymmetric key and the new symmetric cek may be loaded into memory ( 530 ) fig6 a illustrates a first embodiment of a system 600 a having external ssha circuitry 620 . the system includes a semiconductor 610 , ssha circuitry 620 ( e . g ., ssha circuitry 100 of fig1 ), and program code flash memory 630 . in this embodiment , the ssha circuitry 620 is external to the semiconductor 610 and is coupled between the semiconductor 610 and the program code flash memory 630 . in the mode “ oem - approved hardware only runs oem - approved software ,” the external ssha circuitry 620 operates to keep the semiconductor 610 in a reset state along a reset signal path 640 until oem - approved program code from the program code flash 630 is authenticated . in the mode ‘ oem - approved software only runs on oem - approved hardware ,” the external ssha circuitry 620 operates to keep the semiconductor 610 in a reset state along the reset signal path 640 until encrypted oem program code 655 received from a secure location 650 , typically over a network 660 , is decrypted successfully . fig6 b illustrates a second embodiment of a system 600 b having internal ssha circuitry 620 . the system includes a semiconductor 610 , ssha circuitry 620 ( e . g ., ssha circuitry 100 of fig1 ), and program code flash memory 630 . in this embodiment , the ssha circuitry 620 is internal to the semiconductor 610 . in the mode “ oem - approved hardware only runs oem - approved software ,” the internal ssha circuitry 620 operates to halt operation of the semiconductor 610 until oem - approved program code from the program code flash 630 is authenticated . in the mode “ oem - approved software only runs on oem - approved hardware ,” the internal ssha circuitry 620 operates to halt operation of the semiconductor 610 along input / output ( i / o ) 660 until encrypted oem - approved program code 655 received from a secure location 650 , typically over a network 660 , is decrypted successfully . while this invention has been particularly shown and described with references to example embodiments thereof , it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims . implementations of flow diagrams illustrating example embodiments may be implemented in a form of hardware , firmware , software , and combinations thereof . if implemented in software , the software may be any suitable language , stored on a computer - readable medium , and be loaded and executed by a processor . the processor can be any general or application - specific processor that can execute the software in a manner consistent with the principles of the present invention , as claimed and illustrated by the example embodiments presented herein . | 7 |
reference will now be made to the drawings wherein like structures are provided with like reference designations . it will be understood that the drawings included herewith only provide diagrammatic representations of the presently preferred structures of the present invention and that structures falling within the scope of the present invention may include structures different than those shown in the drawings . referring now to fig1 there is shown a cross - sectional diagram of a structure used for forming a container capacitor having an electrode which is roughened on both its inner and outer surfaces , in accordance with a preferred embodiment of the present invention . the structure shown in fig1 is formed of a substrate 10 having a doped ( n +) region 12 disposed therein . a contact 14 , preferably formed of doped silicon , is disposed immediately above region 12 . a bpsg layer 16 having a trench 16a is positioned on top of substrate 10 . an etch stop layer 18 formed of silicon nitride or teos oxide is positioned within bpsg layer 16 . the structure shown in fig1 may be formed by methods well known in the art . in a preferred embodiment of the present invention , the thickness of bpsg layer 16 is about 12 , 000 angstroms , and the thickness of etch stop layer 18 is about 1000 angstroms . in order to form the container capacitor of the present invention , a layer 20 of gebpsg ( shown in fig2 ) is deposited on top of bpsg layer 16 . the germanium doped bpsg layer 20 has a dopant concentration above 1 %, and , in the preferred embodiment , the dopant concentration in gebpsg layer 20 is about 10 %. germanium is preferably incorporated in layer 20 in the form of geo or geo 2 clusters or precipitates . gebpsg layer 20 is preferably formed on top of bpsg layer 16 using a chemical vapor deposition process (&# 34 ; cvd &# 34 ;), although other procedures may alternatively be used . in the preferred embodiment , gebpsg layer 20 has a thickness ranging between 200 to 1000 angstroms . following deposition of gebpsg layer 20 over top of bpsg layer 16 , a space 22 is etched in gebpsg layer 20 , thereby exposing an upper surface of contact 14 . referring now to fig3 following the formation of space 22 , a wet etching step is used to roughen surface 20a of gebpsg layer 20 . the wet etching material used in this step may consist of deionized water . alternatively , a dilute hf solution having a concentration of about 1000 : 1 may be used for the wet etching step . in a still further alternative embodiment , a dry etching process may be used to form roughened surface 20a on gebpsg layer 20 . referring now to fig4 following the formation of roughened surface 20a , a layer of polysilicon 24 is deposited on top of gebpsg layer 20 . in one embodiment , polysilicon layer 24 is formed of amorphous silicon and is deposited on top of gebpsg layer using a cvd step , although other procedures may also be used . polysilicon layer 24 is preferably 250 - 1000 angstroms in thickness and , still more preferably , 400 - 600 angstroms in thickness . in a still further preferred embodiment , polysilicon layer 24 will be about 500 angstroms in thickness . when polysilicon layer 24 is formed of amorphous silicon or smooth polysilicon , the inner surface 24a of polysilicon layer 24 will naturally follow the roughened contour of surface 20a , thereby giving inner surface 24a a roughened texture . outer surface 24b of polysilicon layer 24 will also conform to layer 20a , thereby giving outer surface 24b a roughened texture . in an alternative embodiment , polysilicon having intrinsic surface roughness ( shown in fig4 ) may be used to form layer 24 . in this alternative embodiment , after deposition of polysilicon surface 24 , polysilicon layer 24 is preferably seeded with a disilane and then annealed in order to form roughened inner surface 24a . referring now to fig5 after polysilicon layer 24 ( having roughened surfaces 24a , 24b ) is disposed on top of gebpsg layer 20 , the structure shown in fig4 is subjected to a chemical - mechanical planarization (&# 34 ; cmp &# 34 ;) process wherein the portion of polysilicon layer 24 lying outside trench 16 is removed from the structure . following this cmp step , a wet etch is applied to the bpsg layer 16 , thereby etching away the portion of bpsg layer 16 disposed above etch stop 18 and yielding the capacitor electrode structure shown in fig6 having roughened inner surface 24a and roughened outer surface 24b . a dilute hf solution having a concentration of about 100 : 1 may be used for this wet etching step . in a still further alternative embodiment , a dry etching step may be used to remove the portion of bpsg layer 16 disposed above etch stop 18 . referring now to fig7 there is shown a cross - sectional diagram of a structure used for forming a container capacitor having an electrode which is roughened on both its inner and outer surfaces , in accordance with an alternative preferred embodiment of the present invention . like the structure shown in fig1 the structure shown in fig7 is formed of a substrate 10 having a doped ( n +) region 12 disposed therein . a contact 14 , preferably formed of doped silicon , is disposed immediately above region 12 . a template layer 17 formed from , for example , an insulator such as bpsg or gebpsg , is positioned on top of substrate 10 . since the preferred materials used for forming template layer 17 are bpsg and gebpsg , template layer 17 will be referred to hereafter as bpsg layer 17 , although it will be understood be those skilled in the art that other materials may alternatively be used to form layer 17 . an etch stop layer 18 formed of silicon nitride or teos oxide is positioned within bpsg layer 17 . the structure shown in fig7 may be formed by methods well known in the art . in a preferred embodiment of the present invention where layer 17 is formed of bpsg or gebpsg , the thickness of bpsg layer 17 is about 12 , 000 angstroms , and the thickness of etch stop layer 18 is about 1000 angstroms . in a still further embodiment , bpsg layer 17 may be formed of germanium doped bpsg having a dopant concentration above 1 %, and , still more preferably , the dopant concentration will be about 10 %. germanium may be incorporated in bpsg layer 17 in the form of geo or geo 2 clusters or precipitates . bpsg layer 17 is preferably formed on top of substrate 10 using a cvd process , although other procedures may alternatively be used . although in the preferred embodiment shown in fig7 the portions of layer 17 positioned above and below etch stop layer 18 are formed of the same material , it will be understood by those skilled in the art that the portion of layer 17 disposed above etch stop layer 18 may alternatively be formed of a different material than the portion of layer 17 disposed below etch stop layer 18 . referring now to fig8 a rapid thermal annealing process is used to roughen surface 17a of bpsg layer 17 . in a further alternative embodiment , a sacrificial metal layer or a thin doped polysilicon layer ( both not shown ) having a higher melting temperature than bpsg layer 17 may be deposited on top of bpsg layer 17 prior to the annealing step to create wrinkled or roughened surface 17a . alternatively , a wet etching step may be used to roughen surface 17a of bpsg layer 17 . the wet etching material used in this step may consist of deionized water . alternatively , a dilute hf solution having a concentration of about 1000 : 1 may be used for the wet etching step . in a still further alternative embodiment , a dry etching process may be used to form roughened surface 17a on bpsg layer 17 . referring now to fig9 following the formation of roughened surface 17a , a layer of polysilicon 24 is deposited on top of bpsg layer 17 . in one embodiment , polysilicon layer 24 is formed of amorphous silicon or smooth polysilicon and is deposited on top of bpsg 17 layer using a cvd step , although other procedures may also be used . polysilicon layer 24 is preferably 250 - 1000 angstroms in thickness and , still more preferably , 400 - 600 angstroms in thickness . in a still further preferred embodiment , polysilicon layer 24 will be about 500 angstroms in thickness . when polysilicon layer 24 is formed of amorphous silicon or smooth polysilicon , the inner surface 24a of polysilicon layer 24 will naturally follow the roughened contour of surface 17a , thereby giving inner surface 24a a roughened texture . outer surface 24b of polysilicon layer 24 will also conform to layer 17a , thereby giving outer surface 24b a roughened texture . in an alternative embodiment , polysilicon having intrinsic surface roughness may be used to form surface 24 . in this alternative embodiment , after deposition of polysilicon layer 24 , polysilicon layer 24 is preferably seeded with a disilane and then annealed in order to form roughened inner surface 24a . referring now to fig1 , after polysilicon layer 24 ( having roughened surfaces 24a , 24b ) is disposed on top of bpsg layer 17 , the structure shown in fig9 is subjected to a cmp process wherein portions of polysilicon layer 24 and bpsg layer 17 are removed from the structure . following this cmp step , a wet etch is applied to the bpsg layer 17 , thereby etching away the portion of bpsg layer 17 disposed above etch stop 18 and yielding the capacitor electrode structure shown in fig1 having roughened inner surface 24a and roughened outer surface 24b . a dilute hf solution having a concentration of about 100 : 1 may be used for this wet etching step . in a still further alternative embodiment , a dry etching step may be used to remove the portion of bpsg layer 17 disposed above etch stop 18 . furthermore , it is to be understood that although the present invention has been described with reference to a preferred embodiment , various modifications , known to those skilled in the art , may be made to the structures and process steps presented herein without departing from the invention as recited in the several claims appended hereto . | 7 |
in the following description , various aspects of the present invention will be described . however , it will be apparent to those skilled in the art that the present invention may be practiced with only some or all aspects of the present invention . for purposes of explanation , specific numbers , materials and configurations are set forth in order to provide a thorough understanding of the present invention . however , it will also be apparent to one skilled in the art that the present invention may be practiced without the specific details . in other instances , well known features are omitted or simplified in order not to obscure the present invention . parts of the description will be presented in terms of operations performed by a processor based device , using terms such as receiving , analyzing , determining , instructing , and the like , consistent with the manner commonly employed by those skilled in the art to convey the substance of their work to others skilled in the art . as well understood by those skilled in the art , the quantities take the form of electrical , magnetic , or optical signals capable of being stored , transferred , combined , and otherwise manipulated through mechanical and electrical components of the processor based device ; and the term processor include microprocessors , micro - controllers , digital signal processors , and the like , that are standalone , adjunct or embedded . parts of the description will be described using various acronyms , including but are not limited to : atm asynchronous transfer mode dns domain name service ip internet protocol sonet synchronous optical network tcp transmission control protocol the terms “ routing devices ” and “ route ” are used throughout this application , in the claims as well as in the specification . the terms as used herein are intended to be genus terms that include the conventional routers and conventional routing , as well as all other variations of network trafficking , such as , switches or switching , gateways , hubs and the like . thus , unless particularized , the terms are to be given this broader meaning . various operations will be described as multiple discrete steps in turn , in a manner that is most helpful in understanding the present invention , however , the order of description should not be construed as to imply that these operations are necessarily order dependent . in particular , these operations need not be performed in the order of presentation . further , the description repeatedly uses the phrase “ in one embodiment ”, which ordinarily does not refer to the same embodiment , although it may . referring now to fig1 wherein a block diagram illustrating a network view of the present invention , in accordance with one embodiment , is shown . as illustrated , client devices 108 a - 108 n are coupled to servers 110 a - 110 n through networking fabric 112 , which includes a number of routing devices 106 a - 106 n coupled to each other forming a plurality of network links . client devices 108 a - 108 n , via routing devices 106 a - 106 n , or more specifically , over the network links formed by routing devices 106 a - 106 n , selectively access servers 110 a - 110 n for services . unfortunately , as those skilled in the art would appreciate , the same network links that make servers 110 a - 110 n readily accessible to client devices 108 a - 108 n also render them vulnerable to abuse or misuse by one or more of client devices 108 a - 108 n . for example , one or more client devices 108 a - 108 n may individually or in combination launch an attack , such as a denial of service attack , or otherwise victimize one or more servers 110 a - 110 n , routing devices 106 a - 106 b and / or the links interconnected the elements . in accordance with the present invention , director 102 , complemented by a number of sensors 104 a - 104 n , are employed to detect and prevent such abuse or misuse of the network links , to be described more fully below . for the illustrated embodiment , sensors 104 a - 104 n are disposed in distributed locations . in alternate embodiments , some or all of sensors 104 a - 104 n may be integrally disposed with routing devices 106 a - 106 b . example network 112 represents a broad range of private as well as public networks or interconnected networks , such as an enterprise network of a multi - national corporation , or the internet . networking nodes , such as clients 108 a - 108 n and server 110 a - 110 n represent a broad range of these elements known in the art , including individual user machines , e - commerce sites , and the like . as alluded to earlier , routing devices 106 a - 106 n represent a broad range of network trafficking equipment , including but are not limited to conventional routers , switches , gateways , hubs and the like . while for ease of understanding , only one director 102 , and a handful each of network nodes , clients 108 a - 108 n and servers 110 a - 110 n , routing devices 106 a - 106 n and sensors 104 a - 104 n are included in the illustration , from the description to follow , those skilled in the art will appreciate that the present invention may be practiced with more than one director 102 as well as more or less network nodes , routing devices 106 a - 106 n and sensors 104 a - 104 n . in particular , the present invention may also be practiced with one or more directors 102 . when more than one director 102 is employed , each director 102 may be assigned responsibility for a subset of sensors 104 a - 104 n , and the directors 102 may relate to each other in a master / slave relationship , with one of the directors 102 serving as the “ master ” ( and the others as “ slave ”), or as peers to one another or organized into an hierarchy , to collective discharge the responsibilities described below . referring now also to fig2 wherein a method view of the present invention , in accordance with one embodiment is shown . as illustrated , for a network link of interest , e . g . a network link on a critical path to a server subscriber of the services offered by director 102 , director 102 activates an initial subset of sensors 104 a - 104 n to monitor and collect descriptive data for network traffic routed over the network link of interest and / or related links , block 202 . the selected ones of sensors 104 a - 104 n may monitor the routing devices 106 * that are directly responsible for routing traffic onto the network link of interest , that is the routing devices 106 * to which the network link of interest is directly attached , and / or monitoring the routing devices 106 * that are indirectly responsible for routing traffic onto the network link of interest , that is the routing devices 106 * are remotely disposed , however by virtue of the destination of the traffic being routed , the traffic will eventually be routed over the network link of interest . the selected ones of sensors 104 a - 104 n may also monitor related network links , which traffic patterns may be indicative of the nature of the network traffic being routed over the network link of interest . [ the asterisk employed in the afore description and the description to follow represents a “ wildcard ” portion for the reference , i . e . 106 * may be any one or more of 106 a through 106 n .] periodically , or on demand , director 102 receives from the activated sensors 106 * descriptive data associated with the traffic of interest , i . e . network traffic routed over the network link of interest and / or related network links , block 204 . in response , for the illustrated embodiment , director 102 determines whether the network link of interest is at least suspicious of being abused or misused , block 206 . in various implementations , director 102 performs one or more analyses , using the received descriptive data , to determine whether the network link of interest is at least suspicious of being abused or misused . the descriptive data provided and the analyses performed are interdependent on each other . the precise nature of the descriptive data provided and the interdependent analyses performed are application dependent , i . e . dependent on the type and / or protocol of the network , and / or interest of the service subscriber . examples of descriptive data include source addresses , destination addresses , packet types , packet sizes , volume of packets , and so forth . volume of packets as well as other description data may also be stratified by packet types , addresses , and other stratification criteria . if it is determined that the network link of interest is at least suspicious of being abused or misused , director 102 further determines whether additional monitoring or data collection are needed before definitively concluding that the network link of interest is being misused , and imposes selective regulations to impact on network traffic accordingly , block 208 . if additional monitoring or data collection is “ preferred ”, director 102 launches additional selected ones of sensors 104 a - 104 n to perform the additional monitoring to collect additional data to confirm that indeed the network link of interest is being misused , i . e . returning to block 202 . if additional collection of data is not desired or eventually upon collection of additional data , director 102 becomes sufficiently confident that the network link of interest is being misused , at such time , director 102 determines the location or locations , and amount of regulations to impact on network traffic , to thwart the network link of interest from being misused , block 210 - 212 . back at block 206 , if director 102 is not at least suspicious of the network link of interest is being abused , director 102 further determines if any regulation is in effect , and if so , whether any of the regulation may be relaxed , block 214 . if not , the process continues back at block 204 , where director 102 receives additional report of descriptive data associated with the network traffic routed over the network link of interest and / or related links . from there , director conditionally repeats the earlier described analyses and related operations , blocks 206 - 214 . eventually , director 102 determines at block 214 that at least a portion of the regulation in effect may be relaxed . at such time , director 102 determines the location or locations of de - regulation , and the amount of de - regulation at the respective selected locations , block 216 - 218 . the above described method is repeated by director 102 periodically for each of the network links of interest . before proceeding to describe the present invention further , it should be noted that the phrase network link as used in the present application includes a virtual link as well as a physical link . a virtual link is a collection of physical links . when the network link is a virtual link , director 102 performs the analyses to be described based on the aggregated descriptive data of the corresponding physical links . further , distributed sensing and regulation of network traffic are the subject matters of co - pending u . s . patent applications , ser . no . 09 / 631 , 898 , entitled “ a distributed solution for regulating network traffic ”, filed on aug . 4 , 2000 , and ser . no . 09 / 685 , 518 , entitled “ progressive and distributed regulation of selected network traffic destined for a network node ”, filed on oct . 9 , 2000 , respectively . these applications are hereby fully incorporated by reference . continuing to refer to fig2 as described earlier , in response to the receipt of a new “ round ” or set of descriptive data associated with network traffic relevant to the network link of interest ( provided periodically or on demand ), director 102 performs one or more analyses in determining whether the network link of interest is at least suspicious of being misused . in one embodiment , director 102 determines whether a network link of interest is being misused by comparing the traffic pattern depicted by the provided descriptive data against a set of “ user - defined ” thresholds for a plurality of traffic pattern metrics . more specifically , director 102 concludes that the network link is at least suspicious of being misused if the traffic pattern metrics as measured by the received descriptive data exceed the “ user - defined ” thresholds . in this embodiment , the service subscriber quantitatively defines for director 102 the “ good ” traffic it expects on the network link of interest . the definition may be effectuated using any operational specification techniques known in the art . traffics exceeding the defined level are deemed to be “ suspicious ”. for example , a subscriber may define that a network link of interest is to have no more than 50 mb / s of dns traffic and 1 mb / s of tcp zone transfers . thus , if director 102 receives reporting from sensors 104 * that infer a high volume of traffic for either one of these metrics , director 102 will at least deem the traffic being routed over the network link of interest as suspicious , and increase monitoring . if the excessive pattern persists for a predetermined period , director 102 will deem the network link as being misused , and regulate it accordingly . in one embodiment focusing specifically on ip traffics , director 102 determines whether a network link of interest is being misused in accordance with whether unallocated ip addresses are present as source addresses of the traffic routed over the network link of interest . such presence is likely , as an attacker often uses randomly generated addresses as source addresses of the attack traffic . such randomly generated source addresses are likely to include source addresses that are unallocated . the allocated addresses may be pre - provided to director 102 ( e . g . in the form of a database ) or may be pre - determined by director 102 by systematically pinging trial addresses for responses ( and saving the responded ip addresses in a database ). in one embodiment , director 102 determines whether a network link of interest is being misused in accordance with the distribution profile of the source addresses of the network traffic routed over the network link of interest . more specifically , director 102 considers the network link of interest is at least suspicious of being misused if the source addresses of the network traffic routed over the network link of interest are evenly layered on top of the normal traffic pattern , which typically involves only a relatively small subset of source addresses . such characteristic is likely , as an attacker tends to use randomly generated addresses as source addresses of the attack traffic . such randomly generated source addresses tend to evenly distributed . any one of a number of statistical techniques known in the art may be employed to perform the above described distribution profile analysis . in one embodiment , director 102 determines whether a network link of interest is being misused in accordance with the number and type of packets being sent to a network node or set of nodes from the same source address . more specifically , director 102 considers the network link of interest is at least suspicious of being misused if the number of packets being sent to a network node or set of nodes from the same source address for certain type of packets exceeds a predetermined small threshold . such characteristic is likely in situations where certain servers , such as domain name servers , are being used to launch attack packets against a victim server . in one embodiment , director 102 determines whether a network link of interest is being misused in accordance with the burstiness characteristics of the network traffic routed over the network link of interest , more specifically , the lack thereof . such lack of burstiness characteristic is likely in traffic intensity , intensity per subnet , packet sizes , and / or number of packets per flow , if the traffics routed are attack traffic as opposed to normal traffic . similarly , any one of a number of statistical techniques known in the art may be employed to perform the above described burstiness analysis . in one embodiment , director 102 determines whether a network link of interest is being misused in accordance with a ratio of the packets flowing in one direction to packets flowing in the opposite direction . more specifically , director 102 considers the network link of interest is at least suspicious of being misused if the ratio is imbalanced , i . e . more than a predetermined threshold deviated from the numeric constant “ 1 ”. again such uneven characteristic between the two directions is likely when the network traffics routed are attack traffic as opposed to normal network traffic . in one embodiment , director 102 determines whether a network link of interest is being misused in accordance with a ratio of a first packet type to a second packet type . more specifically , director 102 considers the network link of interest is at least suspicious of being misused if the ratio is imbalanced , i . e . more than a predetermined threshold deviated from a target ratio . such uneven characteristic between the selected pairs of packet types may be indicative of attack traffic . for example , in the case of tcp / ip , during normal operation , tcp ack packets should be about half of data packets . if the ratio is substantially different from the target ratio of 0 . 5 , it is likely the abnormal traffics are attack traffic . in one embodiment , director 102 determines whether a network link of interest is being misused in accordance with response traffics . more specifically , director 102 considers the network link of interest is at least suspicious of being misused if an excess amount of the traffic being routed is recognizable error packets . for example , in the case of tcp / ip traffic , if an excessive amount of rst packets are being routed , which may be indicative of an excess amount of ack packets being sent without the corresponding syn packets . when multiple analyses are employed for the decision making process , a weighted approach may be employed to give different weights to the results of the different analyses in their contributions towards the ultimate conclusion as to whether a network link of interest is at least suspicious of being misused . in alternate embodiment , a more sophisticated modeling approach may be employed instead . that is , the results of the analyses are provided as inputs to the model that models the expected normal behavior of the network links of interest , and predicts whether abnormal behavior are about to occur or occurring . referring back to fig1 as described earlier , sensors 104 a - 104 n are employed to monitor and collect descriptive data associated with network traffic routed over the network links of interest . as described in the incorporated by reference application , sensors 104 a - 104 n may be externally disposed and correspondingly coupled to and monitor routing devices 106 a - 106 n . alternatively , sensors 104 a - 104 n may individually or collectively monitor and report on the network traffic routed through more than one routing device , as opposed to the corresponding configuration . in yet other embodiments , some or all of sensors 104 a - 104 n may be integrally disposed within routing devices 106 a - 106 h instead . sensors 104 a - 104 n , whether externally disposed or integrally disposed , may be coupled to director 102 using any one of a number of communication links known in the art , such as modem links over conventional phone lines , digital subscriber lines ( dsl ), integrated service digital network ( isdn ) connections , asynchronous transfer mode ( asm ) links , frame relay connections , and the like . in one embodiment , sensors 104 a - 104 n use an access control list ( acl ), and commands associated therewith , such as “ access - list ” and “ show access - list ” to gather up the relevant data . similarly , in one embodiment , sensors 104 a - 104 n use interface related commands such as “ show interface rate - limit ” and “ rate - limit ” to regulate and de - regulate an interface . these commands , including their operations and constitutions , are known in the art . see product literatures from routing device manufacturers , such as cisco systems , inc of san jose , calif . in alternate embodiments , for certain routing devices , if supported , the relevant data gathered may also include “ netflow ” data . in other embodiments , the relevant data may also be obtained through known network management services , such as simple network management protocol ( snmp ), remote monitoring ( rmon ), port mirroring , or packet sampling ( if one or more of these service are supported by the routing devices ). for further details , refer to the specification of incorporated by reference application ser . no . 09 / 631 , 898 . referring now to fig3 wherein a functional view of the director , in accordance with one embodiment is shown . as illustrated , director 102 includes send / receive function 302 , analyzer 304 , and regulator 306 , operatively coupled to each other as shown . send / receive function 302 is employed to receive network traffic data ( e . g . reported by the distributively disposed sensors ), and to send monitor instructions to the sensing devices as well as regulation / de - regulation instructions to the routing devices to be regulated ( e . g . through the distributively disposed sensors ). analyzer 304 analyzes the network traffic data reported to determine if a network link of interest is at least suspicious of being misused , and alerts regulator 306 accordingly . regulator 306 is used to determine where and the specific regulation / de - regulation actions to be taken . fig4 - 6 illustrate the operational flow of the relevant aspects of the send / receive , analyzer and regulation functions 302 - 306 , in accordance with one embodiment each . as illustrated in fig4 for the send / receive function , upon start up , it determines if there are network traffic data to be received ( e . g . from the distributively disposed sensors ), block 402 . if there are , send / receive function 302 receives the network traffic data being reported accordingly . if there are not , send / receive function 302 determines if there are monitor or regulation / de - regulation instructions to be sent ( e . g . to the distributively disposed sensors ). if there are , send / receive function 302 sends the monitor or regulation / regulation instructions accordingly . if there are not , send / receive function 302 returns to block 402 to determine if there are data to be received again . as illustrated in fig5 upon start up , analyzer 304 selects a network link of interest to be analyzed , block 502 . analyzer 304 analyzes the received descriptive data , performing one or more of the earlier described analyses , block 504 . based on the results of the analysis , analyzer 304 determines if more data or to be collected , in particular , whether additional sensors 104 * are to be activated for the additional collection of network traffic data , block 506 . if additional sensors 104 * are to be activated for the additional collection of network traffic data , analyzer 304 selects and activates selected ones of the sensors accordingly , block 508 . if sufficient number of sensors 104 * have been activated for the additional collection of network traffic data , analyzer 304 further determines if network traffic are to be regulated , further regulated or de - regulated , block 510 . if not , analyzer 304 returns to block 504 , and continues operation from there . if network traffic is to be regulated , further regulated or de - regulated , analyzer 304 notifies regulator 306 accordingly , block 512 . analyzer 304 repeats this process for each network link of interest to be “ protected ” from misuse . as illustrated in fig6 upon receipt of an alert , regulator 306 determines if the alert is for ( further ) regulation or de - regulation , block 602 . if the alert is for ( further ) regulation , regulator 306 determines the routing devices to be regulated , block 606 . further , regulator 306 determines the regulation to be applied , block 608 . examples of regulations include but are not limited to bandwidth allocation , rate limiting , packet filtering , giving priority to “ good ” traffics , and so forth . note that the regulations may negatively impact the “ good ” traffics , because as long as the “ bad ” traffics are more negatively impacted , the regulations would still be useful to “ good ” traffics . upon making these determinations , regulator 306 provides the regulation instructions to the routing devices to be regulated accordingly ( e . g . through the sensors ), block 614 . on the other hand , if the alert is for de - regulation , regulator 306 determines the location or locations for de - regulation , 610 . further , regulator 306 determines the level of de - regulation ( bandwidth restoration , rate limit relaxation etc . ), block 612 . upon making these determinations , regulator 306 provides the de - regulation instructions to the routing devices to be de - regulated accordingly ( e . g . through the sensors ), block 614 . in one embodiment , regulator 306 regulates and de - regulates in a progressive manner as described in incorporated by reference application ser . no . 09 / 685 , 518 . [ 0052 ] fig7 illustrates an example computer system suitable for use as either a host to a software implementation of a sensor , or the director in accordance with one embodiment . as shown , computer system 700 includes one or more processors 702 ( typically depending on whether it is used as host to sensor or the director ), and system memory 704 . additionally , computer system 700 includes mass storage devices 706 ( such as diskette , hard drive , cdrom and so forth ), input / output devices 708 ( such as keyboard , cursor control and so forth ) and communication interfaces 710 ( such as network interface cards , modems and so forth ). the elements are coupled to each other via system bus 712 , which represents one or more buses . in the case of multiple buses , they are bridged by one or more bus bridges ( not shown ). each of these elements performs its conventional functions known in the art . in particular , system memory 704 and mass storage 706 are employed to store a working copy and a permanent copy of the programming instructions implementing the sensor and / or director teachings of the present invention . the permanent copy of the programming instructions may be loaded into mass storage 706 in the factory , or in the field , as described earlier , through a distribution medium ( not shown ) or through communication interface 710 ( from a distribution server ( not shown ). the constitution of these elements 702 - 712 are known , and accordingly will not be further described . thus , it can be seen from the above descriptions , a novel method and apparatus for detecting misuse of a network has been described . the novel scheme decrease the likelihood of the network links being misused to launch attacks or otherwise victimize a server node or a set of server nodes . while the present invention has been described referencing the illustrated and above enumerated embodiments , the present invention is not limited to these described embodiments . numerous modification and alterations may be made , consistent with the scope of the present invention as set forth in the claims to follow . thus , the above described embodiments are merely illustrative , and not restrictive on the present invention . | 7 |
fig1 shows a cross sectional view of an embodiment of the invention for scanned fluorescence microscopy . u . s . pat . nos . 5 , 777 , 342 , 5 , 866 , 911 , 5 , 952 , 668 and 6 , 259 , 104 contain useful background to the following discussion , and are incorporated herein by reference . light from a femtosecond pulsed titanium - sapphire laser is directed on rotatable half - wave plate 1 , and the emerging beam is directed onto a polarizing beamsplitter 2 . beam 3 , which is one of the beams emerging from the beam splitter 2 will be used for multiphoton excitation . beam 3 is directed onto a chromatic dispersion compensating assembly , as discussed in u . s . pat . no . 6 , 178 , 041 , the disclosures of which are hereby incorporated by reference , consisting of four diffraction gratings 4 , 5 , 6 and 7 . the beam emerging from grating 7 is focused by lens 8 onto one end of an optical fiber 9 , which conducts the light to the scan head 10 . negative chromatic dispersion produced by the gratings 4 , 5 , 6 and 7 compensate for positive dispersion in the fiber 9 , so as to maintain a short pulse width in the pulse directed on the specimen , as discussed in u . s . pat . no . 6 , 178 , 041 . within the scan head 10 , light leaving the exit end of fiber 9 is collimated by lens 11 and reflected by mirror 12 ( which may be a dichroic beam splitter ) onto scanning means 13 and then , onto objective 14 , which focuses the excitation pulse into a spot in specimen 15 . beam 3 ′ emerging from beamsplitter 2 will be used to produce the quenching beam . beam 3 ′ is directed successively to mirrors 16 and 17 , the position of which can be moved in the direction of the axis of the beam 3 ′ to induce a variable path length , and thereby change the time delay between the offset of the excitation pulse and the onset of the quenching pulse . the beam emerging from mirror 17 is reflected by mirror 18 to an assembly consisting of four diffraction gratings 19 , 20 , 21 and 22 that apply negative chromatic dispersion , and the beam emerging from grating 22 is focused by lens 23 onto the end of optical fiber 24 . the negative dispersion produced by the assembly of gratings 19 , 20 , 21 and 22 is greater or smaller than the positive dispersion introduced by fiber 24 , so that the pulse experiences a net stretching . as an alternative , the gratings 19 , 20 , 21 and 22 could be put in a configuration that produces positive dispersion . the stretched pulse conducted by fiber 24 is split by a fiber optical 1 : 4 splitter 25 equally into four fibers . the light emerging from these fibers 26 , 27 , 28 and 29 is collimated by four identical lenses , of which only lenses 30 and 30 ′ are in the plane of this drawing and are shown . the beam emerging from lens 30 is reflected by mirror 31 onto lens 32 , and the converging beam leaving lens 32 enters equilateral prism 33 where it experiences total internal reflection to be directed parallel to the axis of the cone of excitation light emerging from the end of fiber 9 , and it is focused to a spot in the same plane as the end of fiber 9 . the ends of fibers 27 , 28 and 29 also are focused to spots of light in this same plane , so that the spots are at the corners of a square with the tip of fiber 9 at the center . fig2 shows a detail of the passage of rays of quenching light in prism 33 . the rays would form an image of the end of fiber 26 at plane 40 , but total internal reflection from prism face 41 causes the image instead to be formed at position 42 , adjacent to a chisel edge 43 of the prism . fig3 shows a three - dimensional perspective view of different positions of prisms such as prism 33 , showing the chisel edge 43 . each of these prisms could be made by placing them so one face is horizontal , and making two cuts at 45 ° to the edges of the horizontal face , so the cuts almost touch , producing the chisel edge 43 . when four of such prisms are positioned on a horizontal surface so that these four chisel edges , such as edge 43 , make the sides of a square , then they will be in the relative positions required in the device shown in fig1 . the magnified detail of fig1 shown in fig4 , shows how the end of fiber 9 can be tapered , by gradually removing the cladding , so at the tip only the core plus the minimum cladding needed to maintain propagation remains , and this tip just fits into this square , the edges of which are the chisel edges , such as edge 43 . fig5 , shows a plan view , such that the plane of the figure is parallel to the real image plane containing the tip 44 of fiber 9 , and the spot images 45 , 46 , 47 and 48 of the ends of fibers 26 , 27 , 28 and 29 . fig5 shows the relationship between these spot images and the tip of excitation fiber 9 . lenses 11 and 13 and mirror 12 reimage these spot images 45 , 46 , 47 and 48 to the real image plane of the specimen 15 , such that these reimaged spot images in the specimen are at the corners of a square . the reimaged spots diagonally opposite each other have a 180 ° phase difference , so that the light exactly cancels at the central point of the square , which is also the central point that the tip of fiber 9 that is imaged to in the specimen . this phase adjustment can be made , for example , by axially moving fiber 26 with respect to fiber 29 , until the desired cancellation is produced . as discussed in the cited references , it is important that light from one pair of diagonally opposite reimaged spot images does not interfere with light from the remaining pair . one way that this can be accomplished , as discussed for example in u . s . pat . no . 6 , 259 , 104 , is to make the phase relationship between adjacent pairs of reimaged spot images have a 90 ° phase difference , and again the required phase relationships can be produced by axially moving the tips of the fibers 26 , 27 , 28 and 29 relative to each other . the resulting phase can be described as adding 90 ° of phase shift as one moves clockwise in the plane of focus of the specimen from each of the four reimaged spot images to the next one . the cited references describe other ways of providing that light from opposite reimaged spot images cancels but light from one of these opposite pairs cannot interfere with light from the remaining pair . the dimensions are chosen so that the distance between the centers of the reimaged spot images and the center of the image in the specimen of the tip of fiber 9 is about 2 . 3 dimensionless optical units ( a separation of one optical unit equals the inverse of the product of numerical aperture of the objective lens and the wavevector k = 2π / λ ). this geometry will produce a doughnut shaped intensity distribution in the real image plane of the specimen , with a theoretically zero intensity central spot , and where the intensity rises rapidly with distance from that central point . the styryl dye rh414 appears suitable for multiphoton excitation and for quenching at the same wavelength , in this case 760 nm . the paper by dyba and hell ( appl . optics . 42 : 5123 ( 03 )) shows that light of this wavelength will lead to multiphoton fluorescent excitation . an earlier paper by the same authors ( phys . rev . lett . 88 : 163902 ( 02 )) showed that the same dye was susceptible to sted quenching by light around the same wavelength . there are other possible candidate dyes including did , and it appears possible that the ability to be multiphoton excited and quenched by light of the same wavelength will turn out to be a relatively common property of dyes , not presently known only because it has not been looked for . the above discussion has not dealt with the issues of measurement of light emitting from the excited spot , and creation of an image based on scanning of the excited spot . that is because the process is the same as in well known confocal ( e . g . baer , u . s . pat . no . 3 , 705 , 755 ), multiphoton ( e . g . denk et al , u . s . pat . no . 5 , 034 , 613 , the disclosures of which are hereby incorporated by reference ) and the already cited sted patents . as in multiphoton and sted imaging , the light emanating from the excited spot can either be descanned and imaged on a confocal pinhole , or imaged on a detector without descanning or passage through a confocal pinhole , for greater collection efficiency . many alternative methods have been described for producing a sculpting beam with the required zero intensity central point ( or line , in the case of line scanning microscopes ) and any of these could be applied to the present invention , provided the wavelength of the sculpting beam was the same as the excitation wavelength . although the preceding description described a fiber to couple the excitation laser to the microscope scan head , the present invention would also be applicable in instruments where the path between the laser and the scan head did not involve passage through an optical fiber . the same principle of multiphoton excitation and quenching by a lengthened pulse of the same wavelength could be used for scanned beam microlithography and microfabrication . for microlithography , the goal is to quench the peripheral parts of an excited spot in the photosensitive film or emulsion layer , before they have lead to the lasting change . the two - photon - activatable photoacid generator molecule , bsb — s 2 , has been used for two - photon microfabrication ( zhou et al science 296 : 1106 ( 02 )) using light of 705 to 800 nm . this substance also has a relatively long lived singlet state that might be susceptible to single - photon - induced quenching in this general wavelength range , and also has a sufficiently long lived excited singlet state , that quenching should be possible before the acid triggering the lasting change is released . the device of fig1 allows a common wavelength to be used both for excitation and for reducing the excitation in the peripheral parts of the excited spot or line . however because the axial positions of the fibers 26 , 27 , 28 and 29 must be adjusted to create phase differences of 90 °, 180 °, and 270 ° and because the particular distance to create these phases is proportional to the wavelength , the fibers must be repositioned whenever that common wavelength is changed . the device shown in fig6 creates phase differences that do not require mechanical readjustment when the wavelength is changed , and for that reason is a more preferred embodiment of the present invention . those elements in fig6 that are identical to elements in fig1 have been given the same reference numerals . there are some differences . for example , in fig1 , the transmitted component 3 from beam splitter was passed through a chromatic dispersion means and then conducted by an optical fiber in its passage to the scan head 10 . in the device of fig6 , in contrast , there is no intervening optical fiber , and consequently there is no need for the chromatic dispersion means which is required in the fig1 device to compensate for the opposite chromatic dispersion of the fiber , to maintain the short excitation pulse width . the excitation beam instead is conducted by mirrors 51 and 52 , passed through a small transparent hole in segmented mirror 54 , which will be explained more fully in the next paragraph , and focused by lenses 53 and 55 onto the real image plane 33 . the system of conduction by a fiber and compensation by a chromatic dispersion means , as shown in fig1 , has reportedly been found to be difficult to adjust , and so a light conduction method such as shown in fig6 , avoiding such a fiber would probably be preferable in a system where the common wavelength is adjustable . the excitation - reducing beam in the fig6 device , which as in the fig1 device is formed from the reflected output 3 ′ from beam splitter 2 , is passed through the same chromatic dispersion means and optical fiber as in the fig1 device . after collimation by lens 56 , the beam is directed onto a hollow pyramid 57 , which separates the beam into four quarter - pie - shaped segments 58 , 59 , 60 and 61 , separated by a non - illuminated x - shaped region , as shown in fig7 . pyramid 57 is made of four triangles of a transparent material such as glass , with parallel faces , and edges beveled to fill the space at edges where the triangles touch . the cross - sectional plane of fig6 bisects two opposite triangles of pyramid 57 each of the pie - shaped segments of the beam is directed to a separate segment of segmented mirror 54 , shown schematically in fig8 , with an exaggerated spacing between the segments . the central hole 64 of the segmented mirror is formed by making a small bevel at the right angle vertices of each of the four mirror segments . beam segment 58 for example would be directed on mirror segment 62 and beam segment 60 would be directed on mirror segment 63 . the segmented mirror 54 reflects the beam segments onto lens 55 , which forms a real image of the segmented mirror and its central hole on real image plane 33 . therefore an image of the central spot of the excitation beam is formed at plane 33 , surrounded by images of the four beam segments . fig6 is meant to show the relationship between the elements but not their relative sizes . the elements should be arranged so that the images in the plane of focus of the specimen of the “ intensity - weighted central point ” of the beam segments at plane 33 are about 2 . 3 optical units from the center of the excitation spot . the “ intensity - weighted central point ,” roughly speaking , would be the center of mass of a flat piece of pie that had a mass per unit area at each point proportional to the light intensity of the pie shaped segment . as shown in fig9 , which is a magnified detail of fig6 to better show pyramid 57 , the pyramid can rotate about a point 70 , which is the interior vertex point . pyramid 57 can rotate through small angles on two perpendicular axes of rotation , both of them perpendicular to the optical axis , and one of them perpendicular to the plane of fig6 and 9 . it will be appreciated from fig9 that if the pyramid rotates a small angle on the axis perpendicular to the figure , that the angle of incidence of the collimated beam from lens 56 will increase on one pyramid face and decrease on other . because of snell &# 39 ; s law , the angle of refraction will also change , so that after the rotation , the distance the beam travels through the glass of face 71 will be different from the distance the opposite beam travels through face 72 , which will create a phase difference between the beams , that increases with the tilt of the pyramid . for any chosen phase difference , for example the 180 ° phase difference required for the spots of excitation - reducing light on opposite sides of the central spot of excitation , and for any chosen wavelength , whatever relative delay between the opposite faces that is produced by tilting of the pyramid to an arbitrary angle , there is a compensatory translation of the segments of segmented mirror , that when combined with the delay caused by mirror rotation ( which at a very small angle approximates translation ), will restore the net delay to create a 180 ° phase difference . it is possible to imagine a graph where the relative delay caused by the pyramid tilt is plotted on one axis and the compensatory movement of the mirror segments to make the net phase difference 180 ° is plotted on the other axis . the resulting graph will be a sloping line . a change of wavelength of the beam will change the speed of light through the glass , and consequently change the slope such a plotted line . because they have different slopes , the lines corresponding to two chosen wavelengths will intersect at some point . the coordinates of this intersection point indicates a pair of relative delays caused by pyramid tilt and by mirror segment adjustment , such that the net delay is 180 ° for both of these wavelengths . if the pyramid is tilted at the angle needed to produce such a delay and the mirror segments are set at the corresponding positions , not only will the phase delay be exactly 180 ° for both of the chosen wavelengths ( which are chosen to bracket the wavelength band desired for the quenching light ), but additionally it will be nearly 180 ° for all the wavelengths in between . this is the well - known principle of achromatic correction , and it is particularly simple to implement in this case . the result is that not only is the arrangement of fig6 simpler than the arrangement of fig1 , but it also is substantially achromatic for phase delay . it should be understood that to calibrate this system , three separate degrees of freedom are required to produce the required phase delays , but rotation of the pyramid only provides two such degrees of freedom . one possible solution is to cement three of the four triangular faces together , and allow the fourth face to pivot about the common vertex point 70 . it is possible to perform such a calibration of the delays during fabrication of the pyramid , and then in use , the two available degrees of freedom could be used for fine adjustment . in addition to allowing the common wavelength to be changed without need to recalibrate the phase adjustments , an achromatic scheme also insures that when the pulses are spectrally broadened as a side effect of pulse compression and stretching , that each spectral component in the broadened pulse has the same phase delay , and consequence they each form a zero intensity point at the central point . even in a fixed wavelength instrument , this may contribute to a slight improvement in resolution . although this disclosure has described single wavelength sted microscopy with just one illustrative sted microscope design , it will be obvious to one skilled in the art that provided a suitable fluorophore or photosensitizer is used , that the present invention could be applied to nearly any of the many other designs for sted and sted - like microscopes or microlithography exposure tools described in the cited references , including but not limited to devices with multiple simultaneously imaged spots , and a line - shaped rather than spot - shaped area subject to resolution enhancement , and to devices still to be proposed . the breadth of the present invention should not be limited by the particular illustrative examples but rather by the following claims . | 6 |
turning now to the drawings , fig1 is a functional block diagram illustrating a language skills teaching system 10 embodying the present invention . a student learning a target language and a native speaker of the language communicate in the language with respective communication devices 12 , 14 . preferably , communication devices 12 , 14 are personal computers or communication terminals , but they may be any type of communication devices , such as a smart telephone or al pda . preferably , communication is verbal , so communication devices 12 , 14 will include some form of microphone and means for playing an audible signal . the student &# 39 ; s terminal 12 communicates with the native speaker &# 39 ; s terminal 14 by sending thereto a verbal communication in the target language from the student . the native speaker responds , in the target language , and his response is stored in a buffer 16 . the native speaker &# 39 ; s response is also provided to a monitor 18 , which isolates language elements like vocabulary words and grammatical structures from his response and provides them to a query generator 20 . query generator 20 then formulates an appropriate query for a database manager 22 which contains the student &# 39 ; s database , representing his skill in the target language . query generation and database management are well known technologies . similarly , the use of speech recognition used to convert speech to text for use by the database is a well known technology . the student &# 39 ; s database contains a current description of the student &# 39 ; s ability in the target language . it may include the complete vocabulary known by the student and a complete description of his ability in the target language . such a database could be derived from a computerized teaching machine being used by the student to learn the target language . such a system is described in copending application ser . no . 12 / 052 , 435 , owned by the assignee of the present invention , and the contents of which are hereby fully incorporated by reference . alternately , the description may simply include a vocabulary level indicator for the target language , and the query could then be directed to a central database containing the entire vocabulary for that level . in either event , the query containing the words in the native speaker &# 39 ; s response is addressed to the database , and a determination is made whether the student should understand all of the words in the query . those skilled in the art will appreciate that further levels of sophistication may be incorporated within the query . for example , the query could include a description of the sentence structure of the native speaker &# 39 ; s response , and the database could include a description of the sentence structures understood by the student . it would then be possible to determine whether or not , apart from the vocabulary , the student would understand the sentence structure . tense and grammatical form can also be processed in a similar manner . similarly , the database could include information regarding words that the student will be learning soon , so a determination could be made whether it might be beneficial for the student to be exposed to such words . in such a case , an image or other hind can be given to the student , which image or hint would not be given if the words used were already known to the student . in response to the query , database manager 22 provides a response to a controller 24 related to the last query . the response might be a simple indication that the words of the query are all within the vocabulary understood by the student in the target language . in that case , controller 24 enables buffer 16 to transmit the native speaker &# 39 ; s response to the student &# 39 ; s terminal 12 . on the other hand , the response provided to the controller 24 might indicate that one or more words in the query or sentence structure are too sophisticated for the student . the response might also include words understood by the student which could be substituted for words in the query . controller 24 would then cause a message generator 26 to generate an appropriate message on the native speaker &# 39 ; s communication device 14 . the message would inform the native speaker that his response is too complex and suggest an alternate response . the native speaker could then provide the alternate response , which is stored in buffer 16 in place of the original response . he then provides an indication to his terminal that an alternate response has been provided , and his terminal enables the new message in buffer 16 to be sent to the student &# 39 ; s communication device 12 . alternatively , the alternate response could be generated and sent to the student &# 39 ; s communication device 12 automatically . it would be preferable , however , to provide some delay before the alternate response is sent , in order to give the native speaker the opportunity to cancel its transmission . further levels of sophistication could be built into controller 24 . for example , should the response from the database manager 22 indicate that the student does not know one of the words in the query but will be learning it soon , controller 24 could enable the message in buffer 16 to be sent to the students communicational terminal and could simultaneously cause a message generator 28 to send an appropriate message to the student &# 39 ; s communication device 12 . that message could include a definition of the unknown word or , more preferably , a descriptive graphic for the word . it is also contemplated that the message could include an excerpt from a future lesson in which the unknown word or words are taught . a further level of sophistication that could be added in a system involving spoken communication would be to provide voice transformation technology in the student &# 39 ; s computing device . software and devices which perform voice transformation are well known . such technology can speed up or slow down speech without changing the sound of the voice . thus , by entering a code or clicking on an area of a display screen of his computing device the student may slow down the native speaker &# 39 ; s voice until he understands what is being said . preferably , a message would be sent to the native speaker when the student performs this action , in order to notify him that he needs to slow down his speech . as a further level of sophistication , the voice transformer could retain the slower version of the native speaker &# 39 ; s speech after the student has slowed it down a predetermined number of times within a predetermined interval of time . message generators 26 and 28 could have a fixed set of messages , with controller 24 indicating the message to be sent and the content to be inserted . fig2 is a flow chart illustrating the operation of controller 24 . in block 100 , controller 24 awaits a response from database manager 22 and , upon receiving the response , transfers control to block 102 . at block 102 , a test is performed to determine if the response from database manager 22 indicates that all words in the query are known by the student . if so , transmission of the message in buffer 16 is enabled at block 104 , and control returns to block 100 , where receipt of further responses awaited . should the test at block 102 indicate that all of the words in the query were not known by the student , a further test is performed at block 106 to determine if any of the unknown words will be learned soon by the student . if not , control transfers to block 108 , where message generator 26 is caused to generate a message to the native speaker suggesting an alternate response . should the test at block 106 indicate that one or more of the unknown words will be learned by the students soon , control transfers to block 110 where message generator 28 is caused to generate a message to the student defining those words . a test is then performed at block 112 to determine whether all of the unknown words are among those soon to be learned . if so , control transfers to block 104 , where transmission of the message stored in buffer 16 is enabled . if not , control transfers to block 108 for generation of a message to the native speaker and , ultimately , return to block 100 to await receipt of a further response from the database manager . in accordance with an aspect of the present invention , it is contemplated that the native speaker be provided with training and support . fig3 is a block diagram of a preferred training and support module 40 that will achieve this . preferably , this module is provided on the native speaker &# 39 ; s computing device 14 or made accessible to it , such as through a network connection . module 40 includes a speech recognition engine ( sre ) 42 which is preferably part of monitor 18 . sre 42 senses the native speaker &# 39 ; s speech and converts it to text or some other processable form , for communication of information to query generator 20 . a whisper assistant 44 and a presentation module 46 are enhancements to message generator 26 . whisper assistant 44 provides spoken communications , preferably synthesized , to the native speaker in his own language . that is , the communications provided by message generator 26 are presented to the native speaker as spoken messages . similarly , presentation module 46 can present messages in the form of various types of presentations on the screen of the native speaker &# 39 ; s computing device . a training enabler 48 provided in the native speaker &# 39 ; s computing device will place it into a training mode . that is , without receiving any communications from the student &# 39 ; s computing device 12 , the native speaker is enabled to carry on his side of the communication . training enabler 48 could , for example , present prerecorded “ communications ” as if they came from a student , and the native speaker could provide his own responses . system 10 would operate as explained above , monitoring the native speaker &# 39 ; s communications and sending appropriate messages . in the present instance , the messages may also be verbal , via whisperer assistant 44 or a presentation provided via module 46 . those skilled in the art will appreciate that , although fig3 shows sre 42 communicating functionally with whisperer assistant 44 and presentation module 46 , those communications are actually provided through system 10 as described previously . that is , the native speaker &# 39 ; s communications are actually compared against the student &# 39 ; s database and controller 24 causes communications with the native speaker as if he were actually communicating with the student . thus , in preparation for a session with the student , the native speaker is able to get training just as if he were communicating with the student . it is , however , contemplated that a collection of “ standard ” databases would be available to the native speaker . he would merely need to select the level of skill of the student ( for example “ 8 th grade ”) and the system would provide training at that level . this would be particularly useful in a non - teaching environment , such as in business communications . the native speaker need merely estimate the level of skill of the other person , and he would then receive appropriate training . those skilled in the art will appreciate that this type of training could be free - standing , in that it all components could be incorporated into the native speaker &# 39 ; s computing device . whisperer assistant 44 could provide a spoken version of messages that would normally be presented by message generator 26 . for example , it could tell the native speaker when he needed to slow down his rate of speech , or it cold suggest words or phrases for substitution in his communication . presentation module 46 is capable of presenting a collection of available presentation modules on the display in the native speaker &# 39 ; s computing device . for example , it could display any kind of window , including one with an image or audio . it could also display parallel columns 52 , for example , one column showing the native speaker &# 39 ; s communication and the other showing a recommended , modified form . it could also show topic clouds 54 with such topics as “ food ”, “ family ”, or “ hobbies .” the native speaker could click on this and be presented with appropriate vocabulary to be used with the student . among the topic clouds , there could also be a “ browse ” cloud permitting the native speaker to browse for appropriate topics . the presentation module might also present a series of tiles 56 on the screen of the native speaker &# 39 ; s computing device . it will be appreciated that with the flexibility provided to train the native speaker , he could become a “ specialist ” in a very short time . for example , he could specialize in students at a certain level , or he could quickly learn the language associated with a particular line of business . those skilled in the art will appreciate that it would also be beneficial to provide the whisperer assistant 44 and presentation module 46 during actual communications with a student and not limit them to use during training . above , there has been a description of the present invention as embodied in a teaching system . however , those skilled in the art will appreciate that the utility of the present invention is not so limited . it would be useful in any instance in which a higher skilled person in a target language needs to communicate with a lesser skilled person in the language . for example , suppose an english speaker needs must carry out a business communication with a foreign individual whose ability in english is limited . use of the present invention would facilitate communication between these two individuals . it would only be necessary to select the english level of skill for the foreign individual . this could be built in as an adjustment in the english speaker &# 39 ; s communication device . for example , he could be offered a selection of a fifth - grade , eighth - grade or high school level of english proficiency , and he could then commence a verbal communication with the foreign individual at that level . if he suspects a communication is not going well . he could always adjust the level while carrying on the communication . it will also be appreciated that the present invention is not limited to use with verbal communications . it could prove very valuable for written communications , as well . although preferred embodiments of the invention have been disclosed for illustrative purposes , those skilled in the art will appreciate that many additions , modifications , and substitutions are possible without departing from the scope and spirit of the invention as defined by the accompanying claims . | 6 |
a description of the preferred embodiments of the present invention will now be presented with reference to fig1 – 9 . an inductively coupled argon plasma atomic emission spectrometer ( icp - aes ) was equipped and set up as follows : leeman 1000 , power 1 . 9 kw , coolant 13 lpm , nebulizer 46 psi , aux . flow 0 . 20 , pump rate 0 . 9 ml / min , scan integration time 0 . 25 sec , integrations 2 , uptake time 29 sec , mn1 peaking wavelength , acid flexible tubing 0 . 030 id mm , wavelengths and background corrections given in anderson ( 1996 ). the temperature controller / digester used was a digestion system 40 , 1016 digester , and autostep 1012 controller ( tecator , sweden ), fitted with an aluminum adapter plate 3 mm thick with 40 17 - mm holes on top overlaid on the heater block . in another embodiment , inductively coupled plasma - optical emission spectrometry ( icp - oes ) may be used for the determination of multiple metal concentrations in the part - per - million to the upper part - per - billion range . this method can quantify 14 – 18 elements that are useful predictors of geographic origin . in what is currently believed to be a best mode of the present invention , inductively coupled plasma - mass spectrometry ( icp - ms ) is used to determine metal concentrations in the low part - per - billion to upper part - per - trillion range . icp - ms utilizes a much more sensitive detector than the icp - oes and acquires a relatively clean mass spectrum , rather than the more complex and noisy emission spectrum of icp - oes . further , a lower signal - to - noise ratio leads to enhanced sensitivity , which allows quantification of several trace metals that are present at levels below the detection limits of icp - oes . this is an important consideration in geographic origin detection , since trace elements , rather than macro - elements , are more likely to uniquely identify a growing region . in a study comparing icp - oes to icp - ms analysis of approximately 400 potatoes , icp - ms was shown to provide reliable concentrations for an additional eight elements , cd , co , mo , ni , pb , v , ga , and se , that were not detectable by icp - oes . the source of chemicals and reference materials was as follows : concentrated , nitric acid trace metal analysis grade ( j . t . baker , st . louis , mo . ); elemental stock standards solutions ( j . t . baker , st . louis , mo . ); reference materials , nist 1575 pine needles , nist oyster tissue 1566a , nist rice flour 1568a , nist 1577b bovine liver , nist 8433 corn bran ( national institute of standards and technology , gaithersburg , md . ), nrc , tort - 2 lobster hepatopancreas ( national research council canada , institute national measurements standards ). sampling , preparation , and analysis : in order to ensure that only authentic samples with precisely known origin were used , samples were gathered by the idaho potato commission ( ipc ) or one of their delegates directly from farms or producer &# 39 ; s storage units . samples were shipped within days of collection with the chain - of - custody documentation to the university of idaho analytical sciences laboratory . samples were stored under controlled access at 4 ° c . until analysis , typically within two weeks . potatoes were collected from all major fresh market geographic locations in north america ( u . s . and canada ), based primarily on the number of acres in fresh potato production . idaho potatoes are grown primarily in the snake river plain , representing about 400 , 000 acres in current potato production . within this region , sub - regions were identified and 342 samples were collected from the following idaho locations : upper valley , magic valley , and treasure valley . non - idaho potatoes include samples taken from the following geographic locations : colorado , washington , maine , michigan , and canada ( prince edward island and new brunswick ). two hundred sixty - six non - idaho samples were collected . each tuber was hand rinsed under a stream of tap water for 20 – 30 seconds . dirt was removed by gently rubbing by hand under the water stream . after rinsing , the tubers were shaken to remove any excess water , gently blotted with a paper towel and placed in a lab mat covered tub to air dry prior to processing ( 1 – 2 hours ). a ca . 1 . 0 - g cross - sectional slice of whole tuber was taken ( see fig3 ) and the same was digested with 3 . 0 ml nitric acid ( trace metal grade ) in a 10 - ml graduated kimax culture tube on a programmed heating block . similarly a ca . 1 - g sample of pulp only was taken from each potato as a cross - sectional slice and a 1 – 3 - mm - thick slice of peel was taken . these three samples represented the whole tuber , pulp only , and peel only sub - samples , respectively . the samples were allowed to react for ca . 4 – 8 hours in a hood at ambient temperature . then the samples were digested using a heating block ( or programmable digester may be used ). the samples were heated to 180 ° c . for 3 – 4 hours . digestion is confirmed complete when no nitrous oxide gases are evolved ( i . e ., orange gas production ). samples are diluted with type 1 water ( 18 mohm cm ) and mixed thoroughly using a vortexer . analysis is by inductively coupled plasma atomic emission spectrometer ( icp - aes ) or one of the other methods as described above ( icp - oes , icp - ms ) percent moisture for each individual sample was determined in duplicate . the percent moisture method used was a modification of aoac method 984 . 25 ( association of official analytical chemists , 1990 ). mineral and trace element concentrations were standardized to a dry weight , based on the moisture content . quality control : each analytical batch contained a minimum of 25 % quality control samples , including check standards , duplicates , spikes , and standard reference materials ( srm ). percent recovery and percent standard deviation for srm are given in table 1 . during the course of the study over 360 srm samples were analyzed ; srm were dominantly plant matrices where available . in all cases the srm represented analyte concentration ranges typically found in plant tissues . the percent recovery ranged from 86 to 136 %. the percent standard deviation ranged from 2 to 39 %. typical percent standard deviation (% sd ) was & lt ; 10 %, although analytes close to method detection limits ( mdl ) had higher % sd . spike recoveries and check standards were typically within ± 10 % of their true value . there are several unique aspects to optimizing a set of chemical measurements that can be used to determine geographic origin of fresh commodities . this includes the determination of the most appropriate portion of the commodity to test ; determination of factors that might mask or dominate over subtle trends ; as well as determination of the most applicable set of chemical measurements to be made on the sample of choice . fresh commodities may be stored for long periods ( 1 – 9 months ); during storage fresh produce may lose moisture . for example , in a study on walnuts and storage influence , the authors proposed that even at 4 ° c . ( 3 months ) desiccation of the walnuts occurred ( lavedrine et al ., 1997 ). in the case of potato tubers , the percentage water may vary 10 – 20 % from the time of harvest to the time of use ( 1 – 9 months later ). percent moisture content will affect the relative concentration of trace elements ( e . g ., weight / weight ). therefore , the percentage moisture must be equalized such that it does not dominate or mask the variations of the elemental concentrations , which are due to geographic growing conditions of fresh commodities versus effects of dehydration during storage . the potato tuber was not dried prior to sub - sampling due to the difficulty in sub - sampling a portion that had a consistent pulp / skin ratio ( see below ). desiccation by freeze - drying is an alternative method . here the percent moisture was determined ( in duplicate ) for each individual tuber . the percent moisture was then used to determine the elemental concentrations on a dry weight basis for each individual tuber . in this way , the loss or variation of water would not mask the variations that are due to geographic growing conditions . the procedure developed was tested with samples over 4 months , and it was found that when the percent moisture was compensated for , the elemental concentrations were consistent regardless of storage time . this method therefore is robust in its applicability independent of storage time . it has been reported that elemental distribution in a fresh commodity is different for different parts of the commodity ( esechie , 1992 ). for example , the concentration of various elements within a potato will be different in the skin versus the pulp . one of the inventors has found that some elements may be concentrated in the potato skin relative to the potato pulp . in addition , some elements in the skin may be an enhanced ( or distorted ) reflection of geographic conditions . however , the pulp , which represents the largest portion by weight of the commodity , may have unique elemental distribution tendencies relative to other portions of the commodity . therefore , the challenge is to analyze sample components that maximize the effects of geographical conditions and yet are reasonable to prepare for analytical determination . three sample component parts for the potato commodity were analyzed : skin only , pulp only , and whole tuber . a preliminary data analysis using 70 samples ( computational modeling ) was used to screen the viability of each sample component part . in addition , practical aspects such as the reliability and consistency that could be achieved at the bench - level during sample preparation forthe chemical analysis were evaluated . the most optimal sample component type was determined to be whole tuber . however , an important caveat of this sample type was the importance of the ratio of skin to pulp . it was determined that the skin to pulp ratio ( by weight ) should be consistent between all samples . a protocol was developed that provided a method to sub - sample from the tuber that could consistently represent the same pulp / skin ratio ( see fig3 ). elemental distribution within a single commodity component ( e . g ., pulp only ) may vary within the commodity itself . for example , there is evidence that some chemicals within a potato tuber are not evenly distributed in a given potato component ( i . e ., the pulp ) from the stem end to the distal end ( al - saikhan et al ., 1995 ). here we developed a protocol that isolated a consistent potato tuber section . the center section was determined to be the least affected by any variations that might exist between the stem end and the distal end . see fig3 for a graphical representation of the sampling technique developed . the drying of a plant tissue is a balancing act between too low a temperature over a prolonged period , which will encourage and promote biological activity , and too high a temperature over a short period , which may result in the loss of volatile analytes . we performed a 10 - day study ( n = 3 ) of drying times versus temperatures . after 5 days the percentage moisture at 105 ° c . changed by less than 0 . 2 % on average . lower temperatures (& lt ; 85 ° c .) required longer drying times (& gt ; 7 – 8 days ), which risked biological growth , and temperatures & gt ; 105 ° c . were determined to increase the risk of other volatile analytes losses . the above - described procedure therefore was determined to be optimal for fresh commodities by minimizing any volatilization and producing a consistent dried weight while avoiding biological growth . an important attribute of this approach is that all the chemical data can be determined with the use of only a single analytical instrument , one of the icp - aes , icp - oes , and icp - ms . whereas other geographic authenticity approaches require the use of several instruments and sophisticated approaches to data analysis , this technique requires only a single , commonly available instrument . in this approach the data are used directly from the icp - aes into the computational models , requiring no prior mathematical or interpretive analyses as is often the case with other geographic authenticity approaches . the idaho snake river plain is a unique area composed of rich volcanic soil in an arid to semi - arid ( irrigated ) environment . the soils in this region are xerolls , which are unique as compared to other potato producing geographic regions . the soil and environmental growing conditions provide unique mineral and trace element tuber uptake and the necessary chemical profile difference to differentiate between potatoes grown in idaho versus outside idaho . the data were analyzed in an effort to classify potato samples as having originated from idaho orfrom outside idaho based on the trace element profile of each sample . basic statistical analyses and several pattem recognition methods were applied to the data . neural network methods were applied utilizing software from the ward systems group ( neuroshell , release 4 . 6 ). basic statistical analyses and pattern recognition techniques ( not including neural network ) were performed utilizing the sas system for windows analysis package ( release 6 . 11 , sas institute , inc .). neural network analysis included iterative feed - forward back - propagation architectures and included combining classifiers in a “ bagging ” strategy . basic statistical analyses and pattern recognition techniques included the following : descriptive statistics , students t test , assessment of normality of data distribution , principal component analysis , canonical discriminant analysis , discriminate function analysis , and nonparametric k nearest - neighbor analysis . the data set was standardized to account for differing variable scales by subtracting from each entry its associated variable mean and then dividing by the variable standard deviation . the standardized data corresponding to each variable thus have a mean equal to zero and a standard deviation equal to one . descriptive statistics ( the mean , standard deviation , minimum and maximum values ) for each element in each group were determined . the t - test procedure was used to compute a t statistic for testing the hypothesis that the means of the elemental concentration of the two groups of potatoes are equal . the univariate procedure was used to test for normality using the shapiro - wilk statistic and data distribution plots . small values of w lead to the rejection of the null hypothesis . the means , standard deviation , minimum and maximum values for elemental content of potatoes from idaho and non - idaho locations are shown in table 2 . idaho potatoes had higher concentrations of ca , cd , mg , ni , pb , s , and sr compared to non - idaho potatoes , whereas the concentrations of ba , cr , cu , fe , mn , and zn were lower in idaho compared to non - idaho potatoes . the concentrations of co , k , mo , p , and v in the two groups were not significantly different . despite these differences , examination of the minimum and maximum values illustrate that there was not a single element that could correctly classify the potato samples as to location , as the ranges of concentration for each group overlapped for every element . therefore , multivariate classification techniques were examined . the concentrations of several elements in the potato samples were very close to the detection limit of the chemical analysis method . for the purposes of statistical analyses , any value that was below the detection limit was set to a value of zero . this resulted in highly non - normal distributions ( w less than 0 . 8 ) for co , mo , and pb . these variables were subsequently eliminated from parametric analyses ( pca and discriminate function ). cr , ni , and v were also somewhat non - normal , with w less than 0 . 9 . each of these variables was systematically tested for contribution to the parametric discriminate function analysis , as described below . principal component analysis ( pca ) generates principal components that are linear combinations of the original variables . the first principal component ( pc ) describes the maximum possible variation that can be projected onto one dimension , the second pc captures the second most , and so on . the principal components are orthogonal in the original space of variables and the number of principal components can equal the number of original variables . analyzing the data with respect to principal components can thus sometimes effectively reduce the number of variables , especially if a large percentage of the total variation is described by a few principal components . one - or two - dimensional plots of data with respect to selected principal components can sometimes provide visual insight into the data , offering a visual description of group differences or clustering , and outliners . pca has been applied to geographical classification applications of various foods , including processed orange juice ( nikdel et al ., 1988 ), wine ( day et al ., 1995 ; latorre , et al ., 1994 ), honey ( sanz et al ., 1995 ), and cocoa ( hernandez and rutledge , 1994a , b ). pca was applied to our data using the princcomp procedure . pca demonstrated that a small number of variables did not dominate total variability , as the first three principal components accounted for only 49 % of total variability ( table 3 ). some visual clustering by location was observed , though better results were obtained using cds ( see below ), since the cda method optimizes between - class views . a two - dimensional plot of the data using the second and third principal components appear in fig4 . canonical discriminate analysis ( cda ) generates canonical variables , which are linear combinations of the original variables , that describe the variation between prespecified classes in a manner analogous to the way in which pca summarizes the total variation of the data . like pca , cda can be used to effectively reduce the number of variables and is particularly useful for producing one - or two - dimensional visualizations of the data since the “ views ” optimize the between - class differences . the default number of canonical variables generated is the minimum of the number of classes minus one , and the number of original variables . different views of our data were obtained by defining the number of classes to be two ( idaho vs . non - idaho ) as well as multiple classes defined by different states . cda has been applied to data for the purpose of geographical classification of wine ( latorre et al ., 1994 ). the sas procedure used for our analysis was the candisc procedure . cda was first applied to the data using two defined classes , idaho and non - idaho . fig5 shows a frequency chart of the data using the first canonical variable . classes were also defined by state [ and one class for canadian ( can ) samples ]. the data are plotted using the first two canonical variables in fig6 . in this two - dimensional projection co and id tend to overlap significantly and wi and me display significant overlap . fig7 is a “ cleaner ” view without the co and me samples . in fig8 half the data ( without co or me ) were used to generate the canonical variables and then plotted , and , in fig9 , the remaining data ( lower - case letters ) are plotted with respect to the canonical variables generated by the data in fig8 . fig9 thus conveys a visual sense of the consistency and the predictive properties of the data . we emphasize that any overlap depicted in one - or two - dimensional plots is not indicative of any intractable classification task . the predictive pattern recognition methods discussed below utilize all 14 available dimensions , and excellent predictive results are demonstrated . the discrim procedure was used for both parametric and nonparametric discriminate function analyses . the parametric procedure determines a discriminate function of classification criterion by a measure of generalized squared distance ( rao , 1973 ). this procedure assumes a multivariate normal distribution . selection of variables to be included is discussed below . in this case , the classification criterion was based on an individual within - group covariance matrix , yielding a quadratic function . there was no difference in the classification of samples when either equal or prior probabilities of the groups were used ( data not shown ). two error rates are computed . the first is an estimate of the probability of misclassification of future samples using the discriminate function created by the entire training set ( n = 608 ). the second is the error rate incurred during a cross - validation step , in which each sample is removed from the training set and tested against the resultant discriminate function created by the remaining samples ( n = 607 ). in all cases , the error rates given are those from the cross - validation test . validation of the discriminate function was also conducted by withholding one - half of the samples from the training set and using them as a test set against the discriminate function created by the remaining 304 samples . this was then repeated in reverse . the non - parametric procedure used was the k - nearest - neighbor method , where k = 10 . as no assumption is made in this procedure regarding the nature of the data set , all variables were included . the addition of v values to the parametric discriminate function , generated with the 15 remaining elements , increased the number of misclassified samples and was therefore removed from the analyses . elimination of either cr or ni values reduced the number of misclassified samples and therefore these variables were included in the model . the final model included 14 elements ( ba , ca , cd , cr , cu , fe , k , mg , mn , ni , p , s , sr , and zn ). the error rates of the quadratic discriminate function calculated using 14 element concentrations of 342 known idaho potato samples and 266 known non - idaho potato samples were 3 . 5 % and 5 . 6 %, respectively , resulting in 330 idaho ( 97 %) and 251 non - idaho ( 95 %) correctly classified samples in cross - validation testing ( table 4 ). the data set was randomly divided into two halves of 304 samples . cross - validation testing using only 304 samples as the calibration or training set had error rates of 4 . 1 and 4 . 7 % for known idaho potatoes and 4 . 5 and 9 . 3 % for non - idaho potatoes ( table 4 ). when the remaining database of known samples were used as a testing set against the 304 potato training set , error rates were 4 . 7 % for the idaho potatoes and 3 . 8 to 6 . 0 % for non - idaho potatoes ( table 4 ). the nonparametric k nearest - neighbor analyses using all 18 variables and all 608 samples gave low error rates for idaho potatoes ( 1 . 2 %) but had higher error rates for non - idaho potatoes ( 8 . 4 %). feed - forward back - propagation neural network methods were also applied to the data in an effort to classify the samples by geographic origin as idaho or non - ldaho samples . to prevent over - fitting or over - training , an early stopping strategy was employed to enhance the ability of the networks to generalize well ( perform well on new data ). the data were divided into two disjoint subsets : a training set and a test set . networks were trained using half of the data ( training set ). during the training process the remaining half of the data ( test set ) was periodically presented to the networks for classification . the final values of the network parameters were those corresponding to optimum test set performance . further generalization enhancements are possible by employing a bootstrap aggregating (“ bagging ”) strategy ( frieman ). here multiple networks are trained using randomly selected ( sampling with replacement ) training sets corresponding to halfthe data . final classification is then determined by voting . this has the effect of reducing the high variance inherent to neural networks , resulting in improved generalization . originally all 18 candidate trace metals were considered . it was found that superior classification results were obtained by considering only the 14 trace metals used in the parametric discriminate function analysis . this is most likely attributable to the fact that for a large number of samples , the measured quantities of the 4 unused trace metals were below detection limits , resulting in artificially truncated frequency distributions for these metals . an early stopping strategy was first examined . fifty neural network models were generated . each model used 50 % ( 304 samples ) of the data for the training set and 50 % for the test set . the model architecture was the same for each model ; the difference in the models was due to the difference in training and test sets , which were selected randomly ( as disjoint complements ) for each model . individual model classification performance on the known data ( training and validation sets together ) ranged from 92 to 98 %. to investigate a bagging strategy , a universal test set of 46 samples was selected from the original data and set aside . this universal test set was selected so as to represent a typical cross - section of the original data . sixty neural network models were then generated using the remaining data ( 562 samples ), which was now considered as the “ known ” data set . as before , each individual model was generated using 50 % ( 281 randomly selected samples ) of the “ known ” data for training , and the remaining complementary set was used as a test set . individual model performance ranged from 92 – 98 % correctly classified on the “ known ” data ( training and test sets together ) and 89 – 98 % on the universal test set . generally , the relative performance of individual models on the “ known ” data and the universal test set were not strongly correlated . when the 60 independent classifiers were combined (“ bagged ”), the resulting aggregate model correctly classified 98 % of the universal test set samples , missing only one out of the 50 samples . also when the aggregate model was applied to the “ known ” data set , over 99 % of the samples were correctly classified . in order to compare the best neural network strategy ( bagging ) and the optimized parametric discriminate function analysis , the universal test set ( 46 samples ) was removed and parametric discriminate functions were generated using the remaining data . the discriminate function analysis correctly classified 89 % of the universal test set ( 41 out of 46 samples ) and 95 – 96 % of the known data set ( 562 samples ) in cross - validation testing . therefore , neural network bagging does appear to be worthwhile strategy , producing superior results over single model discriminate analysis . it may be appreciated by one skilled in the art that additional embodiments may be contemplated , including similar systems and methods for localizing the geographic origin of virtually any plant or portion thereof that has the ability to take up substances from the soil in which it is grown . extrapolations are also visualized wherein animal products could also be so localized dependent upon their feed source . in the foregoing description , certain terms have been used for brevity , clarity , and understanding , but no unnecessary limitations are to be implied therefrom beyond the requirements of the prior art , because such words are used for description purposes herein and are intended to be broadly construed . moreover , the embodiments of the apparatus illustrated and described herein are by way of example , and the scope of the invention is not limited to the exact details of construction . having now described the invention , the construction , the operation and use of preferred embodiment thereof , and the advantageous new and useful results obtained thereby , the new and useful constructions , and reasonable mechanical equivalents thereof obvious to those skilled in the art , are set forth in the appended claims . | 6 |
as is shown in fig1 , an ink jet printer according to an embodiment of the invention comprises a platen 10 which serves for transporting a recording paper 12 in a subscanning direction ( arrow a ) past a printhead unit 14 . the printhead unit 14 is mounted on a carriage 16 that is guided on guide rails 18 and is movable back and forth in a main scanning direction ( arrow b ) relative to the recording paper 12 . in the example shown , the printhead unit 14 comprises four printheads 20 , one for each of the basic colours cyan , magenta , yellow and black . each printhead has a linear array of nozzles 22 extending in the subscanning direction . the nozzles 22 of the printheads 20 can be energized individually to eject ink droplets onto the recording paper 12 , thereby to print a pixel on the paper . when the carriage 16 is moved in the direction b across the width of the paper 12 , a swath of an image can be printed . the number of pixel lines of the swath corresponds to the number of nozzles 22 of each printhead . when the carriage 16 has completed one pass , the paper 12 is advanced by the width of the swath , so that the next swath can be printed . all the components of the printer are operatively coupled . the printheads 20 are controlled by a processing unit 24 which processes the print data in a manner that will be described in detail hereinbelow . the discussion will be focused on printing in black colour , but is equivalently valid and applicable for printing in other colours . fig2 a shows an array of 6 × 6 pixels 26 , which represents a portion of an image to be printed as an example . the pixels 26 are arranged in lines i − 3 , i − 2 , i − 1 , i , i + 1 , i + 2 and columns j − 3 , j − 2 , j − 1 , j . j + 1 and j + 2 . black pixels are indicated by dots 28 as printed with the ink jet printer shown in fig1 . since the ink droplet forming a dot 28 tends to spread on the recording medium ( e . g ., paper ), the optical density of the dot decreases gradually from the center toward the periphery , and the lighter peripheral portions of the dot extend beyond the area of the pixel , so that neighbouring dots overlap . the image that has been shown in largely magnified scale in fig2 a would give the impression of a uniform grey area . fig2 b shows the same image shown in fig2 a , except that the nozzle needed for printing the line i is defective , so that the dots at the pixel positions ( i , j − 2 ) and ( i , j ) are missing . this would give rise to a perceptible brighter gap in the printed image at the position of the line i . in order to eliminate or at least mitigate this image defect , the processing unit 24 shown in fig1 performs a camouflage step which , in the given example , leads to the insertion of an additional dot 30 ( fig2 c ) at the pixel position ( i − 1 , j − 1 ), i . e . in the pixel line i − 1 directly adjacent to the defective line i . as a result , on the macroscopic scale the image shown in fig2 c resembles the ideal image shown in fig2 a . this camouflage process of the invention will now be explained in detail . at first , it shall be assumed that the print data are supplied to the printer in a multi - level format , in which the grey value of each pixel is indicated by an 8 - bit word , i . e . by an integral number between 0 and 255 . the number 0 represents a white pixel and the number 255 a black pixel with maximum optical density . the print data are thus represented by a multi - level pixel matrix 32 as is schematically shown in fig3 . in the single - pass mode , each pixel line of this pixel matrix will be printed by only one of the nozzles 22 of the printhead . the printer may be equipped with a detection system which automatically detects and locates defective nozzles . as an alternative , the location of a defective nozzle may also be input by the user . when , for example , the nozzle responsible for printing the third line of the pixel matrix is defective , the pixels in that line are non - printable pixels 34 , whereas the other pixels 36 , 38 and 40 are printable . pixels 38 and 40 in the lines directly adjacent to the non - printable pixels 34 are shown in dark hatching in fig3 . the non - printable pixels 34 and pixels 38 and 40 adjacent thereto form a camouflage area that is involved in camouflaging the effect of the defective nozzle . an error propagation halftoning step is used for transforming the multi - level pixel matrix 32 into a bitmap . fig4 illustrates a conventional error propagation scheme 42 ( a floyd steinberg scheme ) that is frequently used for this purpose . as is shown in fig4 , a number of arrows originate from a source pixel 44 and point to four target pixels 46 adjacent to the source pixel . the fractions ( 7 / 16 , etc .) given in the target pixels 46 indicate the weight factors with which the error remaining from the source pixel is distributed over the target pixels . the theshold value ‘ th ’ with which the grey level of the source pixel 44 is compared is 255 , for example . this standard arrow propagation scheme will be used for the printable pixels 36 outside of the camouflage area . it is assumed here that the processing of the source pixels proceeds from left to right and from top to bottom . as is indicated by the arrows , the error is propagated only in “ forward ” direction , i . e . each source pixel is processed earlier than its target pixels . fig5 illustrates a modified error propagation scheme 48 that will be used for the pixels 38 in the line that is processed immediately before the line including the non - printable pixels 34 according to an embodiment of the invention . here , the error from the source pixel 44 is propagated with a weight factor of 1 ( 16 / 16 ) only to the next pixel in the same line . thus , the image information is kept in the line in which it can actually be printed , and the non - printable pixels 34 in the line below are not used as target pixels . the theshold value ‘ th ’ for the source pixel 44 is again 255 . the large weight factor with which the error is propagated horizontally in fig5 increases the likelihood that additional black pixels are added in this line , in order to achieve a camouflage effect similar to the one shown in fig2 c . fig6 shows another modified error propagation scheme 50 that will be used for the non - printable pixels 34 in fig3 . here , the error from the ( non - printable ) target pixel 44 is propagated only into the line below , i . e . the line formed by the pixels 40 in fig3 . the sum of the weight factors is again equal to 1 , so that the error is fully transferred onto the neighbouring line . moreover , in this scheme , the threshold value for the non - printable pixels 34 is increased to a level above 255 . in other words , even when the grey level of such a pixel is equal to 255 , the pixel will nevertheless be made white and the error of 255 will be propagated to the line below . thus , the image information of the line that cannot be printed because of the nozzle defect will be fully transferred to the line immediately therebelow . again , this increases the likelihood that one of the pixels 40 in fig3 will be made black in order to camouflage the nozzle defect . the pixels 40 form part of the camouflage area because they are affected by the error propagation scheme 50 shown in fig6 . however , when the pixels 40 are themselves processed in the error diffusion process , the standard error propagation scheme 42 of fig4 may be used . in the example given above , it has been assumed that the threshold value utilized in the error diffusion process is either 255 ( for the error propagation schemes 42 and 48 ) or infinity ( for the scheme 50 ). in a modified embodiment of the invention , however , it would be possible to use a somewhat lower threshold value for the pixels 38 and / or 40 , in order to further increase the likelihood of black pixels being created . optionally , in order to avoid an over - compensation , it is possible that the weight factors indicated in fig6 are reduced correspondingly . this modified embodiment would have the effect that the likelihood of becoming black is increased for the pixels 38 ( above the line of the nozzle defect ) and decreased for the pixels 40 ( the line below the nozzle defect ). with the error propagation schemes of fig4 to 6 , the target pixels 46 are not more than one line or column away from the source pixel 44 . in a modified scheme , the maximum distance between source and target pixel may be larger , e . g . 2 . then , the camouflage area would also include the first and the fifth line in fig3 . fig7 illustrates the case of a specific two - pass print mode . when one of the two nozzles responsible for printing the third line in the pixel matrix 32 in fig7 is defective , only every second pixel in that line will be a non - printable pixel 34 , and the intervening pixels 52 will belong to the camouflage area . in the error diffusion process according to the invention , the pixel 52 will be treated with an error propagation scheme in which the error is only propagated downward but not horizontally . for the non - printable pixels 34 the error may be propagated horizontally ( as in fig5 ) and / or downwardly . in case of the pixels 38 , two different error propagations schemes have to be used , depending upon whether or not the pixel is located directly above a non - printable pixel 34 . the camouflage process described above is particularly efficient for images which mainly contain small or medium grey levels . in case of very dark images and , in the extreme , in the case of solid black areas , it is increasingly difficult or even impossible to add more black pixels in the camouflage area . nevertheless , the camouflage process may be useful even for dark or black images , depending upon the design of the printer . some known printers are capable of printing a plainly black area even when the percentage of black pixels in the bitmap is somewhat smaller than 100 %. in this case , the modified error propagation schemes for the camouflage area may lead to an over - saturated bitmap which would still mask the nozzle defect to some extent . a specific embodiment of the method according to the invention will now be described by reference to the flow diagram shown in fig8 . in step s 100 , the multi - level pixel matrix 32 is established by reading - in the grey values of the pixels . the pixel lines that are affected by nozzle failures of the printhead are identified in step s 101 . then , in step s 102 , the camouflage area is determined . an optional step s 103 may involve a decrease of the threshold value ‘ th ’, e . g . from 255 to 191 , for the lines ( pixel 38 in fig3 ) preceding the lines affected by the defect . step s 104 identifies the pixels ( such as the pixels 34 and 38 in fig3 ) for which a modified error propagation scheme ( 50 or 48 ) has to be employed and selects the appropriate scheme . in step s 105 , the error diffusion process is performed for all the pixels of the pixel matrix with either the non - modified or the selected one of the modified error propagation schemes . the resulting bitmap is then printed in step s 106 . alternatively , the step s 100 may be performed after the step s 101 or even after the step s 104 . fig9 illustrates another embodiment which is adapted to the case that the print data are presented already in the format of a bitmap , i . e . a matrix of only black and white pixels . the bitmap is read in step s 200 . the steps s 201 and s 202 correspond respectively to the steps s 101 and s 102 discussed above . in step s 203 , the part of the bitmap which corresponds to the camouflage area is reconverted into a multi - level pixel matrix . to this end , a value of 255 is assigned to each of the black pixels of the pixel matrix , i . e . the pixels having the binary value 1 , and the white 0 - pixels are left as they are . all non - printable pixels 34 may be set to 0 . the steps s 204 , s 205 and s 206 correspond again respectively to the steps s 104 , s 105 and s 106 , with the difference that steps s 204 and s 205 are performed only for the camouflage area and for the lines that contain the corresponding target pixels . fig1 a shows an example of the bitmap read in step s 200 of fig9 . again , it is assumed that the nozzle that is responsible for printing the pixels in line i in the single - pass mode is defective . fig1 b illustrates the corresponding multi - level pixel matrix obtained in step s 203 of fig9 . the embodiment of fig9 has been exemplified for the single - pass mode , but it goes without saying that this method is also applicable to a multi - pass mode , as has been described in conjunction with fig7 . the processing steps of the methods of the present invention are implementable using existing computer programming language in , e . g ., the processing unit 24 of fig1 . such computer program ( s ) may be stored in memories such as ram , rom , prom , etc . associated with computers and / or printers . alternatively , such computer program ( s ) may be stored in a different storage medium such as a magnetic disc , optical disc , magneto - optical disc , etc . the computer programs are readable using a known computer or computer - based device . the invention being thus described , it will be obvious that the same may be varied in many ways . such variations are not to be regarded as a departure from the spirit and scope of the invention , and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims . | 1 |
embodiments of the present invention will be described in detail hereinbelow with reference to the drawings . fig1 is a block diagram of an image pickup apparatus using a gamma correction circuit of the present invention . in the diagram , reference numeral 1 denotes a charge coupled device ( ccd ) as an image pickup device in which color separation filters of a complementary color mosaic of y e , c y , m g , and g are arranged on the front surface . reference numeral 2 denotes a sample and hold ( s / h ) circuit to convert an output signal of the ccd 1 into a continuous signal ; numeral 3 is an a / d converter to convert an output signal of the s / h circuit 2 into a digital signal ; numeral 4 is a low pass filter ( lpf ) for allowing only a luminance signal in an image pickup signal from the a / d converter 3 to pass ; numeral 5 is a gamma correction circuit ; numeral 6 is a delay circuit to match delay times of color signals , which will be explained shortly , and the luminance signal ; numeral 7 is a sync adding circuit ; numeral 8 is a d / a converter ; numeral 9 is a luminance signal ( y ) output terminal ; and numeral 10 is a color separation circuit used to separate the color signals from the image pickup signal from the a / d converter 3 . in this embodiment , color signals r , g , and b of pure colors are produced from the signals of the complementary color systems by a color separation matrix operation . reference numeral 11 denotes a multiplier used to match a white balance ; signal with the color signal numeral 12 is a coefficient circuit for providing the white balance signal ; numeral 13 is a gamma correction circuit a time - shared gamma correction of the r , g , and b signals ; numeral 14 is a color difference matrix circuit to synthesize color difference signals ; numeral 15 is a modulator to modulate the color difference signals by a color sub - carrier ; numeral 16 is a burst adder ; numeral 17 is a d / a converter ; and numeral 18 is a color signal ( c ) output terminal . an object image ( not shown ) which has been formed on the ccd 1 by an optical system ( not shown ) is color separated by the ccd 1 . next , it is photoelectrically converted into an electric signal . the electric signal is converted to a continuous signal by the s / h circuit 2 and is analog - to - digital converted by the a / d converter 3 . first , the luminance signal is filtered by the lpf 4 and is gamma corrected by the gamma correction circuit 5 and is delayed a predetermined time by the delay circuit 6 . next , a sync signal is added to the delayed signal by the sync adding circuit 7 . an output signal of the sync adding circuit 7 is then converted to an analog signal by the d / a converter 8 and the analog output signal is provided to an external apparatus ( not shown ) such as a television , vtr , or the like through y output terminal 9 . in addition , the output signal of the a / d converter 3 is separated into primary color signals r , g , and b by the color separation circuit 10 . coefficients set by the coefficient circuit 12 are multiplied to the primary color signals of r , g , and b by the multiplier 11 and a white balance is performed to match the levels of r , g , and b . the resultant signals are gamma corrected by the gamma correction circuit 13 and the color difference signals from the gamma correction circuit 13 are synthesized by the color difference matrix circuit 14 . the synthesized signal is orthogonally orthogonal modulated by the color sub - carrier by the modulator 15 . a color burst is added to the modulated signal from the modulator 15 by the burst adder 16 . an output signal of the burst adder 16 is converted into an analog signal by the d / a converter 17 . the analog signal is provided from the c output terminal 18 in a manner similar to the provision of the y signal . fig2 is a block diagram of an embodiment of the gamma correction circuits 5 and 13 shown in fig1 . in the diagram , reference numerals 101 , 103 , 107 , and 109 denote coefficient devices used to multiply an input signal values of a , b , c and e , respectively . reference numeral 102 denotes a multiplier ; numerals 104 , 105 , and 110 denote adders ; numeral 106 is a means for supplying a coefficient d ; numeral 108 is a selector used as a selecting means ; numeral 111 is a means for supplying a coefficient f ; and numeral 112 is a comparator used as a comparing means . the input signal is first multiplied by a coefficient of value a by the coefficient device 101 and is supplied to a first input terminal of the selector 108 . the coefficient device 101 comprises a first function forming means . the input signal is also multiplied by itself by the multiplier 102 and is then multiplied by a coefficient of value b by the coefficient device 103 . a value of c is multiplied the input signal is also multiplied by a coefficient of value c by the coefficient device 107 . an output signal of the coefficient device 103 is added to an output signal of the coefficient device 107 by the adder 104 . the coefficient d from device 106 is added to an output signal of the adder 104 by the adder 105 . an output signal of the adder 105 is supplied to a second input terminal of the selector 108 . the multiplier 102 , coefficient devices 103 and 107 , adder 104 , coefficient device d , and adder 105 comprise a second function forming means . the input signal is also multiplied by a coefficient of value e by the coefficient device 109 . a coefficient f from the coefficient supplying means 111 is added to an output signal of the coefficient device 109 by the adder 110 . an output signal of the adder 110 is supplied to a third input terminal of the selector 108 . the coefficient device 109 , coefficient device 111 , and adder 110 comprise a third function forming means . the input signal is compared with predetermined signal values ( x 1 and x 2 which will be described shortly ) by the comparator 112 . on the basis of the result of the comparison , either one of the first , second , and third inputs of the selector 108 is selected and generated as a gamma correction output . fig3 is a graph showing gamma characteristics of the gamma correction circuit shown in fig2 . when the above gamma characteristic is approximated as shown in fig3 by using a first straight line y 1 ( x ) ( first function ) of 0 to x 1 , a quadratic curve y 2 ( x ) ( second function ) of x 1 to x 2 , and a second straight line y 3 ( x ) ( third function ) of x 2 to 1 , the following equations ( 1 ) to ( 3 ) are obtained , respectively . first , a = 4 , e = 0 . 5 , and f = 0 . 5 are obtained by the inclinations near x = 0 and x = 1 of the gamma characteristic . subsequently , in order to continuously and smoothly connect the boundaries of the above respective functions , it is desirable to obtain the following equations ( 4 ) to ( 7 ), in which a mark (&# 39 ;) denotes a differentiation . by substituting the above equations ( 4 ) to ( 7 ) in equations ( 1 ) to ( 3 ), the following equations ( 8 ) to ( 11 ) are obtained . in the equations ( 8 ) to ( 11 ), by using x 1 as a parameter , x 2 , b , c , and d can be obtained . by substituting the resultant values of a , b , c , d , e , and f as coefficients in the coefficient devices 101 , 103 , 107 , 106 , 109 and 111 , respectively , in fig2 and by substituting the values in x 1 and x 2 as set values of the comparator 112 in fig2 the gamma characteristics of fig3 can be realized . fig4 is a block diagram of another embodiment of the gamma correction circuits 5 and 13 shown in fig1 . in fig4 the same component elements as those shown in fig2 are designated by the same reference numerals and their descriptions are omitted . in the diagram , reference numeral 113 denotes a coefficient device c . in the embodiment , the coefficient device 103 , adder 104 , coefficient device 113 , multiplier 102 , coefficient device 106 , and adder 105 comprises the second function forming means . the input signal is first multiplied by a coefficient of value a by the coefficient device 101 , and a resultant output signal is supplied to the first input terminal of the selector 108 . the input signal is also multiplied by a coefficient of value b by the coefficient device 103 . the coefficient c from device 113 is added to a resultant output signal of the coefficient device 103 by the adder 104 . an output signal of the adder 104 is multiplied by the input signal by the multiplier 102 and its output signal is added with the coefficient d from device 106 by the adder 105 . a resultant output signal of the adder 105 is supplied to the second input terminal of the selector 108 . the input signal is also multiplied by a coefficient of value e by the coefficient device 109 . the coefficient f from device 111 is added to an output signal of the coefficient device 109 by the adder 110 . an output signal of the adder 110 is supplied to the third input terminal of the selector 108 . the input signal is compared with the predetermined values ( x 1 and x 2 mentioned above ) by the comparator 112 . on the basis of the result of the comparison , either one of the first to third inputs of the selector 108 is selected and generated as a gamma correction output . in fig4 when it is assumed that the first , second , and third inputs of the selector 108 are set to y 4 ( first function ), y 5 ( second function ), and y 6 ( third function ), respectively , the following equations ( 12 ) , ( 13 ), and ( 14 ) are obtained . the developed equation ( 13 ) is developed the same as equation ( 2 ) and the characteristics of fig3 can be obtained in a manner similar to obtaining the characteristics of the circuit of fig2 . when comparing the circuit of fig4 with the circuit of fig2 since the number of coefficient devices can be reduced , a circuit scale can be further reduced . as described above , according to the embodiment , since the gamma correction circuit can be constructed without using a rom , the circuit scale can be reduced resulting in a large advantage such that costs and an electric power consumption can be reduced and the apparatus can be miniaturized . there is also an advantage such that by making the function values coincide at a switching point of the function and also by making the inclinations of the functions coincide , a deterioration of the picture quality due to the switching doesn &# 39 ; t occur . | 7 |
the following disclosure describes an auto correction interface that combines a user &# 39 ; s speech and the user &# 39 ; s touch in a multimodal fashion . the invention may be viewed from two different angles : ( a ) a speech recognition system whose accuracy is significantly increased by providing additional knowledge of the word to recognize in the form of the word &# 39 ; s initial letters and ( b ) an auto correction system whose accuracy is significantly improved by providing additional knowledge of the word to correct in the form of the acoustics of the word spoken by the user . specifically in this invention , a user speaks and types a word substantially at the same time . there is no restriction to the ordering of the spoken word and the letters typed ; a user may first speak and then type the word or may speak while typing the word or may speak after typing the word ; although it is most efficient and fast when a user speaks and types at the same time . on receiving the letters from the user , the system determines a set of letters based upon an ambiguity map . using the set of letters as a filter and further aided by additional constraints including a multimodal language model , the system dynamically narrows the speech recognition search . when the user hits the space - bar key indicating end of word , the process uses the most recently reduced search to perform speech recognition and computes a best hypothesized word along with its nbest choice alternatives . the multimodal language model is used to post process the list of words to yield the best word , which is presented to the application ; a confidence model &# 39 ; s score may also accompany the word in the application to indicate its confidence to the user . an embodiment of the “ speak and touch auto correction interface ” referred to as staci is described . next , three sub - components of staci , namely the method to dynamically reduce the search , the multimodal language model , and the multimodal confidence model are described . fig1 is a conceptual overview of a process 100 of the staci system . for ease of understanding the overview is presented in the form of software designed using object oriented methodologies such as threads . however , one will appreciate that the threads may be thought of as modules too . in fig1 , three threads are illustrated in the system : 1 ) a key - input thread 102 for a keyboard interface for inputting letters ; 2 ) an audio input thread 104 for a microphone interface for collecting audio buffers ; and 3 ) a multimodal recognition thread 106 for implementing a multimodal speech recognition logic of staci . the way the overall interface works in one embodiment is as follows . when a user presses keys on a keyboard , the corresponding letters or symbols or control signals are collected by the key - input thread 102 into a key queue 108 . in parallel , the user could also speak a word ; the microphone is open all the time and the audio - input thread 104 is collecting audio buffers into an audio queue 110 . the multimodal recognition thread 106 is continuously running in a synchronized fashion as shown in fig1 ( as shown with reference to an arrow that connects block 112 back to block 106 ) to check for the letters in the key queue 108 and the audio buffers in the audio queue 110 . the multimodal recognition thread 106 first checks if there is any letter that has not yet been processed from the key queue 108 . if there is no letter , i . e block 160 is reached , then it takes the audio buffer present in the audio queue 110 and passes it to the process and detect audio module 112 . if in the recognition thread 106 , the take and analyze key presses module 120 finds a new letter which corresponds to an alphabet set , i . e ., block 150 , it dynamically reduces the speech recognition active vocabulary using a method described in fig2 . on the other hand if the letter corresponds to a symbol ( i . e ., block 122 ), the system activates a symbol vocabulary in the recognition module 132 . finally , if the process 100 determines that the letter is an end of word indicator 124 ( e . g ., a space - bar ), then the thread 106 carries out the following steps : ( a ) continues to collect any remaining audio buffers ; ( b ) gets an utterance detected segment from an utterance detector module 130 which in turn gets this by processing the output of process and detect module 112 ; ( c ) performs speech recognition on the utterance detected in block 132 ( d ) finds the best word along with the nbest choices and the acoustic scores which is also part of the speech recognition process of block 132 , ( e ) applies the multimodal language model 134 to find the final word and scores , ( f ) computes a recognition confidence score at block 136 , ( g ) presents the final word along with the scores and confidence to the user interface at block 138 , and ( h ) finally resets , at block 140 , the audio queue , the key queue , the recognition searches and other necessary modules . in the above staci process , if the user has typed no letters at all indicated end of word ( e . g . user presses space , says awesome , then presses space again without typing any letters ) then the process backs off to using the base vocabulary of fig2 module 204 ; which may be reduced using the multimodal language model ( module 250 of fig2 ) and zero or more applicable constraints ( module 240 of fig2 ); the speech recognition is then performed just like described before . further on , if the user does not indicate an end of word , then the utterance detector module 112 may be used to signal the end of word automatically ; rest of the process remaining the same . those skilled in art will appreciate that several different architectures , both software and hardware , may be employed to alternatively implement the concept underlying staci . the staci process 100 can be easily extended to handle gesture based typing . this is described next . there are two ways of implementing this extension . one straightforward way is the following . as the user swipes or traces the letters of a word , the corresponding letters and their ambiguous parts are put by the key - input thread 102 into the key queue 108 . as before , in parallel , the user may also speak a word and have the speech collected into the audio queue 110 . as before , the multimodal recognition thread 106 is continuously running in a synchronized fashion , checking for the letters in the key queue 108 and audio buffers in the audio queue 110 . the remaining process remains the same as described above . another approach to extend the staci process 100 for gesture based typing is the following . the key queue 108 waits till the user lifts their finger indicating the end of swiping . for example , to enter the word “ demonstration ” the user swipes over the letters d e m s ( introducing ambiguity due to swiping and also due to sloppy swiping ) while speaking “ demonstration ” and lifting finger . upon lifting their finger , the key - input thread 102 puts the letters with the ambiguous counterparts into the key queue 108 . the staci process 100 then processes these letters in 150 to dynamically reduce the speech recognition vocabulary in 152 and directly calls the “ get utt detect ” 130 followed by the recognition module 132 . thus , the entire procedure is very similar except for ( a ) multiple letters are collected when user lifts finger and ( b ) end of word indicator is not the space - bar but the action by user of “ lifting finger ”. an example that compares staci to other input methods is now presented for further ease of understanding . consider the user is attempting to type the word “ awesome ”. the following are ways to enter the word using the different input methods : ( a ) staci : while typing a q e the use says “ awesome ” and hits space ( b ) staci with gesture typing : while swiping a → q → e the user says “ awesome ” and stops swiping ( c ) qwerty keyboard with auto correction : user types a q e some and hits space ( d ) text prediction : user types a q e then lifts head to select awesome ( if present ) from choices displayed and then finalizes it by touching same or hitting space . fig2 describes a method 200 to dynamically reduce the recognition vocabulary . the method 200 includes a base dictionary object 204 , which may be accomplished by loading a base vocabulary when the application starts for the first time , such as by reading from a file ( or any other memory location ). the base vocabulary and / or the base dictionary object 204 includes a list of words along with their pronunciations , statistical language model counts , and user adapted language model counts . further , the base vocabulary and / or the base dictionary object 204 is sorted based on the words language model counts ; in the event that words have the same count then metrics including length of pronunciation , length of word , the number of times the word appears as an n - gram etc are used to continue sorting . during processing , when a letter is received from the key queue that corresponds to an alphabet , then the base dictionary object 204 is used to create the 1 - letter dictionary object 206 . specifically , this is achieved by applying the letter and its ambiguity filter of block 202 to the words . as an example , if the letter typed is “ a ” then the letter filter is “ a ” and the ambiguity filter may be “ qwaszx ” which are the letter keys surrounding the letter key a on a qwerty keyboard ; filter implies selecting only those words that begin with the letter filter or the ambiguity filter . when the second letter of the word is received , then the 1 - letter dictionary object 206 is used to create the 2 - letter dictionary object 208 . this process is repeated until the end of word signal or the space - bar is received in which case everything is reset to simply retain the base dictionary object state 204 . in each stage , the objects are further used to create the actual active grammars ( e . g ., 210 , 220 , 230 ) and the language model hashmaps ( e . g ., 212 , 222 , 232 ), using a series of constraints 240 such as length of word , length of pronunciation of the word , length of the audio corresponding to the detected utterance , and max # words . the grammars i . e . 210 , 220 , 230 are used by the speech recognition module of fig1 block 132 to carry out recognition and the language model hashmaps i . e . 212 , 222 , 232 are used by the multimodal language module to apply n - gram statistics before finding the best word choice . the entire process beginning from creation of the 1 - letter object 206 is repeated as the user types letters corresponding to the next word . it will be appreciated by those skilled in art that grammars may be replaced by statistical networks , pre - compiled grammars , modifications to the search algorithm in a speech recognition decoder . similarly language model hashmaps may be replaced by other mechanisms to look up language statistics . fig3 describes a multimodal language model 300 . observe that instead of the standard n - gram language model used in speech recognition wherein the probability of words are computed given the previous spoken words , the proposed invention computes the probability of words given the previously finalized word by the user . the advantage of doing so is that the system knows with certainty the previous words . as an example , lets us say a user is intending to type the phrase , “ this is demonstration of multimodal language model ”. using conventional speech to text , the user can speak the whole phrase at once . let &# 39 ; s assume the conventional speech to text system recognizes “ this is demonstration of ” correctly but fails to recognize “ multimodal ” and recognizes “ multiple mode ” instead . this error will now propagate to the recognition of the word “ language model ” because its using “ multiple mode ” as the previous words when in reality “ multimodal ” is the previous word . the proposed invention does not exhibit this problem because its interface is based on a word - by - word interaction where each word is indicated as the final word using an end of word signal such as a space - bar . it can be seen from fig3 that the previously finalized words 302 along with the letters entered 304 are used to compute statistical n - grams in 306 . for example , if the user has typed “ this de ” then “ this ” is part of 302 and the letters “ de ” are part of 304 and they are used to compute bigram scores or load pre - computed bigram scores of all words starting with “ de ” that have “ this ” as the precursor word in their bigram pair . the ngram score is then added to the word &# 39 ; s unigram and other counts like the user counts or topic counts to compute a total lm score in 308 . finally , this is combined with the acoustic scores in 320 ( which are outputted by the recognition module of fig1 block 132 ) to yield a total score 310 . fig4 describes a multimodal confidence model process 400 used in the proposed invention . observe that the overall confidence score is computed by combining traditional confidence metrics known in speech recognition ( difference between nbest scores , number of active hmm nodes , acoustic features like formant location , average frequency , signal to noise ratio etc ) with multimodal features including ( a ) a metric that determines the closeness between acoustic only recognition and text only prediction for e . g . whether the same words were recognized by speech recognition and text prediction ( b ) the user language model score ( c ) the time between key presses and so on . as shown in fig4 , the best hypothesis along with its score from 402 , the nbest choices along with their scores and their difference scores and the total number from 404 , and acoustic features like utterance length and formant frequency locations and formant amplitudes etc from 406 are coupled by block 420 with multimodal features in 408 including whether text prediction and acoustic hypothesis are the same and user count for words and time elapsed between keys during typing the word and whether breath or other sounds detected during audio utterance detection of fig1 block 114 . block 420 computes a final confidence score by sorting the scores for all hypothesis and presents it along with its corresponding best hypothesis to the user interface or application . certain of the components described above may be implemented using general computing devices or mobile computing devices . to avoid confusion , the following discussion provides an overview of one implementation of such a general computing device that may be used to embody one or more components of the system described above . fig5 is a functional block diagram of a sample mobile device 501 that may be configured for use in certain implementations of the disclosed embodiments or other embodiments . the mobile device 501 may be any handheld computing device and not just a cellular phone . for instance , the mobile device 501 could also be a mobile messaging device , a personal digital assistant , a portable music player , a global positioning satellite ( gps ) device , or the like . although described here in the context of a handheld mobile phone , it should be appreciated that implementations of the invention could have equal applicability in other areas , such as conventional wired telephone systems and the like . in this example , the mobile device 501 includes a processor unit 504 , a memory 506 , a storage medium 513 , an audio unit 531 , an input mechanism 532 , and a display 530 . the processor unit 504 advantageously includes a microprocessor or a special - purpose processor such as a digital signal processor ( dsp ), but may in the alternative be any conventional form of processor , controller , microcontroller , state machine , or the like . the processor unit 504 is coupled to the memory 506 , which is advantageously implemented as ram memory holding software instructions that are executed by the processor unit 504 . in this embodiment , the software instructions ( e . g ., computer - readable instructions ) stored in the memory 506 include a display manager 911 , a runtime environment or operating system 510 , and one or more other applications or modules 512 . for example , modules 512 may include a key - input module , a multimodal recognition module , an audio input module , and the like . the memory 506 may be on - board ram , or the processor unit 504 and the memory 506 could collectively reside in an asic . in an alternate embodiment , the memory 906 could be composed of firmware or flash memory . the storage medium 513 may be implemented as any nonvolatile memory , such as rom memory , flash memory , or a magnetic disk drive , just to name a few . the storage medium 513 could also be implemented as a combination of those or other technologies , such as a magnetic disk drive with cache ( ram ) memory , or the like . in this particular embodiment , the storage medium 513 is used to store data during periods when the mobile device 501 is powered off or without power . the storage medium 513 could be used to store contact information , images , call announcements such as ringtones , and the like . the mobile device 501 also includes a communications module 521 that enables bi - directional communication between the mobile device 501 and one or more other computing devices . the communications module 521 may include components to enable rf or other wireless communications , such as a cellular telephone network , bluetooth connection , wireless local area network , or perhaps a wireless wide area network . alternatively , the communications module 521 may include components to enable land line or hard wired network communications , such as an ethernet connection , rj - 11 connection , universal serial bus connection , ieee 1394 ( firewire ) connection , or the like . these are intended as non - exhaustive lists and many other alternatives are possible . the audio unit 531 is a component of the mobile device 501 that is configured to convert signals between analog and digital format . the audio unit 531 is used by the mobile device 501 to output sound using a speaker 532 and to receive input signals from a microphone 533 . the speaker 532 could also be used to announce incoming calls . a display 530 is used to output data or information in a graphical form . the display could be any form of display technology , such as lcd , led , oled , or the like . the input mechanism 532 may be any keypad - style input mechanism . alternatively , the input mechanism 532 could be incorporated with the display 530 , such as the case with a touch - sensitive display device . other alternatives too numerous to mention are also possible . those skilled in the art will appreciate that the proposed invention may be applied to any application requiring text - input , including ( but not limited to ) mobile text - messaging ( sms , mms , email , instant messaging ), mobile search , mobile music download , mobile calendar / task entry , mobile navigation , and similar applications on other machines like the personal digital assistants , pcs , laptops , automobile - telematics systems , accessible technology systems etc . additionally , several implementations of the system including a client - only , a server - only , and client - server architecture may be employed for realizing the system . | 6 |
in practicing the present invention , an auxetic mesh can be molded into a desired three - dimensional configuration . the inventor discovered that the a molded auxetic mesh can be formed into a desired 3 - d shape while preserving the size of the various open spaces in the mesh . as the auxetic mesh attains its three - dimensional shape during molding , the mesh deforms in a fractal manner , substantially retaining the initial mesh appearance , unlike the distortions observed after conventional meshes are formed over bi - curved surfaces . before being molded , the auxetic mesh may be provided in an initial flat two - dimensional form , which is simple to handle and store . converting the initial flat auxetic mesh into a three - dimensional shape may provide a more efficient manufacturing pathway when compared to batch processes that would normally required to fabricate a similar netting substantially free of defects . that is , if a non - auxetic mesh is used to produce a three - dimensional product , without the distortions mentioned above , a batch - type casting or injection molding process typically would be used for that purpose . fig1 shows an example of a molded product , a filtering face - piece respirator 10 , that uses a molded auxetic mesh to provide a three - dimensional shape to the product . the filtering face - piece respirator 10 includes a mask body 12 and a harness 14 . the mask body 12 has a support structure 16 that provides structural integrity to the mask body and that provides support for a filtering structure 18 that resides behind the support structure 16 . the filtering structure 18 removes contaminants from the ambient air when a wearer of the respirator 10 inhales . the support structure 16 includes an auxetic mesh 20 that is molded into a three - dimensional configuration , which defines the shape of the mask body 12 . the molded auxetic mesh 20 can provide the structural integrity sufficient for the mask body 12 to retain its intended configuration . the filtering structure 18 may be secured to the support structure 16 at the mask body perimeter 22 . the filtering structure 18 also may be secured to the support structure 16 at the apex 23 of the mask body when an exhalation valve ( not shown ) is secured thereto . the harness 14 may include one or more straps 24 that enable the mask body 12 to be supported over the nose and mouth of a person . adjustable buckles may be provided on the harness to allow the straps 24 to be adjusted in length . fastening or clasping mechanisms also may be attached to the straps to allow the harness 14 to be disassembled when removing the respirator 10 from a person &# 39 ; s face and reassembled when donning the respirator 10 from a person &# 39 ; s face . further , description of the filter face - piece respirator may be found in u . s . patent application 61 / 291 , 052 entitled filtering face - piece respirator having an auxetic mesh in the mask body . fig2 shows an enlarged view of the open - work auxetic mesh 20 , which may be used in connection with the present invention . as illustrated , the molded auxetic mesh 20 includes a multitude of open spaces 26 that may be defined by polymeric strands 28 . the strands 28 that define each open space 26 may include first and second sides 30 and 32 and third and fourth sides 34 and 36 . the first and second sides 30 and 32 may be linear , whereas the third and fourth sides 34 and 36 may be non - linear and include segments that are offset non - perpendicularly to the first and second sides 30 and 32 . the offset segments do not form right angles to the first and second sides 30 and 32 . rather , they form a chevron end that has angles α that may be about 20 to 80 degrees , more typically about 40 to 70 degrees . each opening typically has a size of about 5 to 50 square millimeters ( mm 2 ), more typically about 10 to 35 mm 2 . other auxetic mesh geometries ( now known or later developed ) also may be suitably used in connection with the present invention . the poisson ratio of the mesh typically is less than − 0 . 2 , more typically less than − 0 . 4 , and still more typically less than − 0 . 7 , but usually is not further less than − 2 . 2 . examples of meshes that exhibit negative poisson ratios and that may be suitable for use in connection with the present invention are described in u . s . patent application publication 2006 / 0129227a2 to hengelmolen and 2006 / 0180505a1 to alderson et al . at the upper end , the poisson ratio is not greater than zero . the multitude of openings in the mesh , after being molded , tend to maintain similar sizes . when tested according to the cell size determination method described below , the standard deviation of cell sizes is less than 0 . 04 , 0 . 03 , and even less than 0 . 025 . fig3 shows a cross - section of the mask body 12 , which includes the support structure 16 and the filtering structure 18 . the support structure 16 typically has a thickness of about 0 . 60 to 0 . 85 millimeters ( mm ), and each strand 28 typically has an average cross - sectional area of about 0 . 1 to 3 . 5 mm 2 , more typically of about 1 . 5 to 2 . 6 mm 2 . the auxetic mesh 20 may be made from a variety of polymeric materials . polymers suitable for auxetic mesh formation are generally either a thermoplastic or a thermoset material . thermoplastic materials are materials which melt and / or flow upon the application of heat , resolidify upon cooling and again melt and / or flow upon the application of heat . the thermoplastic material undergoes only a physical change upon heating and cooling , no appreciable chemical change occurs . thermoset materials , however , are curable materials that irreversibly cure , such as becoming crosslinked , when heated or cured . once cured , the thermoset material will not appreciably melt or flow upon application of heat . examples of thermoplastic polymers that can be used to form auxetic meshes include : polyolefins , such as polyethylenes , polypropylenes , polybutylenes , blends of two or more of such polyolefins , and copolymers of ethylene and / or propylene with one another and / or with small amounts of copolymerizable , higher , alpha olefins , such as pentene , methylpentene , hexene , or octene ; halogenated polyolefins , such as chlorinated polyethylene , poly ( vinylidene fluoride ), poly ( vinylidene chloride ), and plasticized poly ( vinyl chloride ); copolyester - ether elastomers of cyclohexane dimethanol , tetramethylene glycol , and terephthalic acid ; copolyester elastomers such as block copolymers of polybutylene terephthalate and long chain polyester glycols ; polyethers , such as polyphenyleneoxide ; polyamides , such as poly ( hexamethylene adipamide ), e . g ., nylon 6 and nylon 6 , 6 ; nylon elastomers ; such as nylon 11 , nylon 12 , nylon 6 , 10 and polyether block polyamides ; polyurethanes ; copolymers of ethylene , or ethylene and propylene , with ( meth ) acrylic acid or with esters of lower alkanols and ethylenically - unsaturated carboxylic acids , such as copolymers of ethylene with ( meth ) acrylic acid , vinyl acetate , methyl acrylate , or ethyl acrylate ; ionomers , such as ethylene - methacrylic acid copolymer stabilized with zinc , lithium , or sodium counterions ; acrylonitrile polymers , such as acrylonitrile - butadiene - styrene copolymers ; acrylic copolymers ; chemically - modified polyolefins , such as maleic anhydride - or acrylic acid - grafted homo - or co - polymers of olefins and blends of two or more of such polymers , such as blends of polyethylene and poly ( methyl acrylate ), blends of ethylene - vinyl acetate copolymer and ethylene - methyl acrylate ; blends of polyethylene and / or polypropylene with poly ( vinyl acetate ); and thermoplastic elastomer block copolymers of styrene of the a - b or a - b - a type , where a represents a thermoplastic polystyrene block and b represents a rubbery block of polyisoprene , polybutadiene , or poly ( ethylene / butylene ), examples include linear , radial , star and tapered styrene - isoprene block copolymers , linear styrene -( ethylene - butylene ) block copolymers , and linear , radial , and star styrene - butadiene block copolymers . the foregoing polymers are normally solid , generally high molecular weight , and melt - extrudable such that they can be heated to form molten viscous liquids which can be pumped as streams to the extrusion die assembly and readily extruded therefrom under pressure . examples of suitable commercially - available polymers include : those sold as “ elvax ” ethylene - vinyl acetate copolymers , such as elvax 40w , 4320 , 250 , and 350 ; those sold as “ emac ” ethylene - methyl acrylate copolymers , such as emac ds - 1274 , ds - 1176 , ds - 1278 - 70 , sp 2220 and sp - 2260 ; those sold as “ vista flex ” thermoplastic elastomers , such as vista flex 641 and 671 ; those sold as “ primacor ” ethylene - acrylic acid copolymers , such as primacor 3330 , 3440 , 3460 , and 5980 ; those sold as “ fusabond ” maleic anhydride - polyolefin copolymers , such as fusabond mb - 110d and mz - 203d ; those sold as “ himont ” ethylene - propylene copolymers , such as himont ks - 057 , ks - 075 , and ks - 051p ; those sold as “ fina ” polypropylenes , such as fina 3860x ; those sold as “ escorene ” polypropylenes , such as escorene 3445 ; the polymer sold as “ vestoplast 750 ” ethylene - propylene - butene copolymer ; those sold as “ surlyn ” ionomers , such as surlyn 9970 and 1702 ; those sold as “ ultramid ” polyamides , such as ultramid b3 nylon 6 and ultramid a3 nylon 6 , 6 ; those sold as “ zytel ” polyamides , such as zytel fe3677 nylon 6 , 6 ; those sold as “ rilsan ” polyamide elastomers , such as bmno p40 , besno p40 and besno p20 nylon 11 ; those sold as “ pebax ” polyether block polyamide elastomers , such as pebax 2533 , 3533 , 4033 , 5562 and 7033 ; those sold as “ hytrel ” polyester elastomers , such as hytrel 3078 , 4056 and 5526 ; those sold as “ kraton ” and “ europrene sol te ” styrene block copolymers , such as kraton d1107p , g1657 , g1750x , and d1118x and europrene sol te 9110 , and 6205 . as mentioned above , blends of two or more materials also may be used in the manufacture of auxetic meshes . examples of such blends include : a blend of 85 to 15 wt % poly ( ethylene - vinyl acetate ), such as “ elvax ” copolymer , with 15 to 85 wt % poly ( ethylene - acrylic acid ), such as “ primacor ” polymer , the poly ( ethylene - vinyl acetate ) component of the blend generally will have a weight average molecular weight , m w , of 50 , 000 to 220 , 000 and will have 5 to 45 mol % of its interpolymerized units derived from the vinyl acetate comonomer and the balance of units from ethylene , the poly ( ethylene - acrylic acid ) component of the blend generally will have a m w of 50 , 000 to 400 , 000 and have 1 to 10 mol % of its interpolymerized units derived from acrylic acid and the balance from ethylene ; a blend of 20 to 70 wt % poly ( ethylene - propylene - butene ) terpolymer having m w of 40 , 000 to 150 , 000 and derived from equally large amounts of butene and propylene and a small amount of ethylene , such as “ vestoplast 750 ” polymer , with 80 to 30 wt % isotactic polypropylene ; a blend that contains from 15 to 85 wt % poly ( ethylene - vinyl acetate ) and 85 to 15 wt % poly ( ethylene - methyl acrylate ), such as “ emac ” polymer , the poly ( ethylene - vinyl acetate ) component of this blend can have a molecular weight and composition like that described above , the poly ( methyl acrylate ) component can have a m w of 50 , 000 to 200 , 000 and 4 to 40 mole % of its interpolymerized units derived from the methyl acrylate comonomer . polypropylene may be preferred for use in a molded auxetic mesh that is used on a respirator to enable proper welding of the support structure to the filtering structure ( filtering layers often comprise polypropylene as well ). the polymeric materials used to make an auxetic mesh typically have a young &# 39 ; s modulus of about 0 . 3 to 1900 mega pascals ( mpa ), more typically 2 to 250 mpa . as shown in fig3 , the filtering structure 18 may include one or more cover webs 40 a and 40 b and a filtration layer 42 . the cover webs 40 a and 40 b may be located on opposing sides of the filtration layer 42 to capture any fibers that could come loose therefrom . typically , the cover webs 40 a and 40 b are made from a selection of fibers that provide a comfortable feel , particularly on the side of the filtering structure 18 that makes contact with the wearer &# 39 ; s face . the cover webs too often comprise polypropylene . when molding an auxetic mesh in accordance with the present invention , the auxetic mesh may be molded by itself or it may be molded in conjunction with other layers . for example , when making a filtering face - piece respirator , the auxetic mesh may be first molded , and the other layers , such as the filtering structure , may be subsequently joined to the molded mesh . alternatively , the various layers may be stacked together and molded into the desired configuration . further , the auxetic mesh may be cold - molded or hot - molded . when the auxetic mesh is cold - molded , the mesh is first heated before being placed between unheated molding members ( see , for example , u . s . pat . no . 7 , 131 , 422b1 to kronzer et al .). the unheated molding members then conform the heated auxetic mesh to its desired configuration . alternatively , the molding members may be heated , and that heat may be transferred to the auxetic mesh during the molding operation . thus , in a cold - molding operation , the heat and pressure are not necessarily applied to the auxetic mesh contemporaneously , whereas in a hot - molding operation the heat and pressure tend to be applied at the same time . in hot molding , the various layers may become bonded to each other at one or more desired locations when the heat and pressure is applied . alternatively , the various layers may be joined together at one or more desired locations through other operations such as welding ( for example , ultrasonic welding ) or adhesive bonding . the additional layers may be on one or both sides of the auxetic mesh . when making a filtering face - piece respirator , the mask body may be molded into a variety of different shapes and configurations . many of these various shapes and configurations are described in the patent literature and accordingly will not be discussed further here . auxetic mesh cell size was determined using defined diameter rods that were mounted in a fixture to facilitate measurement of the open spaces or cells . the probe rods ranged in diameter from 0 . 0254 cm ( centimeter ) to 0 . 5334 cm , in 0 . 0254 cm increments . the cell size was measured by selecting the maximum size probe that fit into the cell without causing distortion of the cell shape prior to placement of the probe . this size was recorded , and the next cell size was measured and recorded until all cells contained within the molded mesh were measured and the cells tallied at each probe size . an auxetic web was produced using a system 50 that resembles the apparatus shown in fig4 . a 40 mm diameter twin - screw extruder was fitted with a gear pump and was used to deliver a molten polymer blend at melt temperature of approximately 246 ° c . to a slot die 54 , at an extrusion rate of 1 . 43 kg / hr / cm ( kilogram per hour per length of die in centimeters ). the polymer blend contained a three - part polymer composition that included pigment and anti - block agents . the polymer blend formulation is given below in table 1 . at the end of the slot die 54 , the polymer blend is transferred to a casting roll 58 where the auxetic mesh is formed . the resulting mesh 20 is removed from the casting roll 58 where it is transferred to take - off roll 74 . a back - up roll 76 contacts the take - off roll 74 to keep the auxetic mesh on the take - off role until the point of departure from the roll . fig5 shows the orientation of the slot die 54 , doctor blade 56 , and casting roll 58 in greater detail . the slot die 54 was maintained at a temperature of about 246 ° c . and was positioned relative to the casting roll 58 such that a bank 60 of molten polymer was formed along a horizontal plane . the molten polymer 60 was forced into the casting roll cavity 62 by rotating the casting roll 58 against the doctor blade 56 . the doctor blade 56 both forced molten polymer 60 into the casting roll cavity 62 and wiped the outer surface 64 of the casting roll 58 so that the molten polymer 60 was left in the cavity alone . polymer that was removed from the polymer bank 60 via the casting roll 58 was replenished through the resin channel 66 of the slot die 54 . by this process , the auxetic mesh was continually casted . during processing , the doctor blade 56 was forced against the rotating casting roll 58 at a pressure of 0 . 656 kn / cm ( kilo - newtons per lineal cm )— a pressure that forced molten polymer 60 to fill the channels or cavities 62 of the casting roll 58 . the doctor blade 56 was maintained at a temperature of 246 ° c . the polymer bank 60 assured that sufficient polymer was present across the transverse length of the casting roll 58 to fill the channels 62 of the casting roll . as shown in fig4 , the apparatus 50 used a two - roll transfer system , which was composed of a chrome take - off roll 74 and a rubber - surfaced backup role 76 , to extract the cast auxetic mesh 20 from the casting roll 58 and convey it to a collection apparatus . the takeoff role 74 contacted the casting roll 58 at a point 225 ° degrees counter clockwise ( the direction of rotation ) from the point of contact between the slot die 54 and casting roll 58 . the backup roll 76 contacted the take - off roll 74 it a point 135 ° degrees clockwise ( direction of rotation ) from the point of contact between the casting roll 58 and take - off roll 74 . both rolls were maintained at a temperature of approximately 4 . 4 ° c . and had surface speeds of 5 . 0 m / min ( meters per minute ). the nip pressure between the casting roll 58 and take - off roll 74 was maintained at 4 . 37 n / cm ; the nip pressure between the take - off roll 74 and the backup role 76 was 4 . 37 n / cm . after leaving the casting roll , the auxetic mesh 20 was transferred to the take - off roll 74 and was further cooled and conveyed through web handling rolls to a windup roll ( not shown ). the resulting mesh had a thickness of about 1 . 63 mm and a basis weight of 47 g / cm 2 ( grams per square centimeter ). the final wound roll of auxetic mesh contained an intermittent thin film of polymeric material between each of the auxetic pattern elements . all residual inter - element film was removed by hand using a tweezers . other methods of residual film removal could include burning , heating , brushing , punching , etc . as shown in fig6 and 6 a , the casting roll 58 had an auxetic - shaped cavity pattern 62 machined into its face . the cavity pattern 62 was cut into the face 77 of a 23 . 5 cm diameter , chrome - surfaced , steel roll 58 . the auxetic - shaped pattern 62 of interconnecting channels 82 was machined into the face 77 of the casting roll 58 using a harvey tool # 11815 - 30 carbide miniature tapered end mill , harvey tool company llc , rowley , mass . having a 6 ° included angle . the channels 82 of the auxetic pattern 62 were machined to a depth of 1 . 143 mm , with the rectangular channel formed by 3 ° tapered edge . the channels 82 are defined by uncut “ island ” areas 86 in the roll face 77 , whereby the machined area constituted the channels 82 . the unmachined islands 86 on the roll face 84 , onto which the doctor blade 56 rides during mesh formation , were the shape of elongated hexagons that had isosceles concave ‘ chevron ’ ends 87 . as shown in fig7 , islands 86 were oriented on the roll 76 such that their long axis 80 aligned with the circumstantial line of the roll 76 . the islands 86 had an overall height h and width w of 11 . 1 mm and 3 . 1 mm , respectively . two equally length lines , 92 extending 1 . 67 mm from the ends of each major side 94 of the hexagon , and meeting at its long axis centerline 80 , formed the end chevron 87 of an island 86 . islands were spaced apart , relative to their centerlines , either along their long axis 80 or narrow ( short ) axis 89 . the long axes of all islands were parallel to the circumstantial line of the casting roll 76 . the narrow axes 89 , of the islands were oriented along the axis of the casting roll 58 . alternating transverse rows of islands were offset from the row above or below by one half the width of each island . transverse spacing of the islands 81 was 4 . 27 mm from long axis 80 to an adjacent long axis 80 . circumstantial spacing 83 of the islands was 11 . 88 mm from short axis 89 to short axis 89 . angle α was 69 degrees . with the islands 86 formed in this manner , a network of channels 82 was created ; these channels 82 were filled with polymer during the casting process and acted as molds for the auxetic mesh 20 . fig8 shows an image of the molded auxetic mesh 20 produced as described above . auxetic mesh produced as described in the auxetic mesh formation apparatus and process were evaluated for their auxetic properties through a tensile testing procedure . in this procedure , a 10 . 2 cm by 1 . 0 cm section of mesh was cut such that the long axes of the mesh cells were oriented in line with the transverse axis of the tensile testing apparatus . the crosshead speed of the tensile testing apparatus was maintained at 50 . 8 centimeters per minute until the sample was elongated to 50 and 100 percent of its original length . as is indicative of an auxetic structure , when placed under tension , the sample section increased in width in response to axial loading . the sample increased to a width of 105 percent of its original width at both elongations . auxetic mesh produced as described in the auxetic mesh formation apparatus and process section was molded into a three - dimensional cup shape . the auxetic mesh was molded into the cup shape of a respirator by draping a 21 . 5 cm by 25 . 5 cm section of mesh over an aluminum male mold . the mold had a generally hemispherical shape with an elliptical base with a major axis of 13 . 3 cm , and a minor axis of 10 . 5 cm , and a dome height of 4 . 4 cm . the hemispherical - shape mold was fixed to a rectangular aluminum plate that extended approximately 3 . 4 cm beyond the base of the mold . the section of auxetic mesh was draped over the mold so that it &# 39 ; s edges extended beyond the outer perimeter of the base plate . a perimeter aluminum frame , with an interior cutout that mirrored the perimeter of the mold , was placed over the auxetic mesh and mold so that the mesh could be drawn over the mold without significant mesh distortion . the perimeter frame was then fixed to the base plate to hold the mesh in position against the mold . the mold , mesh , and securing plate assembly was placed in a preheated , air circulating oven for 20 minutes at a temperature of 105 c . after heating in the oven for the specified duration , the assembly was removed from the oven and was allowed to cool to room temperature . when the assembly reached room temperature , the perimeter frame was uncoupled from the base plate , and the resultant molded auxetic mesh removed from the mold . it was observed that the molded auxetic mesh retained its general auxetic structure , and it was shape - retaining even after compression in the mold . it was also noted that the auxetic mesh was able to easily adapt to the male mold shape without significant distortions to the mesh , such as folds or creases . a respirator shell mesh was produced as described above in the three - dimensional molding of auxetic mesh section was evaluated for cell size uniformity by surveying the size of the cells over the entirety of the mold structure . the cell size uniformity of the auxetic mesh was compared to the uniformity of shell meshes that were removed from commercially available filtering face - piece respiratory masks . detailed measurements of the cell opening size and size distribution for each of several shell meshes were determined respirator shell mesh was evaluated from a jsp 822 mask , manufactured by jsp ltd , oxfordshire , uk ; a venus 190 mask , produced by nani mumbai - mn , india ; a 2200 mask inner shell , a 2200 mask outer shell , and a 2600 outer shell , all manufactured by moldex - metric , culver city , calif . the meshes were removed from the filter media to enable cell size measurement , the exception being the 3m auxetic mesh which was free standing . each cell opening size was measured and recorded for the entire mesh using gauging probes as described above in cell size determination . the resulting measurements were compiled to provide the number of cells contained within the mesh of a given size , see table 2 . from this data the cell size distribution and standard deviation determined were determined and are given in table 2 . the data shown in table 2 reveals that the molded auxetic mesh has the narrowest distribution of cell size compared to known non - auxetic molded meshes . analysis of the data for standard deviation shows that the inventive auxetic mesh has the smallest standard deviation of all six meshes measured . the reduction of cell size distribution in the auxetic mesh is a result of the deformation characteristics of an auxetic structure , which allows it to more readily conform to highly contoured shapes without gross deformation of the mesh , such as folding or drawing . | 0 |
in fig1 - 4 , reference numeral 10 generally designates the bed clothing assembly in accordance with the principals of the present invention . the bed clothing assembly 10 of the present invention is intended to provide a means for the physically disabled to more easily remove and replace bed clothing . in fig1 , there is illustrated a perspective exploded view of the individual components of the bed clothing assembly 10 and a conventional mattress 12 . the mattress 12 is rectangular , and has top and bottom surfaces 14 and 16 , each with a peripheral edge 18 and 20 , respectively , and a sidewall 22 extending between the peripheral edges . the bottom surface 16 of the mattress 12 is best seen in fig3 . sidewall 22 of the mattress 12 includes end panels 24 and 26 , and side panels 28 and 30 . the bed clothing assembly 10 includes a mattress band 32 , a unitary sheet assembly 34 and a padded sheet or mattress pad 60 . the mattress band 32 is constructed to be securely attached to the mattress 12 and the unitary sheet assembly 34 and the padded sheet 60 are each constructed to be removably attachable to the mattress band 32 in a manner in which they remain secured during usage . the mattress band 32 comprises a sidewall 36 with continuous upper and lower edges 38 and 40 . sidewall 32 can include sides panels 42 and 44 , and end panels 46 and 48 . the adjacent vertical edges of the side panels 42 and 44 and of the end panels 46 and 48 are joined to form vertical corners 50 a , 50 b , 50 c , and 50 d . an upper edge portion 52 extends inwardly from the upper edge 38 , and a lower edge portion 54 extends inwardly from the lower edge 40 . bands 56 of elastic material can be attached around the ends 58 and 60 of the upper and lower edge portions 52 and 54 respectively . bands 56 causes the upper and lower edge portions 52 and 54 to gather and aid in securing the mattress band 32 to the mattress 12 . the sidewall 36 of the mattress band 32 encircles the sidewall 22 of the mattress 12 , and the upper and lower edge portions 52 and 54 extend inwardly and continuously around the peripheral edges 18 and 20 of the top and bottom surfaces 14 and 18 of the mattress , respectively , when the mattress band is installed on the mattress . the length and width of side panels 42 and 44 , and of end panels 46 and 48 are sized to correspond to the length and width of side panels 28 and 30 , and of end panels 24 and 26 , respectively , of the mattress 12 . the mattress band 32 can be partially or entirely constructed of an elastic material , and sized to be slightly smaller than the dimensions of the mattress , and capable of being stretched to conform to the size , shape and dimension of the mattress to which it is attached . the mattress band 32 can be made of an elastic fabric material having a pile that can be removably engaged by a hook fastener portion of a hook - and - loop type fastener . the unitary sheet assembly 34 includes a bottom sheet 58 and a top sheet 62 connected together forming a single unit . the bottom sheet 58 includes a main panel 64 with top and bottom surfaces 66 and 68 , and a peripheral edge 70 . a sidewall 72 extends from the main panel 64 continuously around the peripheral edge 70 , and includes a peripheral bottom edge 84 . sidewall 72 may be integral with main panel 64 . sidewall 72 can include side panels 74 and 76 , and end panels 78 and 80 . adjacent vertical edges of the side panels 74 and 76 , and of the end panels 78 and 80 are joined to form vertical corners 82 a , 82 b , 82 c , and 82 d . main panel 64 is sized to equal the top surface 14 of the mattress 12 . side panels 74 and 76 and end panels 78 and 80 are sized to correspond to the length and width of side panels 42 and 44 , and of end panels 46 and 48 , respectively , of the mattress band 32 . side panels 74 and 76 and end panels 78 and 80 cover side panels 42 and 44 , and of end panels 46 and 48 , respectively , of the mattress band 32 when attached thereto . the top sheet 62 includes a main panel 88 with top and bottom surfaces 90 and 92 , and a peripheral edge 94 . a sidewall 96 extends from the main panel 88 partially around the peripheral edge 94 , and includes a peripheral bottom edge 98 . sidewall 96 may be integral with main panel 88 . sidewall 96 can include a foot panel 100 corresponding to end panel 78 of the bottom sheet 58 , and side panels 102 and 104 corresponding to side panels 74 and 76 , respectively , of the bottom sheet . foot panel 100 is sized to correspond to the length and width of end panel 78 . side panels 102 and 104 can be sized to correspond the length and width of side panels 74 and 76 , respectively , can be sized to have a greater width to drape downward beyond the peripheral bottom edge 84 of the bottom sheet 58 , and can be sized to have a greater length to extend beyond the peripheral edge 64 to permit the top sheet opposite of the foot panel 100 to be folded back upon itself . main panel 88 of the top sheet 62 can be sized to be equal to main panel 64 of the bottom sheet 58 . the peripheral bottom edge 98 along the foot panel 100 of the top sheet 62 and the peripheral bottom edge 84 along end panel 78 of the bottom sheet 58 are continuously stitched together along the lengths thereof with the remaining portion of the peripheral bottom edge 98 along the side panels 102 and 104 of the top sheet free from attachment with the bottom sheet 58 . the adjacent vertical edges of foot panel 100 and side panel 102 are separate from each other forming a vertical gap therebetween , and the adjacent vertical edges of foot panel 100 and side panel 104 are separate from each other forming a vertical gap therebetween to permit the side panels 102 and 104 of top sheet 62 to be movable independently from the foot panel 100 . a plurality of hook fasteners 106 , such as the hook fastener of a hook - and - loop type fastener , are spaced along the sidewall 72 of the bottom sheet 58 . fasteners 106 are releasably attachable to the fabric material of the sidewall 36 of the mattress band 32 enabling the unitary sheet assembly 34 to be securely attached to the mattress band and remain taut throughout usage . the sidewall 72 of the bottom sheet 58 is continuously coextensive with the sidewall 36 of the mattress band 32 and the bottom surface 66 of the bottom sheet 58 is coextensive with the top surface 14 of the mattress 12 when the unitary sheet assembly 34 is secured to the mattress band . to make detachment easier and to prevent in advent reattachment of the unitary sheet assembly 34 with the mattress band 32 , each fastener 106 can be spaced along the peripheral bottom edge 70 of the bottom sheet 58 . even further , the fasteners 106 can be sized such that they do not extend completely up sidewall 72 , and are spaced from the upper edge 38 and peripheral edge 70 . in this manner , as side panels 74 and 76 and end panels 78 and 80 are sequentially detached from side panels 28 and 30 and end panels 24 and 26 , and lifted up it is less likely for prior detached panels to become inadvertently reattached . the padded sheet 60 has a panel area 86 sized equal to the upper surface 12 of the mattress 12 . the padded sheet 60 may have a waterproof barrier layer . a plurality of separate securment straps 110 are spaced along and extend from the peripheral edge 112 of the padded sheet 60 . each strap 110 can be looped to have an opening 114 of a sufficient size to permit the insertion of a hand through the loop to more easily grip the strap . each strap 110 includes a fastener portion 116 for releasable attachment to the sidewall 36 of the mattress band 32 . in operation , the mattress band 32 is first attached to the mattress 12 by stretching the mattress band 32 over the corners and sides of the mattress such that sidewall 32 encircles the sidewall 22 of the mattress , and the lower edge portion 54 and the upper edge portion 52 extend inwardly and continuously around the peripheral edges 18 and 20 of the top and bottom surfaces 14 and 18 of the mattress , respectively . once the mattress band 32 is attached to the mattress 12 , the mattress no longer needs to be lifted or otherwise maneuvered in the attachment or detachment of the unitary sheet assembly 34 , thereby making changing of the bedding easier and with less strain . with the mattress band 32 attached to the mattress 12 , the unitary sheet assembly 34 can be placed on top of the mattress with the foot panel 100 at the foot of the mattress . sidewall 72 can then be attached to the sidewall 36 of the mattress band 32 by simply pulling the sidewall 72 down and about sidewall 36 and engaging the cooperating fasteners 106 . in this manner , the bottom sheet 58 , the padded sheet 60 and the top sheet 62 are each simultaneously positioned correctly on the mattress in a single step without requiring lifting of the mattress . the top sheet 62 may need to be adjusted and pulled upward along the top of the mattress 12 as desired . a number of embodiments of the present invention have been described . nevertheless , it will be understood that various modifications may be made without departing from the spirit and scope of the invention . accordingly , other embodiments are within the scope of the following claims . | 0 |
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